Composition, molding material, multilayer structure, molded body, food package, and method for producing composition and multilayer structure

Abstract

The present invention provides a composition excellent in thermal stability.　This composition contains an ethylene-vinyl alcohol copolymer and a titanium compound, wherein at least a part of the ethylene-vinyl alcohol copolymer is derived from biomass, and the titanium element content of the titanium compound is 0.0001 ppm or more and less than 1 ppm with respect to the mass of the composition.

Description

Composition, molding material, multilayer structure, molded article, food packaging, composition and method for producing multilayer structure

[0001] The present invention relates to a composition, a molding material, a multilayer structure, a molded article, a food packaging material, a composition, and a method for producing a multilayer structure.

[0002] Ethylene-vinyl alcohol copolymers (hereinafter, sometimes referred to as "EVOH resins") are excellent in transparency, gas barrier properties such as oxygen and other gases, aroma retention, solvent resistance, oil resistance, mechanical strength, and the like, and are formed into films, sheets, bottles, and the like, and are widely used as various packaging materials such as food packaging materials, pharmaceutical packaging materials, industrial chemical packaging materials, and agricultural chemical packaging materials.

[0003] Meanwhile, in recent years, with the aim of realizing a recycling-oriented society, there has been an increasing demand for bioplastics made from carbon-neutral biomass-derived raw materials. However, it is known that biomass-derived synthetic resins often have inferior performance compared to fossil fuel-derived synthetic resins. Therefore, efforts are being made to develop biomass-derived resins that are comparable in performance to fossil fuel-derived resins by combining biomass-derived raw materials with fossil fuel-derived raw materials.

[0004] For example, Patent Documents 1 and 2 disclose gas barrier resin compositions in which ethylene and vinyl ester, which are raw materials for EVOH resin, are partly derived from biomass, and disclose that the compositions have gas barrier properties and long-run properties comparable to those of compositions made using only raw materials derived from fossil fuels.

[0005] JP 2022-13857 A JP 2022-27726 A

[0006] According to the inventors' investigations, the techniques disclosed in the above Patent Documents 1 and 2 have insufficient thermal stability, and there is room for further improvement in thermal stability.

[0007] In view of this, the present invention provides a resin composition having excellent thermal stability, even if it is an EVOH resin made from a raw material derived from biomass.

[0008] However, in view of the above circumstances, the present inventors have conducted extensive research and have found that excellent thermal stability can be achieved by blending a specific trace amount of a titanium compound with an EVOH resin partly made from raw materials derived from biomass.

[0009] That is, the present invention has the following aspects. [1] A composition containing an EVOH resin and a titanium compound, wherein at least a portion of the EVOH resin is derived from biomass, and the content of the titanium compound in terms of metal is 0.0001 ppm or more and less than 1 ppm based on the mass of the composition. [2] The composition according to [1], wherein the content of the titanium compound in terms of metal is 0.0001 ppm or more and 0.8 ppm or less based on the mass of the composition. [3] The composition according to [1] or [2], further comprising an alkaline earth metal compound (A), wherein the mass ratio of the content of the alkaline earth metal compound (A) in terms of metal to the content of the titanium compound in terms of metal is 500 to 55,000. [4] The composition according to any one of [1] to [3], further comprising a metal compound (B) belonging to the d block of Period 4 of the long form periodic table other than the titanium compound, wherein the mass ratio of the metal-equivalent content of the metal compound (B) belonging to the d block of Period 4 of the long form periodic table to the metal-equivalent content of the titanium compound is 2 to 45,000. [5] The composition according to any one of [1] to [4], further comprising a lubricant (C) other than the alkaline earth metal compound (A), wherein the mass ratio of the lubricant (C) to the metal-equivalent content of the titanium compound is 500 to 280,000. [6] The composition according to any one of [1] to [5], further comprising a polyamide-based resin (D). [7] The composition according to any one of [1] to [6], further comprising a polyolefin-based resin (E). [8] The composition according to any one of [1] to [7], further comprising an olefin-based elastomer (F). [9] The composition according to any one of [1] to [8], wherein the EVOH resin has a biobased content of 0.01 to 99%.

[10] The composition according to any one of [1] to [8], wherein the EVOH resin has a biobased content of 1 to 99%.

[11] A molding material comprising the composition according to any one of [1] to

[10] .

[12] A multilayer structure having a layer comprising the composition according to any one of [1] to

[10] .

[13] The multilayer structure according to

[12] , further comprising an adhesive resin layer.

[14] A molded article comprising the multilayer structure according to

[12] or

[13] .

[15] A food packaging product comprising the multilayer structure according to

[12] or

[13] .

[16] A method for producing the composition according to any one of [1] to

[10] , comprising a step of mixing the EVOH resin and the titanium compound.

[17] A method for producing the multilayer structure according to

[12] or

[13] , comprising a step of melt-molding a layer comprising the composition.

[0010] The composition of the present invention has excellent thermal stability. In addition, molding materials formed from the composition of the present invention, as well as multilayer structures, molded articles, and food packages having a layer containing the composition of the present invention, also have excellent thermal stability.

[0011] The present invention will be described below based on examples of embodiments for carrying out the present invention, but the present invention is not limited to the embodiments described below.

[0012] In this specification, "x and / or y (x and y are optional)" refers to at least one of x and y, and can mean either x alone, y alone, or both x and y. When "X to Y" (X and Y are optional numbers) is used, unless otherwise specified, it also encompasses "X or more and Y or less," as well as "preferably more than X" or "preferably less than Y." When "X or more" (X is optional number) or "Y or less" (Y is optional number) is used, it also encompasses "preferably more than X" or "preferably less than Y." Regarding the numerical ranges described in stages in this specification, the upper or lower limit of a certain numerical range can be arbitrarily combined with the upper or lower limit of another numerical range. Furthermore, in the numerical ranges described in this specification, the upper or lower limit of the numerical range can be replaced with the value shown in the examples. In this specification, the term "layer" refers to a thick layer as well as a relatively thin layer such as a "film," "tape," or "sheet."

[0013] <Composition> A composition according to one embodiment of the present invention (hereinafter sometimes referred to as "the composition") contains an EVOH resin as an essential component and a specific trace amount of a titanium compound. That is, the content of the EVOH resin in the composition is usually 1% by mass or more, preferably 10% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, particularly preferably 70% by mass or more, especially preferably 80% by mass or more, especially more preferably 90% by mass or more, and still more preferably 95% by mass or more. The upper limit is 100% by mass, and may be 99% by mass, for example, 1 to 100% by mass or 10 to 99% by mass.

[0014] As described above, the present composition will be described in the following order: a "first embodiment" when the composition contains an EVOH resin as an essential component and a specific trace amount of a titanium compound; a "second embodiment" when the first embodiment further contains an alkaline earth metal compound (A); a "third embodiment" when the first embodiment further contains a metal compound (B) belonging to the d block of Period 4 of the long form periodic table other than a titanium compound; a "fourth embodiment" when the first embodiment further contains a lubricant (C) other than an alkaline earth metal compound; a "fifth embodiment" when the first embodiment further contains a polyamide resin (D); a "sixth embodiment" when the first embodiment further contains a polyolefin resin (E); and a "seventh embodiment" when the first embodiment further contains an olefin elastomer (F).

[0015] <<First Aspect>> The first aspect includes the following aspects [I-1] to [I-11]. [I-1] A composition containing an EVOH resin and a titanium compound, wherein at least a portion of the EVOH resin is derived from biomass, and the content of the titanium compound, calculated as metal, is 0.0001 ppm or more and less than 1 ppm, based on the mass of the composition. [I-2] The composition according to [I-1], wherein the content of the titanium compound, calculated as metal, is 0.0001 ppm or more and 0.8 ppm or less, based on the mass of the composition. [I-3] The composition according to [I-1] or [I-2], wherein the EVOH resin has a bio-based content of 0.01 to 99%. [I-4] The composition according to any one of [I-1] to [I-3], wherein the EVOH resin has a bio-based content of 1 to 99%. [I-5] A molding material comprising the composition according to any one of [I-1] to [I-4]. [I-6] A multilayer structure having a layer comprising the composition according to any one of [I-1] to [I-4]. [I-7] The multilayer structure according to [I-6], further comprising an adhesive resin layer. [I-8] A molded article comprising the multilayer structure according to [I-6] or [I-7]. [I-9] A food package comprising the multilayer structure according to [I-6] or [I-7]. [I-10] A method for producing the composition according to any one of [I-1] to [I-4], comprising a step of mixing the EVOH resin and the titanium compound. [I-11] A method for producing the multilayer structure according to [I-6] or [I-7], comprising a step of melt-molding a layer comprising the composition.

[0016] The first aspect will be described below based on examples of modes for carrying out the first aspect, although the present invention is not limited to the embodiments described below.

[0017] <Composition> The composition according to the first aspect of the present invention (hereinafter, sometimes referred to as "the composition (1)") contains an EVOH resin as an essential component and a specific trace amount of a titanium compound. That is, the content of the EVOH resin in the composition (1) is usually 1% by mass or more, preferably 10% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, particularly preferably 70% by mass or more, especially preferably 80% by mass or more, especially more preferably 90% by mass or more, and still more preferably 95% by mass or more. The upper limit is 100% by mass, and may be 99% by mass, for example, 1 to 100% by mass, or 10 to 99% by mass. Each component will be described below.

[0018] [EVOH Resin] The EVOH resin used in this embodiment is at least partially derived from biomass. More specifically, this refers to an EVOH resin in which at least a portion of the ethylene structural units, vinyl alcohol structural units, and vinyl ester structural units of the EVOH resin are derived from biomass.

[0019] The EVOH resin is a water-insoluble thermoplastic resin obtained by saponifying an ethylene-vinyl ester copolymer, which is a copolymer of ethylene and vinyl ester, at least a portion of which is derived from biomass.

[0020] The biomass-derived origin of ethylene and / or vinyl esters used as raw materials can be confirmed by measuring the biobased content. The biobased content is an index that indicates the proportion of biomass-derived raw materials, and in this specification, it is determined by measuring the radiocarbon [ １４ The biobased carbon content is determined by measuring the concentration of carbon-14 (hereinafter referred to as "carbon-14"). Specifically, the biobased content can be measured according to the method described in ASTM D6866-18. That is, when the biobased content of an EVOH resin is more than 0% and 100% or less, it can generally be said that the ethylene and / or vinyl ester used as the raw material contains biomass-derived components.

[0021] "Biomass" refers to organic resources derived from plants and animals, excluding those derived from fossil fuels (fossil resources). From the standpoint of cost and the environment, it is preferable that biomass is an organic resource derived from plants, i.e., derived from biological raw materials.

[0022] Biomass-derived ethylene can be produced, for example, by purifying bioethanol from a biomass raw material and then subjecting it to a dehydration reaction, etc. Biomass-derived vinyl esters can be produced, for example, by a common industrial method of reacting ethylene, acetic acid, and molecular oxygen using a palladium catalyst.

[0023] Biomass raw materials include waste materials, unused materials, resource crop materials, etc., such as cellulosic crops (pulp, kenaf, wheat straw, rice straw, waste paper, papermaking residues, etc.), wood, charcoal, compost, natural rubber, cotton, sugarcane, soybean refuse, oils and fats (rapeseed oil, cottonseed oil, soybean oil, coconut oil, castor oil, etc.), carbohydrate crops (corn, potatoes, wheat, rice, rice husks, rice bran, used rice, cassava, sago palm, etc.), bagasse, buckwheat, soybeans, essential oils (pine oil, orange oil, eucalyptus oil, etc.), pulp black liquor, vegetable oil cakes, etc. These can be used alone or in combination of two or more.

[0024] Examples of methods for producing bioethanol include pre-treating biomass raw materials as needed (compressed hot water treatment, acid treatment, alkali treatment, saccharification treatment using saccharifying enzymes), followed by yeast fermentation to produce bioethanol, and then purifying the bioethanol through a distillation process and a dehydration process. When saccharification treatment is performed during bioethanol production, sequential saccharification and fermentation, in which saccharification and fermentation are carried out in stages, may be used, or parallel saccharification and fermentation, in which saccharification and fermentation are carried out simultaneously, but from the perspective of production efficiency, parallel saccharification and fermentation is preferred for producing bioethanol.

[0025] The proportion of biomass-derived ethylene structural units in all ethylene structural units constituting the EVOH resin may be biomass-derived, but is typically 0.001 to 100 mol%, preferably 5 to 98 mol%, more preferably 15 to 97 mol%, even more preferably 25 to 96 mol%, and particularly preferably 35 to 95 mol%. The proportion of fossil fuel-derived ethylene structural units in all ethylene structural units constituting the EVOH resin is typically 99.999 mol% or less, preferably 95 mol% or less, more preferably 85 mol% or less, even more preferably 75 mol% or less, and particularly preferably 65 mol% or less. The lower limit is 0 mol%, for example, 0 to 99.999 mol%. Fossil fuel-derived ethylene structural units may not be present in all ethylene structural units. As the proportion of biomass-derived ethylene structural units in all ethylene structural units constituting the EVOH resin increases, the biobased content of the present composition (1) increases, which tends to reduce the environmental impact. When the EVOH resin contains biomass-derived vinyl ester structural units and / or vinyl alcohol structural units, the proportion of biomass-derived ethylene structural units in all ethylene structural units may be 0.

[0026] As a vinyl ester other than biomass-derived vinyl esters, vinyl acetate is typically used because of its availability on the market and the efficiency of impurity treatment during production. Examples of vinyl esters other than vinyl acetate include aliphatic vinyl esters such as vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl versatate, and aromatic vinyl esters such as vinyl benzoate. Typically, an aliphatic vinyl ester having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and more preferably 4 to 7 carbon atoms is used. These are typically used alone, but multiple types may be used simultaneously as necessary.

[0027] Examples of biomass-derived vinyl esters include vinyl esters produced using biomass-derived ethylene, such as vinyl acetate, in which the carbon in the vinyl group is derived from biomass.

[0028] Examples of methods for producing biomass-derived vinyl esters include a common industrial method of reacting ethylene, acetic acid, and molecular oxygen using a palladium catalyst. The biomass-derived vinyl ester may also be a vinyl ester produced using a biomass-derived carboxylic acid. When the saponification degree of the EVOH resin is not 100 mol%, acyl groups derived from the biomass remain.

[0029] The proportion of biomass-derived vinyl alcohol structural units in all vinyl alcohol structural units (vinyl ester structural units) constituting the EVOH resin is typically 0.001 to 100 mol%, preferably 5 to 98 mol%, more preferably 15 to 97 mol%, even more preferably 25 to 96 mol%, and particularly preferably 35 to 95 mol%. The proportion of fossil fuel-derived vinyl alcohol structural units in all vinyl alcohol structural units constituting the EVOH resin is typically 99.999 mol% or less, preferably 95 mol% or less, more preferably 85 mol% or less, even more preferably 75 mol% or less, and particularly preferably 65 mol% or less. The lower limit is 0 mol%, for example, 0 to 99.999 mol%. Fossil fuel-derived vinyl alcohol structural units may not be present in all vinyl alcohol structural units. As the proportion of biomass-derived vinyl alcohol structural units in all vinyl alcohol structural units constituting the EVOH resin increases, the biobased content of the present composition (1) increases, tending to reduce the environmental impact.

[0030] In addition, when the EVOH resin contains biomass-derived ethylene structural units, the ratio of the total of the biomass-derived vinyl ester structural units and the biomass-derived vinyl alcohol structural units to the total of the vinyl ester structural units and the vinyl alcohol structural units may be 0.

[0031] The biomass-derived EVOH resin can be confirmed by confirming the presence of "sulfur compounds" and / or "carbon-14" in the present composition (1). "Sulfur compounds" and / or "carbon-14" are impurities derived from biomass, and their presence cannot be confirmed in petroleum-derived EVOH resins, but can be confirmed in biomass-derived EVOH resins.

[0032] It is believed that EVOH resin has a problem with thermal stability, and it is speculated that the main cause of thermal decomposition in particular is the polyene structure formed in the main chain of the EVOH resin due to a dehydration reaction initiated by a hydroxyl group. In this composition (1), it is speculated that the use of biomass-derived EVOH resin reduces the thermal decomposition rate of the EVOH resin itself due to the primary isotope effect of carbon-14 (increase in bond energy), thereby improving thermal stability.

[0033] The ethylene structural unit content of the EVOH resin is usually 20 to 60 mol%, preferably 25 to 50 mol%, and particularly preferably 25 to 35 mol%. When the content is equal to or greater than the lower limit, the EVOH resin tends to have excellent gas barrier properties and melt moldability under high humidity conditions, while when the content is equal to or less than the upper limit, the EVOH resin tends to have excellent gas barrier properties. In this embodiment, the ethylene structural unit content of the EVOH resin means a value measured in accordance with ISO 14663.

[0034] The saponification degree of the EVOH resin is usually 90 to 100 mol%, preferably 95 to 100 mol%, and more preferably 99 to 100 mol%. When the saponification degree is equal to or greater than the lower limit, the EVOH resin tends to have excellent gas barrier properties, thermal stability, moisture resistance, etc. The saponification degree of the EVOH resin can be measured in accordance with JIS K6726 (wherein the EVOH resin is used as a solution uniformly dissolved in a water / methanol solvent).

[0035] The melt flow rate (MFR) (210°C, 2160 g load) of the EVOH resin is usually 0.5 to 100 g / 10 min, preferably 1 to 50 g / 10 min, and more preferably 3 to 35 g / 10 min. When the MFR is equal to or less than the upper limit, the resin tends to have excellent stability during film formation, while when the MFR is equal to or greater than the lower limit, the resin tends to have an appropriate viscosity and be excellent in melt extrusion. The MFR is an index of the degree of polymerization of the EVOH resin, and can be adjusted by the amount of polymerization initiator and the amount of solvent used when copolymerizing ethylene and vinyl ester.

[0036] The bio-based content of the EVOH resin is usually 0.001 to 100%, preferably 1 to 99%, more preferably 20 to 86%, still more preferably 38 to 76%, and particularly preferably 58 to 66%, with the upper limit being 100%.

[0037] The EVOH resin may further contain structural units derived from the comonomers shown below (for example, 10 mol % or less of the EVOH resin) within the range that does not impair the effects of the present invention.Examples of the comonomer include olefins such as propylene, 1-butene, and isobutene; hydroxy group-containing α-olefins such as 3-butene-1-ol, 3-butene-1,2-diol, 4-pentene-1-ol, and 5-hexene-1,2-diol, and derivatives thereof such as esters and acylation products; hydroxyalkylvinylidenes such as 2-methylenepropane-1,3-diol and 3-methylenepentane-1,5-diol; 1,3-diacetoxy-2-methylenepropane, 1,3-dipropionyloxy-2-methylenepropane, and 1,3-dibutyl hydroxyalkylvinylidene diacetates such as methyloxy-2-methylenepropane; unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, or their salts or mono- or di-alkyl esters in which the alkyl group has 1 to 18 carbon atoms; acrylamide, N-alkylacrylamide in which the alkyl group has 1 to 18 carbon atoms, N,N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or its salts, acrylamidopropyldimethylamine or its acid salts or quaternary salts thereof acrylamides such as methacrylamide, N-alkylmethacrylamides in which the alkyl group has 1 to 18 carbon atoms, N,N-dimethylmethacrylamide, 2-methacrylamidopropanesulfonic acid or its salts, methacrylamidepropyldimethylamine or its acid salts or its quaternary salts; N-vinylamides such as N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide; vinyl cyanides such as acrylonitrile and methacrylonitrile; alkyl vinyl ethers in which the alkyl group has 1 to 18 carbon atoms, hydrochloric acid vinyl ethers such as alkoxyalkyl vinyl ether and alkoxyalkyl vinyl ether; halogenated vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and vinyl bromide; vinyl silanes such as trimethoxyvinylsilane; halogenated allyl compounds such as allyl acetate and allyl chloride; allyl alcohols such as allyl alcohol and dimethoxyallyl alcohol; and comonomers such as trimethyl-(3-acrylamido-3-dimethylpropyl)-ammonium chloride and acrylamido-2-methylpropanesulfonic acid.These may be used alone or in combination of two or more.

[0038] Among these, hydroxy group-containing α-olefins are preferred, and 3-butene-1,2-diol and 5-hexene-1,2-diol are particularly preferred. When the hydroxy group-containing α-olefins are copolymerized, the resulting EVOH resin has primary hydroxyl groups in the side chains. Such EVOH resins having primary hydroxyl groups in the side chains, particularly EVOH resins having a 1,2-diol structure in the side chains, are preferred in that they exhibit good secondary moldability while maintaining gas barrier properties.

[0039] When the EVOH resin has a primary hydroxyl group in a side chain, the content of the structural unit derived from the monomer having the primary hydroxyl group is usually 0.1 to 20 mol %, preferably 0.5 to 15 mol %, particularly preferably 1 to 10 mol %, of the EVOH resin.

[0040] Furthermore, as the EVOH resin, EVOH resins that have been "post-modified" by esterification, urethanization, acetalization, cyanoethylation, oxyalkylenation, or the like can also be used.

[0041] When the post-modified EVOH resin is used, the modification rate is usually 10 mol% or less, preferably 4 mol% or less. The lower limit is usually 0.01 mol% or more, preferably 0.1 mol% or more, for example, 0.01 to 10 mol%, preferably 0.1 to 4 mol%. When the modification rate of the EVOH resin is within the above range, the resin tends to have excellent heat degradation resistance and long-run properties.

[0042] Furthermore, the EVOH resin may be a mixture of EVOH resins having different ethylene structural unit contents, saponification degrees, polymerization degrees, copolymerization components, and the like.

[0043] As described above, the EVOH resin used in this embodiment is obtained by saponifying a copolymer of ethylene and vinyl ester, at least a part of which is derived from biomass. The copolymerization can be carried out by any known polymerization method, such as solution polymerization, suspension polymerization, or emulsion polymerization.

[0044] Examples of the polymerization solvent include lower alcohols such as methanol, ethanol, propanol, and butanol, and ketones such as acetone and methyl ethyl ketone, and these may be used alone or in combination of two or more. Methanol is preferably used as the polymerization solvent in industrial applications.

[0045] The amount of the polymerization solvent used may be appropriately selected in accordance with the degree of polymerization of the target copolymer, taking into consideration the chain transfer constant of the polymerization solvent. For example, when the polymerization solvent is methanol, the amount is selected from the range of S (polymerization solvent) / M (monomer)=0.01 to 10 (mass ratio), preferably about 0.05 to 7 (mass ratio).

[0046] Examples of the polymerization catalyst include known radical polymerization catalysts such as azobisisobutyronitrile, acetyl peroxide, benzoyl peroxide, and lauryl peroxide, as well as low-temperature active radical polymerization catalysts. Examples of the low-temperature active radical polymerization catalyst include peroxyesters such as t-butylperoxyneodecanoate, t-butylperoxypivalate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, and t-hexylperoxypivalate; di-n-propylperoxydicarbonate, di-iso-propylperoxydicarbonate, di-sec-butylperoxydicarbonate, bis(4- Examples of the low-temperature active radical polymerization catalyst include peroxydicarbonates such as di(t-butylcyclohexyl)peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, dimethoxybutyl peroxydicarbonate, and di(3-methyl-3-methoxybutylperoxy)dicarbonate; organic peroxides such as diacyl peroxides such as 3,3,5-trimethylhexanoyl peroxide, diisobutyryl peroxide, and lauroyl peroxide; and azo compounds such as 2,2'-azobis-(2,4-dimethylvaleronitrile) and 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile). The low-temperature active radical polymerization catalyst refers to an organic compound having a half-life at 60°C of 10 to 300 minutes. These polymerization catalysts may be used alone or in combination of two or more.

[0047] The amount of the polymerization catalyst used varies depending on the type of catalyst and cannot be generally determined, but is selected arbitrarily depending on the polymerization rate. For example, when azobisisobutyronitrile or acetyl peroxide is used, the amount is preferably 0.001 to 0.2 parts by mass, more preferably 0.005 to 0.1 parts by mass, per 100 parts by mass of the vinyl ester monomer.

[0048] The method for introducing ethylene into the copolymer may be a conventional pressurized polymerization of ethylene, and the amount of ethylene introduced can be controlled by the pressure of ethylene, which is usually selected from the range of 2.0 to 8.0 MPa, although it depends on the target content of ethylene structural units.

[0049] Although the reaction temperature of the copolymerization reaction varies depending on the polymerization solvent and pressure used and cannot be generally determined, it is usually carried out at a temperature equal to or lower than the boiling point of the polymerization solvent, and is usually preferably 40 to 80° C., particularly preferably 55 to 80° C. If the temperature is equal to or higher than the lower limit, the polymerization proceeds appropriately, and there is no need to set a large amount of catalyst to shorten the polymerization time. Conversely, if the temperature is equal to or lower than the upper limit, there is a tendency for polymerization control to be excellent.

[0050] In addition, in the case of a batch process, the polymerization time is usually 4 to 10 hours, and more preferably 6 to 9 hours. If the polymerization time is equal to or greater than the lower limit, there is a tendency that it is not necessary to increase the polymerization temperature or set a large amount of catalyst, and conversely, if the polymerization time is equal to or less than the upper limit, there is a tendency that productivity is excellent. In the case of a continuous process, the average residence time in the polymerization vessel is usually 2 to 8 hours, and more preferably 2 to 6 hours. If the residence time is equal to or greater than the lower limit, there is a tendency that it is not necessary to increase the polymerization temperature or set a large amount of catalyst, and conversely, if the polymerization time is equal to or less than the upper limit, there is a tendency that productivity is excellent.

[0051] The polymerization rate is set as high as possible within the range where polymerization control is possible from the viewpoint of productivity, and is preferably 30 to 60%. When the polymerization rate is equal to or higher than the lower limit, productivity is excellent and a large amount of unpolymerized vinyl ester monomer tends to be prevented from remaining. Conversely, when the polymerization rate is equal to or lower than the upper limit, polymerization control tends to be excellent.

[0052] The ethylene-vinyl ester copolymer thus obtained is saponified to obtain the EVOH resin of the present embodiment. The saponification is carried out using a saponification catalyst in a state where the ethylene-vinyl ester copolymer obtained above is dissolved in alcohol or aqueous alcohol.

[0053] Examples of the alcohol include lower alcohols having 1 to 5 carbon atoms, such as methanol, ethanol, and propanol. These may be used alone or in combination of two or more. Of these, methanol is preferred.

[0054] The concentration of the ethylene-vinyl ester copolymer in the alcohol is appropriately selected depending on the viscosity, and is usually 5 to 60% by mass.

[0055] Examples of the saponification catalyst include alkali catalysts such as hydroxides and alcoholates of alkali metals, such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium methylate, and potassium ethylate; and acid catalysts such as sulfuric acid, hydrochloric acid, nitric acid, metasulfonic acid, zeolite, and cation exchange resins. These may be used alone or in combination of two or more. Among these, alkali catalysts such as hydroxides and alcoholates of alkali metals are preferred.

[0056] The temperature at which the saponification is carried out is not limited, but is preferably 20 to 140° C., and the saponification time is preferably 1 to 5 hours.

[0057] The EVOH resin produced in this manner may be at least partially derived from biomass, and preferably the ethylene structural units and / or vinyl alcohol structural units are derived from biomass. More preferably, from the viewpoint of availability, the vinyl alcohol structural units are derived from biomass. Such an EVOH resin is mainly composed of ethylene structural units and vinyl alcohol structural units, and optionally contains a small amount of vinyl ester structural units remaining without being saponified. When another comonomer is copolymerized, the EVOH resin further contains structural units derived from the comonomer.

[0058] In this specification, the term "mainly" refers to the component that accounts for the largest proportion in the target substance, and typically, it is preferably 50% by mass or more of the target substance, more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, and especially preferably 90% by mass or more, and may even be 100% by mass.

[0059] The EVOH resin produced by the above-described production method is contained in an alcohol-based solvent, and the content of the EVOH resin in the EVOH resin solution is preferably about 10 to 50 mass % from the viewpoint of producing the EVOH resin pellets described below.

[0060] The EVOH resin used in the composition (1) may be the alcohol solvent of the EVOH resin produced by the above-mentioned production method, but is preferably in the form of pellets. The shape and size of the pellets are preferably the same as those of the composition (1) described below.

[0061] The produced pellets are preferably washed by immersing them in an aqueous solution of an acid and / or its salt, and examples of such an acid include formic acid, acetic acid, adipic acid, phosphoric acid, boric acid, or salts thereof, with acetic acid being preferred. After that, the pellets are preferably washed with water.

[0062] The chemically treated and washed pellets may then be dried appropriately, preferably using a fluidized hot air dryer or a stationary hot air dryer, to produce EVOH resin pellets.

[0063] [Titanium Compound] Examples of the titanium compound include inorganic titanium compounds and organic titanium compounds. The titanium compounds may be used alone or in combination of two or more. Among these, inorganic titanium compounds are preferred.

[0064] Examples of the inorganic titanium compound include titanium oxide, titanium hydroxide, titanium chloride, and inorganic salts of titanium.

[0065] Examples of the titanium oxides include titanium(II) oxide, titanium(III) oxide, titanium(IV) oxide, and titanium zincate. Examples of the titanium hydroxides include titanium(II) hydroxide and titanium(II) hydroxide. Examples of the titanium chlorides include titanium(II) chloride and titanium(II) chloride. Examples of the titanium inorganic salts include titanium phosphate and titanium sulfate. Among these, titanium oxides are preferred, titanium(IV) oxide is more preferred, and rutile titanium(IV) oxide is particularly preferred.

[0066] Examples of the organic titanium compounds include titanium carboxylates such as titanium acetate, titanium butyrate, and titanium stearate.

[0067] The titanium compound may exist in the composition (1) as a titanium compound, or may exist in an ionized state or in the form of a complex interacting with the EVOH resin or other ligands.

[0068] The average particle size of the titanium compound is usually 0.001 to 100 μm, preferably 0.01 to 50 μm, and more preferably 0.015 to 20 μm. When the average particle size of the titanium compound is within the above range, the coloration suppression effect tends to be more excellent. The average particle size can be measured by a predetermined method, such as dynamic light scattering (DLS) or sedimentation velocity method.

[0069] The content of the titanium compound in terms of metal, relative to the mass of composition (1), is 0.0001 ppm or more and less than 1 ppm, preferably 0.0001 to 0.8 ppm, more preferably 0.0005 to 0.5 ppm, even more preferably 0.001 to 0.3 ppm, particularly preferably 0.005 to 0.2 ppm, and especially preferably 0.01 to 0.1 ppm. When the content of the titanium compound is equal to or less than the upper limit, thermal decomposition of the EVOH resin tends to be prevented and coloration prevention properties tend to be excellent, while when the content is equal to or more than the lower limit, thermal degradation tends to be suppressed. The content of the titanium compound in terms of metal is, in other words, the content of elemental titanium.

[0070] The content of the titanium compound in terms of metal can be determined by weighing out composition (1) into a platinum crucible, ashing it successively with a burner and an electric furnace, thermally decomposing the ashed material with nitric acid and hydrofluoric acid, treating it with a mixed acid of dilute nitric acid and dilute hydrofluoric acid, and measuring the titanium in the constant volume solution obtained by ICP mass spectrometry using an ICP mass spectrometer (Agilent 8800, manufactured by Agilent Technologies).

[0071] Titanium is stable as a tetravalent ion, and even a small amount of titanium is stabilized by coordinating to the double bond when a polyene structure is formed in the main chain of the EVOH resin as described above and forming a chelate, etc., and is therefore presumed to inhibit the formation of a polyene structure in the main chain of the EVOH resin.

[0072] [Other Thermoplastic Resins] The present composition (1) may contain a thermoplastic resin other than EVOH resin within a range that does not impair the effects of the present invention (for example, typically 50% by mass or less of the present composition (1), preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less; the lower limit is 0% by mass, e.g., 0 to 50% by mass). As the other thermoplastic resin, known thermoplastic resins may be used, such as polyester resins, polystyrene resins, polyvinyl chloride resins, polycarbonate resins, ionomers, polyvinylidene chloride, polyester elastomers, polyurethane elastomers, chlorinated polyethylene, and chlorinated polypropylene. These may be used alone or in combination of two or more.

[0073] [Other Compounding Agents] The composition (1) may also contain compounding agents generally compounded with EVOH resins (however, the term "compounding agent" as used herein excludes titanium compounds) within a range that does not impair the effects of the present invention (for example, 5% by mass or less, preferably 3% by mass or less, with the lower limit being 0% by mass, for example, 0 to 5% by mass). Examples of the compounding agents include inorganic double salts (for example, hydrotalcite, etc.), plasticizers (for example, aliphatic polyhydric alcohols such as ethylene glycol, glycerin, and hexanediol), oxygen absorbers [for example, inorganic oxygen absorbers such as aluminum powder and potassium sulfite; ascorbic acid, its fatty acid esters and metal salts, etc.; gallic acid; polyhydric phenols such as hydroxyl group-containing phenolaldehyde resins; terpene compounds; blends of tertiary hydrogen-containing resins and transition metals (for example, a combination of polypropylene and cobalt); blends of carbon-carbon unsaturated bond-containing resins and transition metals; Polymeric oxygen absorbers such as polymeric oxygen absorbers, such as polymeric compounds (e.g., a combination of polybutadiene and cobalt), photooxidatively degradable resins (e.g., polyketones), anthraquinone polymers (e.g., polyvinyl anthraquinone), and combinations thereof to which photoinitiators (e.g., benzophenone), antioxidants other than those mentioned above, and deodorants (e.g., activated carbon), heat stabilizers (boric acid, phosphoric acid), light stabilizers, ultraviolet absorbers, colorants, antistatic agents, surfactants (excluding those used as lubricants), antibacterial agents, antiblocking agents, and fillers (e.g., aluminum, inorganic fillers). These compounds may be used alone or in combination of two or more.

[0074] [Method for Producing Composition] The present composition (1) can be produced, for example, by mixing the EVOH resin and the titanium compound by a known method such as a dry blending method, a melt mixing method, a solution mixing method, an impregnation method, etc. Among these, it is preferable to produce the composition by including a step of mixing the EVOH resin and the titanium compound. Furthermore, these production methods can be used in any combination.

[0075] The dry blending method may be, for example, (i) a method in which a pelletized EVOH resin and a titanium compound are dry blended using a tumbler or the like.

[0076] Examples of the melt-mixing method include (ii) a method in which a pellet-shaped EVOH resin is dry-blended with a titanium compound, and the resulting dry blend is melt-kneaded; and (iii) a method in which a titanium compound is added to a molten EVOH resin, and the resulting mixture is melt-kneaded.

[0077] Examples of the solution mixing method include (iv) a method in which a solution is prepared using a commercially available EVOH resin, a titanium compound is blended therein, the mixture is coagulated and molded, and then the mixture is subjected to solid-liquid separation by known means and dried; and (v) a method in which a titanium compound is added to an ethylene-vinyl ester copolymer solution before saponification or a homogeneous solution of EVOH resin (such as a water / alcohol solution) during the production process of EVOH resin, the mixture is coagulated and molded, and then the mixture is subjected to solid-liquid separation by known means and dried.

[0078] The impregnation method includes, for example, (vi) a method in which pellets of EVOH resin are brought into contact with an aqueous solution containing a titanium compound to incorporate the titanium compound into the EVOH resin, followed by drying. The aqueous solution containing a titanium compound may be an aqueous solution of a titanium compound or a titanium compound immersed in water containing various chemicals to elute titanium ions.

[0079] In the impregnation method, the content of the titanium compound (in terms of metal) can be controlled by the concentration of the titanium compound in the aqueous solution in which the EVOH resin is immersed, the immersion temperature, the immersion time, etc. The immersion temperature and the immersion time are usually 0.5 to 48 hours, preferably 1 to 36 hours, and the immersion temperature is usually 10 to 40°C, preferably 20 to 35°C.

[0080] As the drying method in each of the above-mentioned production methods, various drying methods can be used, and either static drying or fluidized drying may be used, or these may be used in combination.

[0081] As described above, in this embodiment, the above-mentioned different methods can be combined. Among them, the melt mixing method is preferred, and method (ii) is particularly preferred, in terms of productivity and the fact that a resin composition with more pronounced effects of the present invention can be obtained. Furthermore, when using the other thermoplastic resins and other compounding agents, they may be compounded by a conventional method according to the above-mentioned manufacturing method.

[0082] The shape of the present composition (1) obtained by each of the above-mentioned production methods may be any shape, but is preferably pellets. The pellets may be, for example, spherical, oval, cylindrical, die-shaped, or rectangular. They are typically oval or cylindrical. From the viewpoint of convenience when subsequently used as a molding material, the size of the pellets is such that, in the case of an oval shape, the minor axis is typically 1 to 10 mm, preferably 2 to 6 mm, and more preferably 2.5 to 5.5 mm, and the major axis is typically 1.5 to 30 mm, preferably 3 to 20 mm, and more preferably 3.5 to 10 mm. In the case of a cylindrical shape, the diameter of the base is typically 1 to 6 mm, preferably 2 to 5 mm, and the length is typically 1 to 6 mm, preferably 2 to 5 mm. In the case of a die-shaped shape, the length of one side is typically 1 to 6 mm, preferably 2 to 5 mm. The shape and size of the pelletized EVOH resin used in each of the above-mentioned production methods are also preferably similar.

[0083] The water content of the composition (1) is not particularly limited, but is usually 0.01 to 0.5% by mass, preferably 0.05 to 0.35% by mass, and particularly preferably 0.1 to 0.3% by mass.

[0084] The water content of the composition (1) is measured and calculated by the following method. １ ) was weighed on an electronic balance, dried in a hot air dryer at 150°C for 5 hours, and allowed to cool in a desiccator for 30 minutes, after which the mass (W ２ ) is weighed and calculated using the following formula: [Formula] Water content (mass%) = [(W １ -W ２ ) / W １ ]×100

[0085] When the composition (1) is in the form of pellets, it is also preferable to apply a known lubricant to the surface of the pellets in order to stabilize the feedability during melt molding. Examples of lubricants include higher fatty acids having 12 or more carbon atoms (e.g., lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc.), higher fatty acid esters (methyl esters, isopropyl esters, butyl esters, octyl esters of higher fatty acids, etc.), higher fatty acid amides (e.g., saturated higher fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, etc.; unsaturated higher fatty acid amides such as oleic acid amide, erucic acid amide, etc.; bis-higher fatty acid amides such as ethylene bisstearic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, ethylene bislauric acid amide, etc.), low-molecular-weight polyolefins (e.g., low-molecular-weight polyethylene or low-molecular-weight polypropylene having a molecular weight of about 500 to 10,000, or acid-modified products thereof), higher alcohols having 6 or more carbon atoms, ester oligomers, and fluorinated ethylene resins. These compounds can be used alone or in combination of two or more. The content of such lubricants is usually 5% by mass or less, preferably 1% by mass or less, of the composition (1). The lower limit is usually 0% by mass, for example, 0 to 5% by mass.

[0086] The composition (1) thus obtained has excellent thermal stability, and the temperature difference (°C) when the mass of the composition (1) decreases by 10% from the temperature when the mass decreases by 5% is usually 12°C or more, preferably 12.5°C or more, and more preferably 13°C or more. The upper limit of the temperature difference (°C) when the mass decreases by 10% from the temperature when the mass decreases by 5% is the higher the better, but it may usually be 20°C or less, or 16°C or less, for example, 12 to 20°C, or 12.5 to 16°C.

[0087] <Molding material> The present composition (1) thus obtained is prepared into various forms such as pellets, powder, or liquid, and is provided as a molding material for various molded products. In particular, in this embodiment, when it is provided as a material for melt molding, the effects of the present invention tend to be more efficiently obtained, which is preferable.

[0088] Examples of the molded article include a monolayer film molded from the present composition (1), as well as a multilayer structure having a layer made of the present composition (1).

[0089] <Multilayer structure> The multilayer structure according to the first aspect of the present invention (hereinafter referred to as "the present multilayer structure (1)") contains the present composition (1) and has at least one layer made of the present composition (1). The layer made of the present composition (1) in the present multilayer structure (1) (hereinafter simply referred to as "the present composition layer (1)") may be a single layer or multiple layers. Furthermore, the present composition layer (1) can be laminated with another substrate (hereinafter, the resin used for the substrate may be abbreviated as "substrate resin") containing a thermoplastic resin other than EVOH resin as a main component to impart further strength, protect the present composition layer (1) from the effects of moisture, etc., or impart other functions.

[0090] Examples of the base resin include polyethylene-based resins such as linear low-density polyethylene, low-density polyethylene, very low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-propylene (block and random) copolymers, and ethylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymers; polypropylene-based resins such as polypropylene and propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymers; (unmodified) polyolefin-based resins such as polybutene, polypentene, and polycyclic olefin-based resins (polymers having a cyclic olefin structure in at least one of the main chain and side chain); and polyolefins obtained by dissolving these polyolefins in an unsaturated carboxylic acid or Examples include polyolefin resins in the broad sense, including modified olefin resins such as unsaturated carboxylic acid-modified polyolefin resins graft-modified with an ester thereof, ionomers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, polyester resins, polyamide resins (including copolymerized polyamides), polyvinyl chloride, polyvinylidene chloride, acrylic resins, polystyrene resins, vinyl ester resins, polyester elastomers, polyurethane elastomers, polystyrene elastomers, halogenated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, aromatic or aliphatic polyketones, etc. These may be used alone or in combination of two or more.

[0091] Of these, hydrophobic resins such as polyamide-based resins, polyolefin-based resins, polyester-based resins, and polystyrene-based resins are preferred, and more preferred are polyolefin-based resins such as polyethylene-based resins, polypropylene-based resins, polycyclic olefin-based resins, and unsaturated carboxylic acid-modified polyolefin-based resins thereof.

[0092] The layer structure of the multilayer structure (1) can be any combination, such as a / b, b / a / b, a / b / a, a1 / a2 / b, a / b1 / b2, b2 / b1 / a / b1 / b2, or b2 / b1 / a / b1 / a / b1 / b2, where a denotes the composition layer (1) and b denotes the base resin layer (b1, b2, etc.). Furthermore, when R denotes a recycled layer containing a mixture of the composition (1) and a thermoplastic resin other than EVOH resin, obtained by remelting and molding edges or defective products generated during the manufacturing process of the multilayer structure (1), b / R / a, b / R / a / b, b / R / a / R / b, b / a / R / a / b, b / R / a / R / a / R / b, or b / R / a / R / a / R / b, etc. The total number of layers in the multilayer structure (1) is usually 2 to 15, and preferably 3 to 10. In the above layer structure, an adhesive resin layer containing an adhesive resin may be interposed between the respective layers, if necessary.

[0093] Known adhesive resins can be used, and may be selected appropriately depending on the type of thermoplastic resin used in the base resin layer "b." Representative examples include modified polyolefin polymers containing carboxy groups, which are obtained by chemically bonding an unsaturated carboxylic acid or its anhydride to a polyolefin resin via addition reaction, graft reaction, or the like. Examples of modified polyolefin polymers containing carboxy groups include maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, maleic anhydride-grafted ethylene-propylene (block and random) copolymers, maleic anhydride-grafted ethylene-ethyl acrylate copolymers, maleic anhydride-grafted ethylene-vinyl acetate copolymers, maleic anhydride-grafted polycyclic olefin resins, and maleic anhydride-grafted polyolefin resins. These may be used alone or in combination of two or more.

[0094] In the present multilayer structure (1), when an adhesive resin layer is used between the present composition layer (1) and the base resin layer, it is preferable to use an adhesive resin with excellent hydrophobicity, since the adhesive resin layers are located on both sides of the present composition layer (1).

[0095] The base resin and adhesive resin may contain conventionally known plasticizers, fillers, clay (montmorillonite, etc.), colorants, antioxidants, antistatic agents, lubricants, nucleating agents, antiblocking agents, waxes, etc., within a range that does not impair the spirit of the present invention (for example, usually 30% by mass or less, preferably 10% by mass or less, with the lower limit being 0% by mass, e.g., 0 to 30% by mass, based on the total resin). These may be used alone or in combination of two or more.

[0096] The lamination of the present composition layer (1) and the above-mentioned substrate resin layer (including the case where an adhesive resin layer is interposed) can be carried out by a known method. For example, there can be mentioned a method of melt-extrusion laminating the substrate resin onto a film, sheet, etc. of the present composition (1), a method of melt-extrusion laminating the present composition (1) onto a substrate resin layer, a method of co-extruding the present composition (1) and the substrate resin, a method of dry-laminating the present composition (1) (the present composition layer (1)) and the substrate resin (substrate resin layer) using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, a polyurethane compound, etc., a method of applying a solution of the present composition (1) onto the substrate resin and then removing the solvent, etc. Among these, in consideration of cost and environmental aspects, it is preferable to produce the layer including the present composition layer (1) by a step of melt-molding it, and specifically, a co-extrusion method is preferred.

[0097] The multilayer structure (1) may be subjected to a (heat) stretching treatment, if necessary. The stretching treatment may be either uniaxial stretching or biaxial stretching, and in the case of biaxial stretching, it may be simultaneous stretching or sequential stretching. Furthermore, the stretching method may be a roll stretching method, tenter stretching method, tubular stretching method, stretch-blow method, vacuum pressure forming, or the like, whichever provides a higher stretch ratio. The stretching temperature is a temperature near the melting point of the multilayer structure (1), and is usually selected from the range of 40 to 170°C, preferably about 60 to 160°C. When the stretching temperature is equal to or higher than the lower limit, the stretchability tends to be excellent, and when the stretching temperature is equal to or lower than the upper limit, a stable stretched state tends to be easily maintained.

[0098] The stretched multilayer structure (1) may be heat-set for the purpose of imparting dimensional stability. Heat-setting can be performed by known means, for example, by subjecting the stretched multilayer structure (1) to heat treatment while maintaining tension, usually at 80 to 180°C, preferably 100 to 165°C, for usually 2 to 600 seconds.

[0099] When the stretched multilayer structure (1) is used as a shrink film, in order to impart heat shrinkability, the above-mentioned heat setting is not carried out, but rather a treatment such as cooling and setting the stretched multilayer structure (1) by applying cold air thereto may be carried out.

[0100] The thickness of the present multilayer structure (1) (including a stretched one), as well as the thickness of the present composition layer (1), base resin layer, and adhesive resin layer constituting the multilayer structure (1), cannot be generally determined depending on the layer configuration, type of base resin, type of adhesive resin, intended use, packaging form, required physical properties, etc., but the thickness of the present multilayer structure (1) (including a stretched one) is usually 10 to 5,000 μm, preferably 30 to 3,000 μm, and particularly preferably 50 to 2,000 μm. The present composition layer (1) is usually 1 to 500 μm, preferably 3 to 300 μm, and particularly preferably 5 to 200 μm; the base resin layer is usually 5 to 3,000 μm, preferably 10 to 2,000 μm, and particularly preferably 20 to 1,000 μm; and the adhesive resin layer is usually 0.5 to 250 μm, preferably 1 to 150 μm, and particularly preferably 3 to 100 μm.

[0101] Furthermore, the thickness ratio of the present composition layer (1) to the base resin layer in the present multilayer structure (1) (present composition layer (1) / base resin layer), expressed as the ratio between the thickest layers when there are multiple layers of each, is usually 1 / 99 to 50 / 50, preferably 5 / 95 to 45 / 55, and particularly preferably 10 / 90 to 40 / 60. Furthermore, the thickness ratio of the present composition layer (1) to the adhesive resin layer in the present multilayer structure (1) (present composition layer (1) / adhesive resin layer), expressed as the ratio between the thickest layers when there are multiple layers of each, is usually 10 / 90 to 99 / 1, preferably 20 / 80 to 95 / 5, and particularly preferably 50 / 50 to 90 / 10.

[0102] <Molded Article> It is also possible to obtain a cup- or tray-shaped molded article using the present multilayer structure (1). In this case, a drawing method is usually employed, specifically vacuum forming, pressure forming, vacuum-pressure forming, plug-assisted vacuum-pressure forming, etc. Furthermore, when a tube- or bottle-shaped multilayer container (laminate structure) is obtained from a multilayer parison (a hollow tubular preform before blowing), a blow molding method is employed. Specific examples include extrusion blow molding (two-head type, mold-moving type, parison-shift type, rotary type, accumulator type, horizontal parison type, etc.), cold parison blow molding, injection blow molding, and biaxial stretch blow molding (extrusion-type cold parison biaxial stretch blow molding, injection-type cold parison biaxial stretch blow molding, injection-molding in-line biaxial stretch blow molding, etc.). The resulting laminate may be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making, deep drawing, box processing, tube processing, splitting processing, etc. as required.

[0103] <Packaging> Packaging such as a single layer film formed from the present composition (1) or a container or lid material formed from a bag, cup, tray, tube, bottle, etc., made from the present multilayer structure (1) is useful as a variety of packaging material containers (e.g., food packaging, drug packaging, cosmetic packaging) for general foods as well as seasonings such as mayonnaise and dressing, fermented foods such as miso, oily foods such as salad oil, beverages, cosmetics, pharmaceuticals, etc.

[0104] <<Second Aspect>> The second aspect includes the following aspects [II-1] to [II-12]. [II-1] An EVOH resin composition containing an EVOH resin, a titanium compound, and an alkaline earth metal compound (A), wherein at least a portion of the EVOH resin is derived from biomass, the titanium compound has a metal-equivalent content of 0.0001 ppm or more and less than 1 ppm relative to the mass of the composition, and the mass ratio of the metal-equivalent content of the alkaline earth metal compound (A) to the metal-equivalent content of the titanium compound is 500 to 55,000. [II-2] The composition according to [II-1], wherein the titanium compound has a metal-equivalent content of 0.0001 ppm or more and 5,000 ppm or less relative to the mass of the composition. [II-3] The composition according to [II-1] or [II-2], wherein the titanium compound has a metal-equivalent content of 0.0001 ppm or more and 0.8 ppm or less relative to the mass of the composition. [II-4] The composition according to any one of [II-1] to [II-3], wherein the EVOH resin has a biobased content of 0.01 to 99%. [II-5] The composition according to any one of [II-1] to [II-4], wherein the EVOH resin has a biobased content of 1 to 99%. [II-6] A molding material comprising the composition according to any one of [II-1] to [II-5]. [II-7] A multilayer structure having a layer comprising the composition according to any one of [II-1] to [II-5]. [II-8] The multilayer structure according to [II-7], further comprising an adhesive resin layer. [II-9] A molded article comprising the multilayer structure according to [II-7] or [II-8]. [II-10] A food package comprising the multilayer structure according to [II-7] or [II-8]. [II-11] A method for producing the composition according to any one of [II-1] to [II-5], comprising the step of mixing the EVOH resin and the titanium compound. [II-12] A method for producing the multilayer structure according to [II-7] or [II-8], comprising the step of melt-molding a layer containing the composition.

[0105] The second aspect will be described below based on examples of modes for carrying out the second aspect, although the present invention is not limited to the embodiments described below.

[0106] <Composition> The composition according to the second aspect of the present invention (hereinafter, sometimes referred to as "the composition (2)") contains an EVOH resin as an essential component, a specific trace amount of a titanium compound, and the alkaline earth metal compound (A) and the titanium compound in a specific mass ratio. That is, the content of the EVOH resin in the composition (2) is usually 1 mass% or more, preferably 10 mass% or more, more preferably 50 mass% or more, even more preferably 60 mass% or more, particularly preferably 70 mass% or more, especially preferably 80 mass% or more, especially more preferably 90 mass% or more, and still more preferably 95 mass% or more. The upper limit is 100 mass%, and may be 99 mass%, for example, 1 to 100 mass%, or 10 to 99 mass%. Each component will be described below.

[0107] [EVOH Resin] The EVOH resin used in this embodiment is at least partly biomass-derived, and the same EVOH resin as described in the first embodiment can be used. In addition, "present composition (1)" in the description of the [EVOH resin] in the first embodiment can be read as "present composition (2)."

[0108] [Titanium Compound] The titanium compound used in this embodiment may be the same as the [titanium compound] described in the first embodiment. In addition, "the present composition (1)" in the description of the [titanium compound] in the first embodiment may be read as "the present composition (2)."

[0109] [Alkaline earth metal compound (A)] Examples of the alkaline earth metal compound (A) include salts and oxides of alkaline earth metals. These may be used alone or in combination of two or more. Among these, alkaline earth metal oxides are preferred from the standpoints of economy and dispersibility.

[0110] Examples of the alkaline earth metal salts include inorganic salts of alkaline earth metals and carboxylates of alkaline earth metals.

[0111] Examples of the inorganic salts of alkaline earth metals include alkaline earth metal carbonates, hydrogencarbonates, phosphates, borates, sulfates, and chlorides. Examples of the carboxylates of alkaline earth metals include saturated or unsaturated carboxylates having typically 2 to 25 carbon atoms, preferably saturated or unsaturated carboxylates having 2 to 22 carbon atoms, and particularly preferably saturated or unsaturated carboxylates having 6 to 20 carbon atoms. Specific examples include monocarboxylic acid salts such as acetate, butyrate, propionate, enanthate, caprate, laurate, palmitate, stearate, 12-hydroxystearate, behenate, and montanate, and dicarboxylic acid salts such as oxalate, malonate, succinate, adipate, suberate, and sebacate. Among these, linear saturated carboxylates are preferred in terms of commercial availability, and linear saturated monocarboxylic acid salts are more preferred.

[0112] Examples of the alkaline earth metal species of the alkaline earth metal compound (A) include beryllium, magnesium, calcium, strontium, barium, and radium. Among these, magnesium and calcium are preferred in terms of market availability and economic efficiency, and magnesium is particularly preferred.

[0113] Among these, magnesium oxide is preferred as the alkaline earth metal compound (A). From the viewpoints of economy and dispersibility, it is preferred that the alkaline earth metal compound (A) does not include layered inorganic compounds such as montmorillonite and double salts such as hydrotalcite.

[0114] The alkaline earth metal compound (A) may be in any form, such as a solid (powder, fine powder, flakes, etc.), a semi-solid, a liquid, a paste, a solution, or an emulsion (aqueous dispersion). Of these, a powder form is preferred.

[0115] The content of the alkaline earth metal compound (A) in terms of metal, relative to the mass of composition (2), is preferably 1 to 10,000 ppm, more preferably 5 to 3,000 ppm, even more preferably 10 to 2,000 ppm, particularly preferably 20 to 500 ppm, and especially preferably 30 to 300 ppm. When the content of the alkaline earth metal compound (A) in terms of metal is equal to or less than the upper limit, the thermal stability of composition (2) tends to be excellent, and when it is equal to or more than the lower limit, the moldability of composition (2) tends to be excellent.

[0116] The content of the alkaline earth metal compound (A) in terms of metal can be measured by, for example, heating and ashing the present composition (2), treating the resulting solution with an acid such as hydrochloric acid, adding pure water to the resulting solution, and measuring the volume of the solution with an atomic absorption spectrophotometer. The content of the alkaline earth metal compound (A) in terms of metal is the content of the alkaline earth metal element.

[0117] The mass ratio of the metal-equivalent content of the alkaline earth metal compound (A) to the metal-equivalent content of the titanium compound is preferably 500 to 55,000, more preferably 800 to 50,000, even more preferably 1,000 to 40,000, and particularly preferably 1,000 to 30,000. When the mass ratio is equal to or less than the upper limit, coloration tends to be easily suppressed, and when the mass ratio is equal to or greater than the lower limit, the effect of suppressing thermal degradation tends to be obtained.

[0118] It is generally known that blending an alkaline earth metal compound (A) with an EVOH resin tends to cause a decrease in viscosity over time when heated. Although the mechanism is not clear, it is presumed that blending the alkaline earth metal compound (A) makes the composition (2) basic, and some anion acts as a nucleophile, abstracting hydrogen atoms bonded to carbon atoms in the main chain of the EVOH resin, thereby causing a decomposition reaction of the main chain and severing the main chain of the EVOH resin. It is presumed that the deterioration of the EVOH resin after heating occurs because double bond structures are formed in the main chain of the EVOH resin during the reaction, and these structures again act as reaction starting points, causing dehydration reactions and the like, resulting in the formation of polyene structures in the main chain of the EVOH resin.

[0119] In contrast, the present composition (2) contains a specific trace amount of a titanium compound and the alkaline earth metal compound (A) and the titanium compound in a specific mass ratio, thereby suppressing the deterioration of the thermal stability of the EVOH resin. Normally, when a titanium compound is contained in composition (2), it is thought that the composition (2) will be colored by titanium ions, and therefore it is common technical knowledge for a person skilled in the art to avoid the use of a titanium compound.

[0120] However, in the present embodiment, contrary to such common technical knowledge, it has been found that a composition (2) having excellent thermal stability can be obtained by using a specific trace amount of a titanium compound and the alkaline earth metal compound (A) and the titanium compound in a specific mass ratio.

[0121] Titanium is stable as a tetravalent ion, and is thought to inhibit the formation of a polyene structure in the main chain of EVOH resin, as it stabilizes the resin by coordinating with the double bond in the main chain of EVOH resin and forming a chelate, etc. On the other hand, when the amount of titanium compound is within a specific range, it is thought that deterioration of EVOH resin due to thermal decomposition caused by titanium tends to be inhibited.

[0122] [Other Thermoplastic Resins] The present composition (2) may contain a thermoplastic resin other than the EVOH resin within a range that does not impair the effects of the present invention (for example, usually 50% by mass or less of the present composition (2), preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The lower limit is 0% by mass, for example, 0 to 50% by mass). As the other thermoplastic resin, the same ones as those described in the first embodiment of the present invention as [Other Thermoplastic Resins] can be used.

[0123] [Other Compounding Agents] The composition (2) may also contain compounding agents generally compounded with EVOH resins (however, the term "compounding agent" as used herein means excluding titanium compounds and alkaline earth metal compounds (A)) within a range that does not impair the effects of the present invention (for example, 5% by mass or less, preferably 3% by mass or less, with the lower limit being 0% by mass, for example, 0 to 5% by mass). Examples of the compounding agents include inorganic double salts (for example, hydrotalcite, etc.), plasticizers (for example, aliphatic polyhydric alcohols such as ethylene glycol, glycerin, and hexanediol), oxygen absorbers [for example, inorganic oxygen absorbers such as aluminum powder and potassium sulfite; ascorbic acid, its fatty acid esters and metal salts, etc.; gallic acid; polyhydric phenols such as hydroxyl group-containing phenolaldehyde resins; terpene compounds; blends of tertiary hydrogen-containing resins and transition metals (for example, a combination of polypropylene and cobalt); blends of carbon-carbon unsaturated bond-containing resins and transition metals; Polymeric oxygen absorbers such as polymeric oxygen absorbers, such as polymeric compounds (e.g., a combination of polybutadiene and cobalt), photooxidatively degradable resins (e.g., polyketones), anthraquinone polymers (e.g., polyvinyl anthraquinone), and combinations thereof to which photoinitiators (e.g., benzophenone), antioxidants other than those mentioned above, and deodorants (e.g., activated carbon), heat stabilizers (boric acid, phosphoric acid), light stabilizers, ultraviolet absorbers, colorants, antistatic agents, surfactants (excluding those used as lubricants), antibacterial agents, antiblocking agents, and fillers (e.g., aluminum, inorganic fillers). These compounds may be used alone or in combination of two or more.

[0124] [Method for Producing Composition] The present composition (2) can be produced, for example, by mixing the EVOH resin, titanium compound, and alkaline earth metal compound (A) by a known method such as a dry blending method, a melt mixing method, a solution mixing method, an impregnation method, etc. Among these, a method including a step of mixing the EVOH resin and the titanium compound is preferred. Furthermore, these production methods can be used in any combination.

[0125] The dry blending method may be, for example, (i) a method in which a pelletized EVOH resin is dry blended with a titanium compound and / or an alkaline earth compound using a tumbler or the like.

[0126] Examples of the melt-mixing method include (ii) a method in which a pelletized EVOH resin is dry-blended with a titanium compound and / or an alkaline earth compound, and the resulting dry blend is melt-kneaded; and (iii) a method in which a titanium compound and / or an alkaline earth compound is added to a molten EVOH resin, and the resulting mixture is melt-kneaded.

[0127] Examples of the solution mixing method include (iv) a method in which a solution is prepared using a commercially available EVOH resin, a titanium compound and / or an alkaline earth compound is blended therein, the mixture is coagulated and molded, and then the mixture is subjected to solid-liquid separation by known means and dried; and (v) a method in which a titanium compound and / or an alkaline earth compound is added to an ethylene-vinyl ester copolymer solution before saponification or a homogeneous solution of EVOH resin (such as a water / alcohol solution) during the production of EVOH resin, the mixture is coagulated and molded, and then the mixture is subjected to solid-liquid separation by known means and dried.

[0128] The impregnation method includes, for example, (vi) a method in which pellets of EVOH resin are brought into contact with an aqueous solution containing a titanium compound and / or an alkaline earth compound to incorporate the titanium compound and / or the alkaline earth compound into the EVOH resin, followed by drying. The aqueous solution containing a titanium compound may be an aqueous solution of a titanium compound or a titanium compound immersed in water containing various chemicals to elute titanium ions.

[0129] In the impregnation method, the content of the titanium compound (in terms of metal) can be controlled by the concentration of the titanium compound in the aqueous solution in which the EVOH resin is immersed, the immersion temperature, the immersion time, etc. The immersion temperature and the immersion time are usually 0.5 to 48 hours, preferably 1 to 36 hours, and the immersion temperature is usually 10 to 40°C, preferably 20 to 35°C.

[0130] As the drying method in each of the above-mentioned production methods, various drying methods can be used, and either static drying or fluidized drying may be used, or these may be used in combination.

[0131] As described above, in this embodiment, the above-mentioned different methods can be combined. Among them, the melt mixing method is preferred, and method (ii) is particularly preferred, in terms of productivity and the fact that a resin composition with more pronounced effects of the present invention can be obtained. Furthermore, when using the other thermoplastic resins and other compounding agents, they may be compounded by a conventional method according to the above-mentioned manufacturing method.

[0132] The shape of the present composition (2) obtained by each of the above-mentioned production methods may be any shape, but is preferably pellets. The pellets may be, for example, spherical, oval, cylindrical, die-shaped, or rectangular, but are typically oval or cylindrical. From the viewpoint of convenience when subsequently used as a molding material, the size of the pellets is such that, in the case of an oval shape, the minor axis is typically 1 to 10 mm, preferably 2 to 6 mm, and more preferably 2.5 to 5.5 mm, and the major axis is typically 1.5 to 30 mm, preferably 3 to 20 mm, and more preferably 3.5 to 10 mm. In the case of a cylindrical shape, the diameter of the base is typically 1 to 6 mm, preferably 2 to 5 mm, and the length is typically 1 to 6 mm, preferably 2 to 5 mm. In the case of a die-shaped shape, the length of one side is typically 1 to 6 mm, preferably 2 to 5 mm. The shape and size of the pelletized EVOH resin used in each of the above-mentioned production methods are also preferably similar.

[0133] The water content of the composition (2) is not particularly limited, but is usually 0.01 to 0.5% by mass, preferably 0.05 to 0.35% by mass, and particularly preferably 0.1 to 0.3% by mass.

[0134] The water content of the composition (2) is measured and calculated by the following method. １ ) was weighed on an electronic balance, dried in a hot air dryer at 150°C for 5 hours, and allowed to cool in a desiccator for 30 minutes, after which the mass (W ２ ) is weighed and calculated using the following formula: [Formula] Water content (mass%) = [(W１ -W ２ ) / W １ ]×100

[0135] When the composition (2) is in the form of pellets, it is also preferable to apply a known lubricant to the surface of the pellets in order to stabilize the feedability during melt molding. Examples of lubricants include higher fatty acids having 12 or more carbon atoms (e.g., lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc.), higher fatty acid esters (methyl esters, isopropyl esters, butyl esters, octyl esters of higher fatty acids, etc.), higher fatty acid amides (e.g., saturated higher fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, etc.; unsaturated higher fatty acid amides such as oleic acid amide, erucic acid amide, etc.; bis-higher fatty acid amides such as ethylene bisstearic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, ethylene bislauric acid amide, etc.), low-molecular-weight polyolefins (e.g., low-molecular-weight polyethylene or low-molecular-weight polypropylene having a molecular weight of about 500 to 10,000, or acid-modified products thereof), higher alcohols having 6 or more carbon atoms, ester oligomers, and fluorinated ethylene resins. These compounds can be used alone or in combination of two or more. The content of such lubricants is usually 5% by mass or less, preferably 1% by mass or less, of the composition (2). The lower limit is usually 0% by mass, for example, 0 to 5% by mass.

[0136] The composition (2) thus obtained has excellent thermal stability, and the composition (2) was analyzed by a visual analyzer IRIS VA400 (Alpha). The ratio ("1381" + "1382") / ("1636" + "1637" + "1638") of the sum of color numbers "1381" (R: 88, G: 104, B: 88) and "1382" (R: 88, G: 104, B: 104) to the sum of color numbers "1636" (R: 104, G: 104, B: 72), "1637" (R: 104, G: 104, B: 88), and "1638" (R: 104, G: 104, B: 104), measured using a fluororesin (manufactured by MOS), is usually 1.0 or less, preferably 0.8 or less, and more preferably 0.6 or less. The lower limit is usually 0, for example, usually 0 to 1.0. The smaller the ratio, the more suppressed is the coloration due to thermal degradation, and the higher the thermal stability tends to be. A difference of 0.1 in the ratio is very large, since it appears as a large difference in yield in actual production.

[0137] <Molding material> The present composition (2) thus obtained is prepared into various forms such as pellets, powder, or liquid, and is provided as a molding material for various molded products. In particular, in this embodiment, when it is provided as a material for melt molding, the effects of the present invention tend to be more efficiently obtained, which is preferable.

[0138] Examples of the molded article include a monolayer film molded from the present composition (2), as well as a multilayer structure having a layer made of the present composition (2).

[0139] <Multilayer structure> The multilayer structure according to the second aspect of the present invention (hereinafter referred to as "the multilayer structure") contains the present composition (2) and has at least one layer made of the present composition (2). The layer made of the present composition (2) in the present multilayer structure (hereinafter simply referred to as "the present composition layer") may be a single layer or multiple layers. Furthermore, the present composition layer can be laminated with another substrate containing a thermoplastic resin other than EVOH resin as a main component (hereinafter, the resin used for the substrate may be abbreviated as "substrate resin") to further impart strength, protect the present composition layer from the effects of moisture, etc., or impart other functions.

[0140] Examples of the base resin include polyethylene-based resins such as linear low-density polyethylene, low-density polyethylene, very low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-propylene (block and random) copolymers, and ethylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymers; polypropylene-based resins such as polypropylene and propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymers; (unmodified) polyolefin-based resins such as polybutene, polypentene, and polycyclic olefin-based resins (polymers having a cyclic olefin structure in at least one of the main chain and side chain); and polyolefins obtained by dissolving these polyolefins in an unsaturated carboxylic acid or Examples include polyolefin resins in the broad sense, including modified olefin resins such as unsaturated carboxylic acid-modified polyolefin resins graft-modified with an ester thereof, ionomers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, polyester resins, polyamide resins (including copolymerized polyamides), polyvinyl chloride, polyvinylidene chloride, acrylic resins, polystyrene resins, vinyl ester resins, polyester elastomers, polyurethane elastomers, polystyrene elastomers, halogenated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, aromatic or aliphatic polyketones, etc. These may be used alone or in combination of two or more.

[0141] Of these, hydrophobic resins such as polyamide-based resins, polyolefin-based resins, polyester-based resins, and polystyrene-based resins are preferred, and more preferred are polyolefin-based resins such as polyethylene-based resins, polypropylene-based resins, polycyclic olefin-based resins, and unsaturated carboxylic acid-modified polyolefin-based resins thereof.

[0142] The layer structure of the present multilayer structure can be any combination, such as a / b, b / a / b, a / b / a, a1 / a2 / b, a / b1 / b2, b2 / b1 / a / b1 / b2, or b2 / b1 / a / b1 / a / b1 / b2, where a represents the composition layer and b represents the base resin layer. Furthermore, when R represents a recycled layer containing a mixture of the present composition and a thermoplastic resin other than EVOH resin, obtained by remelting and molding edges or defective products generated during the production of the present multilayer structure, the layer structure can also be b / R / a, b / R / a / b, b / R / a / R / b, b / a / R / a / b, b / R / a / R / a / R / b, or b / R / a / R / a / R / b. The total number of layers in the present multilayer structure is usually 2 to 15, and preferably 3 to 10. In the above layer structure, an adhesive resin layer containing an adhesive resin may be interposed between the respective layers, if necessary.

[0143] Known adhesive resins can be used, and may be selected appropriately depending on the type of thermoplastic resin used in the base resin layer "b." Representative examples include modified polyolefin polymers containing carboxy groups, which are obtained by chemically bonding an unsaturated carboxylic acid or its anhydride to a polyolefin resin via addition reaction, graft reaction, or the like. Examples of modified polyolefin polymers containing carboxy groups include maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, maleic anhydride-grafted ethylene-propylene (block and random) copolymers, maleic anhydride-grafted ethylene-ethyl acrylate copolymers, maleic anhydride-grafted ethylene-vinyl acetate copolymers, maleic anhydride-grafted polycyclic olefin resins, and maleic anhydride-grafted polyolefin resins. These may be used alone or in combination of two or more.

[0144] In the present multilayer structure, when an adhesive resin layer is used between the present composition layer and the base resin layer, since the adhesive resin layers are located on both sides of the present composition layer, it is preferable to use an adhesive resin with excellent hydrophobicity.

[0145] The base resin and adhesive resin may contain conventionally known plasticizers, fillers, clay (montmorillonite, etc.), colorants, antioxidants, antistatic agents, lubricants, nucleating agents, antiblocking agents, waxes, etc., within a range that does not impair the spirit of the present invention (for example, usually 30% by mass or less, preferably 10% by mass or less, with the lower limit being 0% by mass, e.g., 0 to 30% by mass, based on the total resin). These may be used alone or in combination of two or more.

[0146] The lamination of the present composition layer and the above-mentioned substrate resin layer (including the case where an adhesive resin layer is interposed) can be carried out by a known method. For example, there can be mentioned a method of melt-extrusion laminating the substrate resin onto a film, sheet, etc. of the present composition (2), a method of melt-extrusion laminating the present composition (2) onto a substrate resin layer, a method of co-extruding the present composition (2) and the substrate resin, a method of dry-laminating the present composition (2) (the present composition layer) and the substrate resin (substrate resin layer) using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, a polyurethane compound, etc., a method of applying a solution of the present composition (2) onto the substrate resin and then removing the solvent, etc. Among these, in consideration of cost and environmental aspects, it is preferable to produce the layer including the present composition layer by providing a step of melt-molding the layer, and specifically, a co-extrusion method is preferable.

[0147] The multilayer structure may be subjected to a (heat) stretching treatment, if necessary. The stretching treatment may be either uniaxial stretching or biaxial stretching, and in the case of biaxial stretching, it may be simultaneous stretching or sequential stretching. Furthermore, the stretching method may be a roll stretching method, tenter stretching method, tubular stretching method, stretch-blow method, vacuum pressure forming, or the like, whichever provides a higher stretch ratio. The stretching temperature is a temperature near the melting point of the multilayer structure, and is usually selected from the range of 40 to 170°C, preferably about 60 to 160°C. When the stretching temperature is equal to or higher than the lower limit, the stretchability tends to be excellent, and when it is equal to or lower than the upper limit, a stable stretched state tends to be easily maintained.

[0148] The stretched multilayer structure may be heat-set to provide dimensional stability. Heat-setting can be performed by known means, for example, by subjecting the stretched multilayer structure to heat treatment while maintaining tension, typically at 80 to 180°C, preferably 100 to 165°C, for typically 2 to 600 seconds.

[0149] When the stretched multilayer structure is to be used as a shrink film, the heat-shrinkability can be imparted by, for example, applying cold air to the stretched multilayer structure to cool and fix it, without carrying out the heat-setting process described above.

[0150] The thickness of the present multilayer structure (including a stretched structure), as well as the thickness of the present composition layer, base resin layer, and adhesive resin layer constituting the multilayer structure, cannot be generally determined depending on the layer configuration, type of base resin, type of adhesive resin, intended use, packaging form, required physical properties, etc., but the thickness of the present multilayer structure (including a stretched structure) is usually 10 to 5,000 μm, preferably 30 to 3,000 μm, and particularly preferably 50 to 2,000 μm. The present composition layer is usually 1 to 500 μm, preferably 3 to 300 μm, and particularly preferably 5 to 200 μm; the base resin layer is usually 5 to 3,000 μm, preferably 10 to 2,000 μm, and particularly preferably 20 to 1,000 μm; and the adhesive resin layer is usually 0.5 to 250 μm, preferably 1 to 150 μm, and particularly preferably 3 to 100 μm.

[0151] Furthermore, the thickness ratio of the present composition layer to the base resin layer in the present multilayer structure (present composition layer / base resin layer), expressed as the ratio between the thickest layers when there are multiple layers of each type, is usually 1 / 99 to 50 / 50, preferably 5 / 95 to 45 / 55, and particularly preferably 10 / 90 to 40 / 60. Furthermore, the thickness ratio of the present composition layer to the adhesive resin layer in the present multilayer structure (present composition layer / adhesive resin layer), expressed as the ratio between the thickest layers when there are multiple layers of each type, is usually 10 / 90 to 99 / 1, preferably 20 / 80 to 95 / 5, and particularly preferably 50 / 50 to 90 / 10.

[0152] <Molded Article> The multilayer structure can also be used to obtain cup- or tray-shaped molded articles. In this case, a drawing method is usually used, specifically vacuum forming, pressure forming, vacuum-pressure forming, plug-assisted vacuum-pressure forming, etc. Furthermore, when a tube- or bottle-shaped multilayer container (laminate structure) is obtained from a multilayer parison (a hollow tubular preform before blowing), a blow molding method is used. Specific examples include extrusion blow molding (two-head type, mold-moving type, parison-shift type, rotary type, accumulator type, horizontal parison type, etc.), cold parison blow molding, injection blow molding, and biaxial stretch blow molding (extrusion-type cold parison biaxial stretch blow molding, injection-type cold parison biaxial stretch blow molding, injection-molding in-line biaxial stretch blow molding, etc.). The resulting laminate may be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making, deep drawing, box processing, tube processing, splitting processing, etc. as required.

[0153] <Packaging> Packaging such as a single layer film formed from the present composition (2) or a container or lid material formed from a bag, cup, tray, tube, bottle, etc. made of the present multilayer structure is useful as a variety of packaging material containers (e.g., food packaging, drug packaging, cosmetic packaging) for general foods as well as seasonings such as mayonnaise and dressing, fermented foods such as miso, oily foods such as salad oil, beverages, cosmetics, pharmaceuticals, etc.

[0154] <<Third Aspect>> The third aspect includes the following aspects [III-1] to [III-13]. [III-1] A composition containing an EVOH resin, a titanium compound, and a metal compound (B) belonging to the d block of Period 4 of the long periodic table other than a titanium compound, wherein at least a portion of the EVOH resin is derived from biomass, the content of the titanium compound in terms of metal is 0.0001 ppm or more and less than 1 ppm relative to the mass of the composition, and the mass ratio of the content of the titanium compound in terms of metal (B) belonging to the d block of Period 4 of the long periodic table to the content of the titanium compound in terms of metal is 2 to 45,000. [III-2] The composition according to [III-1], wherein the content of the titanium compound in terms of metal is 0.0001 ppm or more and 0.8 ppm or less relative to the mass of the composition. [III-3] The composition according to [III-1] or [III-2], wherein the metal compound (B) belonging to the d block of Period 4 of the long periodic table is a zinc compound. [III-4] The composition according to any one of [III-1] to [III-3], wherein the metal compound (B) belonging to the d-block of Period 4 of the Long Periodic Table is a carboxylate. [III-5] The composition according to any one of [III-1] to [III-4], wherein the EVOH resin has a biobased content of 0.01 to 99%. [III-6] The composition according to any one of [III-1] to [III-5], wherein the EVOH resin has a biobased content of 1 to 99%. [III-7] A molding material comprising the composition according to any one of [III-1] to [III-6]. [III-8] A multilayer structure having a layer comprising the composition according to any one of [III-1] to [III-6]. [III-9] The multilayer structure according to [III-8], further comprising an adhesive resin layer. [III-10] A molded article comprising the multilayer structure according to [III-8] or [III-9]. [III-11] A food packaging product comprising the multilayer structure according to [III-8] or [III-9]. [III-12] A method for producing the composition according to any one of [III-1] to [III-6], comprising a step of mixing the EVOH resin and the titanium compound.[III-13] A method for producing the multilayer structure according to [III-8] or [III-9], comprising a step of melt-molding a layer containing the composition.

[0155] The third aspect will be described below based on examples of embodiments for carrying out the third aspect, although the present invention is not limited to the following embodiments.

[0156] <Composition> The composition according to the third aspect of the present invention (hereinafter, sometimes referred to as "the composition (3)") contains an EVOH resin as an essential component, a specific trace amount of a titanium compound, and a specific mass ratio of a metal compound (B) belonging to the d block of Period 4 of the long form periodic table other than the titanium compound and a titanium compound. That is, the content of the EVOH resin in the composition (3) is usually 1 mass% or more, preferably 10 mass% or more, more preferably 50 mass% or more, even more preferably 60 mass% or more, particularly preferably 70 mass% or more, especially preferably 80 mass% or more, especially more preferably 90 mass% or more, and still more preferably 95 mass% or more. The upper limit is 100 mass%, and may be 99 mass%, for example, 1 to 100 mass%, or 10 to 99 mass%. Each component is described below.

[0157] [EVOH Resin] The EVOH resin used in this embodiment is at least partly biomass-derived, and the same EVOH resin as described in the first embodiment can be used. In addition, "the present composition (1)" in the description of the [EVOH resin] in the first embodiment can be read as "the present composition (3)."

[0158] [Titanium Compound] The titanium compound used in this embodiment may be the same as the [titanium compound] described in the first embodiment. In addition, "the present composition (1)" in the description of the [titanium compound] in the first embodiment may be read as "the present composition (3)."

[0159] [Metal Compound (B) Belonging to the 4th Period d Block of the Long Periodic Table Other than Titanium Compounds] Examples of the metal compound (excluding titanium compounds, the same applies hereinafter) belonging to the 4th Period d Block of the Long Periodic Table (hereinafter sometimes referred to as the "specific d block") used in this embodiment include scandium compounds, vanadium compounds, chromium compounds, manganese compounds, cobalt compounds, copper compounds, zinc compounds, etc. Zinc compounds are particularly preferred because they make it easier to achieve the effects of the invention.

[0160] Examples of the metal compound (B) belonging to the specific periodic d block include salts, oxides, hydroxides, etc. of the metals belonging to the specific periodic d block. Among these, oxides and salts of metals belonging to the specific periodic d block are preferred from the standpoints of economy and dispersibility. In particular, salts of metals belonging to the specific periodic d block are preferred from the standpoint of facilitating the achievement of the effects of the present invention.

[0161] Examples of the metal salt belonging to the specific periodic d-block include inorganic salts such as carbonates, hydrogencarbonates, phosphates, borates, sulfates, and chlorides, and organic salts such as carboxylates. Of these, carboxylates are particularly preferred because they can easily achieve the effects of the present invention.

[0162] As the carboxylate, saturated carboxylates are usually used in terms of commercial availability, but unsaturated carboxylates may also be used. Examples of the saturated carboxylate include monocarboxylic acid salts such as acetate, butyrate, propionate, enanthate, caprylate, caprate, laurate, palmitate, stearate, 12-hydroxystearate, behenate, and montanate, and dicarboxylic acid salts such as oxalate, malonate, succinate, adipate, suberate, and sebacate. These may be used alone or in combination of two or more. Among these, in terms of commercial availability, linear carboxylates are preferred, and monocarboxylic acid salts are more preferred, with butyrate, caproate, caprylate, caprate, laurate, and stearate being even more preferred, and caproate, caprylate, caprate, and laurate being particularly preferred.

[0163] The carboxylate salt has an anion having usually 2 to 25 carbon atoms, preferably 2 to 22 carbon atoms, more preferably 4 to 20 carbon atoms, and even more preferably 6 to 18 carbon atoms, from the viewpoint of productivity.

[0164] For these reasons, the metal compound (B) belonging to the specific periodic d block is preferably a zinc compound, more preferably a zinc carboxylate, still more preferably a zinc carboxylate having an anion with 2 to 25 carbon atoms, particularly preferably a zinc carboxylate having an anion with 2 to 22 carbon atoms, particularly preferably a zinc carboxylate having an anion with 4 to 20 carbon atoms, and even more particularly preferably a zinc carboxylate having an anion with 6 to 18 carbon atoms.

[0165] The molecular weight of the metal compound (B) belonging to the specific periodic d block is generally 100 to 10,000, from the viewpoints of dispersibility in the composition (3) and productivity, and is preferably 150 to 1,000, and more preferably 200 to 800. From the viewpoints of economy and dispersibility, it is preferable that the metal compound (B) belonging to the specific periodic d block used in this embodiment does not include layered inorganic compounds such as montmorillonite and double salts such as hydrotalcite.

[0166] The metal compound (B) belonging to the specific periodic d-block may be in any form, such as a solid (powder, fine powder, flakes, etc.), a semi-solid, a liquid, a paste, a solution, an emulsion (aqueous dispersion), etc. Among these, a powder form is preferred because of its ease of handling.

[0167] The metal compound (B) belonging to the specific periodic d block may be used alone or in combination of two or more kinds. When a plurality of types of metal compounds (B) belonging to the specific periodic d block are used, the content thereof is the total content, in terms of metal mass, of the plurality of types of metal compounds (B) belonging to the specific periodic d block.

[0168] The content of the metal compound (B) belonging to the specific periodic d block, calculated as metal mass, relative to the mass of composition (3), is usually 0.0001 to 1000 ppm, preferably 0.01 to 980 ppm, more preferably 0.05 to 940 ppm, even more preferably 0.1 to 920 ppm, particularly preferably 0.15 to 900 ppm, and especially preferably 1 to 800 ppm. When the content of the metal compound (B) belonging to the specific periodic d block is equal to or less than the upper limit, the thermal stability tends to be excellent, whereas when the content is equal to or more than the lower limit, the effects of the present invention tend to be even better.

[0169] The composition (3) that serves as the basis for the content of the metal compound (B) belonging to the specific periodic d block is the composition (3) as a final product that contains an EVOH resin, a metal compound (B) belonging to the specific periodic d block, a titanium compound, and various additives that are blended as necessary.

[0170] The content of the metal compound (B) belonging to the specific periodic d block in composition (3) in terms of metal can be determined, for example, by heating and ashing composition (3), treating the resulting solution with an acid such as hydrochloric acid, adding pure water to the resulting solution, and measuring the test solution with an atomic absorption spectrophotometer. The metal content of the metal compound (B) belonging to the specific periodic d block is the content of the metal element belonging to the specific periodic d block.

[0171] The mass ratio of the metal-equivalent content of the metal compound (B) belonging to the specific periodic d-block to the metal-equivalent content of the titanium compound is preferably 2 to 45,000, more preferably 2.2 to 40,000, even more preferably 2.5 to 30,000, particularly preferably 10 to 25,000, and especially preferably 1,000 to 20,000. When the mass ratio is equal to or less than the upper limit, coloration tends to be easily suppressed, and when the mass ratio is equal to or greater than the lower limit, the effect of suppressing thermal degradation tends to be obtained.

[0172] It is generally known that EVOH resin deteriorates due to heat. This is because EVOH resin deteriorates due to heat, generating radicals, which cause dehydration reactions in the hydroxyl groups of the EVOH resin, resulting in the formation of double bond structures in the main chain of the EVOH resin. These sites then become reaction initiation sites, which further induce dehydration reactions and the like, resulting in the formation of polyene structures in the main chain of the EVOH resin.

[0173] In contrast, the present composition (3) contains a specific trace amount of a titanium compound, which inhibits discoloration of the EVOH resin due to thermal degradation and has excellent long-run properties. Generally, when a titanium compound is added to composition (3), it is believed that titanium ions will cause discoloration of composition (3), and therefore it is common technical knowledge for a person skilled in the art to avoid the use of titanium compounds.

[0174] However, in the present embodiment, contrary to such common technical knowledge, it has been found that a composition (3) having excellent thermal stability can be obtained by using a specific trace amount of a titanium compound, the metal compound (B) belonging to the specific periodic d block, and a titanium compound in a specific mass ratio.

[0175] Titanium is stable as a tetravalent ion and stabilizes the EVOH resin by coordinating to the double bonds in the main chain and forming a chelate, which is thought to inhibit the formation of a polyene structure in the main chain of the EVOH resin. Furthermore, it is thought that the coexistence of the metal compound (B) belonging to the specific periodic d block with the titanium compound more effectively exerts the stabilizing effect of the titanium compound. On the other hand, it is thought that when the content of the titanium compound is within a specific range, deterioration of the EVOH resin due to thermal decomposition caused by the titanium compound tends to be inhibited.

[0176] [Other Thermoplastic Resins] The present composition (3) may contain a thermoplastic resin other than the EVOH resin within a range that does not impair the effects of the present invention (for example, usually 50% by mass or less of the present composition (3), preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The lower limit is 0% by mass, for example, 0 to 50% by mass). As the other thermoplastic resin, the same ones as those described in the first embodiment of the present invention as [Other Thermoplastic Resins] can be used.

[0177] [Other Compounding Agents] Composition (3) may also contain compounding agents generally compounded with EVOH resins (however, the term "compounding agent" as used herein means excluding titanium compounds and the metal compound (B) belonging to a specific periodic d-block) within a range that does not impair the effects of the present invention (for example, 5% by mass or less, preferably 3% by mass or less, with a lower limit of 0% by mass, e.g., 0 to 5% by mass). Examples of such compounding agents include inorganic double salts (e.g., hydrotalcite, etc.), plasticizers (e.g., aliphatic polyhydric alcohols such as ethylene glycol, glycerin, and hexanediol), oxygen absorbers [e.g., inorganic oxygen absorbers such as aluminum powder and potassium sulfite; ascorbic acid, its fatty acid esters and metal salts, etc.; gallic acid; polyhydric phenols such as hydroxyl group-containing phenolaldehyde resins; terpene compounds; blends of tertiary hydrogen-containing resins and transition metals (e.g., a combination of polypropylene and cobalt); blends of carbon-carbon unsaturated bond-containing resins and transition metals; Polymeric oxygen absorbers such as polymeric oxygen absorbers, such as polymeric compounds (e.g., a combination of polybutadiene and cobalt), photooxidatively degradable resins (e.g., polyketones), anthraquinone polymers (e.g., polyvinyl anthraquinone), and combinations thereof to which photoinitiators (e.g., benzophenone), antioxidants other than those mentioned above, and deodorants (e.g., activated carbon), heat stabilizers (boric acid, phosphoric acid), light stabilizers, ultraviolet absorbers, colorants, antistatic agents, surfactants (excluding those used as lubricants), antibacterial agents, antiblocking agents, and fillers (e.g., aluminum, inorganic fillers). These compounds may be used alone or in combination of two or more.

[0178] [Method for Producing Composition] The composition (3) can be produced, for example, by mixing the EVOH resin, the titanium compound, and the metal compound (B) belonging to the specific periodic d-block by a known method such as a dry blending method, a melt mixing method, a solution mixing method, an impregnation method, etc. Among these, a method including a step of mixing the EVOH resin and the titanium compound is preferred. These production methods can also be used in any combination.

[0179] The dry blending method may be, for example, (i) a method in which a pelletized EVOH resin and a titanium compound and / or a metal compound (B) belonging to a specific periodic d block are dry blended using a tumbler or the like.

[0180] Examples of the melt-mixing method include (ii) a method in which a pellet-shaped EVOH resin is dry-blended with a titanium compound and / or a metal compound (B) belonging to a specific periodic d block, and the dry-blended product is melt-kneaded; and (iii) a method in which a titanium compound and / or a metal compound (B) belonging to a specific periodic d block is added to a molten EVOH resin, and the mixture is melt-kneaded.

[0181] Examples of the solution mixing method include (iv) a method in which a solution is prepared using a commercially available EVOH resin, a titanium compound and / or a metal compound (B) belonging to a specific periodic d block is blended therein, the mixture is solidified and molded, and then the mixture is subjected to solid-liquid separation by known means and dried; and (v) a method in which a titanium compound and / or a metal compound (B) belonging to a specific periodic d block is added to an ethylene-vinyl ester copolymer solution before saponification or a homogeneous solution of EVOH resin (e.g., a water / alcohol solution), the mixture is solidified and molded, and then the mixture is subjected to solid-liquid separation by known means and dried during the production of EVOH resin.

[0182] The impregnation method includes, for example, (vi) a method in which pellets of EVOH resin are contacted with an aqueous solution containing a titanium compound and / or a metal compound (B) belonging to a specific periodic d block to incorporate the titanium compound and / or the metal compound (B) belonging to a specific periodic d block into the EVOH resin, followed by drying. The aqueous solution containing the titanium compound may be an aqueous solution of a titanium compound or a titanium compound immersed in water containing various chemicals to elute titanium ions.

[0183] In the impregnation method, the content of the titanium compound (in terms of metal) can be controlled by the concentration of the titanium compound in the aqueous solution in which the EVOH resin is immersed, the immersion temperature, the immersion time, etc. The immersion temperature and the immersion time are usually 0.5 to 48 hours, preferably 1 to 36 hours, and the immersion temperature is usually 10 to 40°C, preferably 20 to 35°C.

[0184] As the drying method in each of the above-mentioned production methods, various drying methods can be used, and either static drying or fluidized drying may be used, or these may be used in combination.

[0185] As described above, in this embodiment, the above-mentioned different methods can be combined. Among them, the melt mixing method is preferred, and method (ii) is particularly preferred, in terms of productivity and the fact that a resin composition with more pronounced effects of the present invention can be obtained. Furthermore, when using the other thermoplastic resins and other compounding agents, they may be compounded by a conventional method according to the above-mentioned manufacturing method.

[0186] The shape of the present composition (3) obtained by each of the above-mentioned production methods may be any shape, but is preferably pellets. The pellets may be, for example, spherical, oval, cylindrical, die-shaped, or rectangular, but are typically oval or cylindrical. From the viewpoint of convenience when subsequently used as a molding material, the size of the pellets is such that, in the case of an oval shape, the minor axis is typically 1 to 10 mm, preferably 2 to 6 mm, and more preferably 2.5 to 5.5 mm, and the major axis is typically 1.5 to 30 mm, preferably 3 to 20 mm, and more preferably 3.5 to 10 mm. In the case of a cylindrical shape, the base diameter is typically 1 to 6 mm, preferably 2 to 5 mm, and the length is typically 1 to 6 mm, preferably 2 to 5 mm. In the case of a die-shaped shape, one side is typically 1 to 6 mm, preferably 2 to 5 mm. The shape and size of the pelletized EVOH resin used in each of the above-mentioned production methods are also preferably similar.

[0187] The water content of the composition (3) is not particularly limited, but is usually 0.01 to 0.5% by mass, preferably 0.05 to 0.35% by mass, and particularly preferably 0.1 to 0.3% by mass.

[0188] The water content of the composition (3) is measured and calculated by the following method. １ ) was weighed on an electronic balance, dried in a hot air dryer at 150°C for 5 hours, and allowed to cool in a desiccator for 30 minutes, after which the mass (W ２ ) is weighed and calculated using the following formula: [Formula] Water content (mass%) = [(W １ -W ２ ) / W １ ]×100

[0189] When the composition (3) is in the form of pellets, it is also preferable to apply a known lubricant to the surface of the pellets in order to stabilize the feedability during melt molding. Examples of lubricants include higher fatty acids having 12 or more carbon atoms (e.g., lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc.), higher fatty acid esters (methyl esters, isopropyl esters, butyl esters, octyl esters of higher fatty acids, etc.), higher fatty acid amides (e.g., saturated higher fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, etc.; unsaturated higher fatty acid amides such as oleic acid amide, erucic acid amide, etc.; bis-higher fatty acid amides such as ethylene bisstearic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, ethylene bislauric acid amide, etc.), low-molecular-weight polyolefins (e.g., low-molecular-weight polyethylene or low-molecular-weight polypropylene having a molecular weight of about 500 to 10,000, or acid-modified products thereof), higher alcohols having 6 or more carbon atoms, ester oligomers, and fluorinated ethylene resins. These compounds can be used alone or in combination of two or more. The content of such lubricants is usually 5% by mass or less, preferably 1% by mass or less, of the composition (3). The lower limit is usually 0% by mass, for example, 0 to 5% by mass.

[0190] The composition (3) thus obtained has excellent thermal stability. When the composition (3) is measured using a visual analyzer IRIS VA400 (manufactured by Alphamos), the ratio of the sum of color numbers "1347" (R: 88, G: 72, B: 56), "1348" (R: 88, G: 72, B: 72), and "1349" (R: 88, G: 72, B: 88) to the sum of color numbers "1381" (R: 88, G: 104, B: 88) and "1382" (R: 88, G: 104, B: 104), i.e., ("1347" + "1348" + "1349") / ("1381" + "1382"), is usually 4 or less, preferably 3 or less, and more preferably 2 or less. The lower limit is usually 0, for example, usually 0 to 4. The smaller the ratio, the more suppressed is the coloration due to thermal degradation, and the thermal stability tends to be higher. Note that a difference of 1 in the ratio results in a large difference in yield in actual production, and therefore the difference is very large.

[0191] <Molding Material> The present composition (3) thus obtained is prepared into various forms, such as pellets, powder, or liquid, and provided as a molding material for various molded products. In particular, in this embodiment, when it is provided as a material for melt molding, the effects of the present invention tend to be more efficiently obtained, which is preferable. Examples of the molded product include a monolayer film molded from the present composition (3), as well as a multilayer structure having a layer made of the present composition (3).

[0192] <Multilayer structure> The multilayer structure according to the third aspect of the present invention (hereinafter referred to as "the present multilayer structure (3)") contains the present composition (3) and has at least one layer made of the present composition (3). The layer made of the present composition (3) in the present multilayer structure (3) (hereinafter simply referred to as "the present composition layer (3)") may be a single layer or multiple layers. Furthermore, the present composition layer (3) can be laminated with another substrate (hereinafter, the resin used for the substrate may be abbreviated as "substrate resin") containing a thermoplastic resin other than EVOH resin as a main component to impart further strength, protect the present composition layer (3) from the effects of moisture, etc., or impart other functions. Examples of the base resin include polyethylene-based resins such as linear low-density polyethylene, low-density polyethylene, very low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-propylene (block and random) copolymers, and ethylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymers; polypropylene-based resins such as polypropylene and propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymers; (unmodified) polyolefin-based resins such as polybutene, polypentene, and polycyclic olefin-based resins (polymers having a cyclic olefin structure in at least one of the main chain and side chain); and polyolefins obtained by dissolving these polyolefins in an unsaturated carboxylic acid or Examples include polyolefin resins in the broad sense, including modified olefin resins such as unsaturated carboxylic acid-modified polyolefin resins graft-modified with an ester thereof, ionomers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, polyester resins, polyamide resins (including copolymerized polyamides), polyvinyl chloride, polyvinylidene chloride, acrylic resins, polystyrene resins, vinyl ester resins, polyester elastomers, polyurethane elastomers, polystyrene elastomers, halogenated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, aromatic or aliphatic polyketones, etc. These may be used alone or in combination of two or more.

[0193] Of these, hydrophobic resins such as polyamide-based resins, polyolefin-based resins, polyester-based resins, and polystyrene-based resins are preferred, and more preferred are polyolefin-based resins such as polyethylene-based resins, polypropylene-based resins, polycyclic olefin-based resins, and unsaturated carboxylic acid-modified polyolefin-based resins thereof.

[0194] The layer structure of the multilayer structure (3) can be any combination, such as a / b, b / a / b, a / b / a, a1 / a2 / b, a / b1 / b2, b2 / b1 / a / b1 / b2, or b2 / b1 / a / b1 / a / b1 / b2, where a denotes the composition layer (3) and b denotes the base resin layer (b1, b2, etc.). Furthermore, when R denotes a recycled layer containing a mixture of the composition (3) and a thermoplastic resin other than EVOH resin, obtained by remelting and molding edges or defective products generated during the manufacturing process of the multilayer structure (3), b / R / a, b / R / a / b, b / R / a / R / b, b / a / R / a / b, b / R / a / R / a / R / b, or b / R / a / R / a / R / b, etc. The total number of layers in the multilayer structure (3) is usually 2 to 15, and preferably 3 to 10. In the above layer structure, an adhesive resin layer containing an adhesive resin may be interposed between the respective layers, if necessary.

[0195] Known adhesive resins can be used, and may be selected appropriately depending on the type of thermoplastic resin used in the base resin layer "b." Representative examples include modified polyolefin polymers containing carboxy groups, which are obtained by chemically bonding an unsaturated carboxylic acid or its anhydride to a polyolefin resin via addition reaction, graft reaction, or the like. Examples of modified polyolefin polymers containing carboxy groups include maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, maleic anhydride-grafted ethylene-propylene (block and random) copolymers, maleic anhydride-grafted ethylene-ethyl acrylate copolymers, maleic anhydride-grafted ethylene-vinyl acetate copolymers, maleic anhydride-grafted polycyclic olefin resins, and maleic anhydride-grafted polyolefin resins. These may be used alone or in combination of two or more.

[0196] In the present multilayer structure (3), when an adhesive resin layer is used between the present composition layer (3) and the base resin layer, it is preferable to use an adhesive resin with excellent hydrophobicity, since the adhesive resin layers are located on both sides of the present composition layer (3).

[0197] The base resin and adhesive resin may contain conventionally known plasticizers, fillers, clay (montmorillonite, etc.), colorants, antioxidants, antistatic agents, lubricants, nucleating agents, antiblocking agents, waxes, etc., within a range that does not impair the spirit of the present invention (for example, usually 30% by mass or less, preferably 10% by mass or less, with the lower limit being 0% by mass, e.g., 0 to 30% by mass, based on the total resin). These may be used alone or in combination of two or more.

[0198] The lamination of the present composition layer (3) and the above-mentioned base resin layer (including the case where an adhesive resin layer is interposed) can be carried out by a known method. For example, there can be mentioned a method of melt-extrusion laminating the base resin onto a film, sheet, etc. of the present composition (3), a method of melt-extrusion laminating the present composition (3) onto a base resin layer, a method of co-extruding the present composition (3) and the base resin, a method of dry-laminating the present composition (3) (the present composition layer (3)) and the base resin (base resin layer) using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, a polyurethane compound, etc., a method of applying a solution of the present composition (3) onto the base resin and then removing the solvent, etc. Among these, in consideration of cost and environmental considerations, it is preferable to produce the layer including the present composition layer (3) by a step of melt-molding it, and specifically, a co-extrusion method is preferred.

[0199] The multilayer structure (3) may be subjected to a (heat) stretching treatment, if necessary. The stretching treatment may be either uniaxial stretching or biaxial stretching, and in the case of biaxial stretching, it may be simultaneous stretching or sequential stretching. Furthermore, the stretching method may be a roll stretching method, tenter stretching method, tubular stretching method, stretch-blow method, vacuum pressure forming, or the like, whichever provides a higher stretch ratio. The stretching temperature is a temperature near the melting point of the multilayer structure (3), and is usually selected from the range of 40 to 170°C, preferably about 60 to 160°C. When the stretching temperature is equal to or higher than the lower limit, the stretchability tends to be excellent, and when the stretching temperature is equal to or lower than the upper limit, a stable stretched state tends to be easily maintained.

[0200] The stretched multilayer structure (3) may be heat-set to provide dimensional stability. Heat-setting can be performed by known means, for example, by subjecting the stretched multilayer structure (3) to heat treatment while maintaining tension, typically at 80 to 180°C, preferably 100 to 165°C, for typically 2 to 600 seconds.

[0201] When the stretched multilayer structure (3) is used as a shrink film, in order to impart heat shrinkability, the above-mentioned heat setting is not carried out, but rather a treatment such as cooling and setting the stretched multilayer structure (3) by applying cold air thereto may be carried out.

[0202] The thickness of the present multilayer structure (3) (including a stretched one), as well as the thickness of the present composition layer (3), base resin layer, and adhesive resin layer constituting the multilayer structure (3), cannot be generally determined depending on the layer configuration, type of base resin, type of adhesive resin, intended use, packaging form, required physical properties, etc., but the thickness of the present multilayer structure (3) (including a stretched one) is usually 10 to 5,000 μm, preferably 30 to 3,000 μm, and particularly preferably 50 to 2,000 μm. The present composition layer (3) is usually 1 to 500 μm, preferably 3 to 300 μm, and particularly preferably 5 to 200 μm; the base resin layer is usually 5 to 3,000 μm, preferably 10 to 2,000 μm, and particularly preferably 20 to 1,000 μm; and the adhesive resin layer is usually 0.5 to 250 μm, preferably 1 to 150 μm, and particularly preferably 3 to 100 μm.

[0203] Furthermore, the thickness ratio of the present composition layer (3) to the base resin layer in the present multilayer structure (3) (present composition layer (3) / base resin layer), expressed as the ratio between the thickest layers when there are multiple layers of each, is usually 1 / 99 to 50 / 50, preferably 5 / 95 to 45 / 55, and particularly preferably 10 / 90 to 40 / 60. Furthermore, the thickness ratio of the present composition layer (3) to the adhesive resin layer in the present multilayer structure (3) (present composition layer (3) / adhesive resin layer), expressed as the ratio between the thickest layers when there are multiple layers of each, is usually 10 / 90 to 99 / 1, preferably 20 / 80 to 95 / 5, and particularly preferably 50 / 50 to 90 / 10.

[0204] <Molded Article> It is also possible to obtain a cup- or tray-shaped molded article using the present multilayer structure (3). In this case, a drawing method is usually employed, specifically vacuum forming, pressure forming, vacuum-pressure forming, plug-assisted vacuum-pressure forming, etc. Furthermore, when a tube- or bottle-shaped multilayer container (laminate structure) is obtained from a multilayer parison (a hollow tubular preform before blowing), a blow molding method is employed. Specific examples include extrusion blow molding (two-head type, mold-moving type, parison-shift type, rotary type, accumulator type, horizontal parison type, etc.), cold parison blow molding, injection blow molding, and biaxial stretch blow molding (extrusion-type cold parison biaxial stretch blow molding, injection-type cold parison biaxial stretch blow molding, injection-molding in-line biaxial stretch blow molding, etc.). The resulting laminate may be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making, deep drawing, box processing, tube processing, splitting processing, etc. as required.

[0205] <Packaging> Packaging such as a single layer film formed from the present composition (3) or a container or lid material formed from a bag, cup, tray, tube, bottle, etc., made from the present multilayer structure (3) is useful as a variety of packaging material containers (e.g., food packaging, drug packaging, cosmetic packaging) for general foods as well as seasonings such as mayonnaise and dressing, fermented foods such as miso, oily foods such as salad oil, beverages, cosmetics, pharmaceuticals, etc.

[0206] <<Fourth Aspect>> The present invention includes the following aspects [IV-1] to [IV-11]. [IV-1] A composition containing an EVOH resin, a titanium compound, and a lubricant (C), wherein at least a portion of the EVOH resin is derived from biomass, the content of the titanium compound in terms of metal is 0.0001 ppm or more and less than 1 ppm relative to the mass of the composition, and the mass ratio of the content of the lubricant (C) to the content of the titanium compound in terms of metal is 500 to 280,000. [IV-2] The composition according to [IV-1], wherein the content of the titanium compound in terms of metal is 0.0001 ppm or more and 0.8 ppm or less relative to the mass of the composition. [IV-3] The composition according to [IV-1] or [IV-2], wherein the EVOH resin has a biobased content of 0.01 to 99%. [IV-4] The composition according to any one of [IV-1] to [IV-3], wherein the EVOH resin has a biobased content of 1 to 99%. [IV-5] A molding material comprising the composition according to any one of [IV-1] to [IV-4]. [IV-6] A multilayer structure having a layer comprising the composition according to any one of [IV-1] to [IV-4]. [IV-7] The multilayer structure according to [IV-6], further comprising an adhesive resin layer. [IV-8] A molded article comprising the multilayer structure according to [IV-6] or [IV-7]. [IV-9] A food package comprising the multilayer structure according to [IV-6] or [IV-7]. [IV-10] A method for producing the composition according to any one of [IV-1] to [IV-4], comprising a step of mixing the EVOH resin and the titanium compound. [IV-11] A method for producing the multilayer structure according to [IV-6] or [IV-7], comprising a step of melt-molding a layer comprising the composition.

[0207] The fourth aspect will be described below based on examples of embodiments for carrying out the fourth aspect, although the present invention is not limited to the following embodiments.

[0208] <Composition> The composition according to the fourth aspect of the present invention (hereinafter, sometimes referred to as "the composition (4)") contains an EVOH resin as an essential component, a specific trace amount of a titanium compound, and the lubricant (C) and the titanium compound in a specific mass ratio. That is, the content of the EVOH resin in the composition (4) is usually 1 mass% or more, preferably 10 mass% or more, more preferably 50 mass% or more, even more preferably 60 mass% or more, particularly preferably 70 mass% or more, especially preferably 80 mass% or more, especially more preferably 90 mass% or more, and still more preferably 95 mass% or more. The upper limit is 100 mass%, and may be 99 mass%, for example, 1 to 100 mass%, or 10 to 99 mass%. Each component will be described below.

[0209] [EVOH Resin] The EVOH resin used in this embodiment is at least partly biomass-derived, and the same EVOH resin as described in the first embodiment can be used. In addition, "the present composition (1)" in the description of the [EVOH resin] in the first embodiment can be read as "the present composition (4)."

[0210] [Titanium Compound] The titanium compound used in this embodiment may be the same as the [titanium compound] described in the first embodiment. In addition, "composition (1)" in the description of the [titanium compound] in the first embodiment may be read as "composition (4)."

[0211] [Lubricant (C)] Examples of the lubricant (C) include higher fatty acids having 12 to 25 carbon atoms, preferably higher fatty acids having 13 to 23 carbon atoms, and more preferably higher fatty acids having 15 to 20 carbon atoms. Examples of the higher fatty acids include higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid; metal salts of higher fatty acids such as aluminum salts, calcium salts, zinc salts, magnesium salts, and barium salts of these higher fatty acids; esters of higher fatty acids such as methyl esters, isopropyl esters, butyl esters, and octyl esters of the above higher fatty acids; saturated higher fatty acid amides such as stearamide and behenic acid amide; unsaturated higher fatty acid amides such as oleamide and erucamide; and amides of higher fatty acids such as bis-higher fatty acid amides such as ethylene bisstearamide, ethylene bisoleamide, ethylene biserucamide, and ethylene bislauamide. Examples of lubricants (C) other than the higher fatty acids include low-molecular-weight polyethylene and low-molecular-weight polypropylene having a molecular weight of about 500 to 10,000 (preferably less than 10,000, more preferably 9,000 or less), low-molecular-weight polyolefins such as acid-modified products thereof, higher alcohols, ester oligomers, fluorinated ethylene resins, etc. These lubricants (C) can be used alone or in combination of two or more kinds.

[0212] From the viewpoint of extrusion stability and commercial availability, the valence of the higher fatty acids is usually 1 to 5, preferably 1 to 3, and more preferably 1 to 2. The valence refers to the number of structures derived from higher fatty acids contained in one molecule of the compound used in the lubricant (C), and for example, when bisstearic acid amide is used as the lubricant (C), it has two structures derived from a higher fatty acid molecule having 18 carbon atoms in one molecule, and therefore is an amide of a higher fatty acid having 18 carbon atoms, and the valence of the higher fatty acid is considered to be 2.

[0213] Among the lubricants (C), preferred are higher fatty acids, metal salts of higher fatty acids, esters of higher fatty acids, and amides of higher fatty acids, more preferred are metal salts of higher fatty acids and amides of higher fatty acids, and from the viewpoint of extrusion stability, even more preferred are amides of higher fatty acids, and particularly preferred is ethylene bisstearamide.

[0214] The lubricant (C) may be in any form, such as a solid (powder, fine powder, flakes, etc.), semi-solid, liquid, paste, solution, or emulsion (aqueous dispersion). Powder form is preferred. The particle size of the powdered lubricant (C) is usually 0.1 to 100 μm, preferably 1 to 75 μm, and more preferably 5 to 50 μm.

[0215] The content of the lubricant (C) is preferably 10,000 ppm or less, more preferably 9,500 ppm or less, even more preferably 9,000 ppm or less, particularly preferably 8,500 ppm or less, and most preferably 100 ppm or less, relative to the mass of the composition (4). When the content of the lubricant (C) is equal to or less than the upper limit, the composition tends to have excellent thermal stability. The lower limit of the content of the lubricant (C) is usually 1 ppm, preferably 10 ppm or more, more preferably 30 ppm or more, and even more preferably 50 ppm or more, and the range is, for example, usually 1 to 10,000 ppm. When the content of the lubricant (C) is equal to or more than the lower limit, the composition (4) tends to have excellent moldability.

[0216] The content of the lubricant (C) can be measured, for example, by the following method. When the lubricant (C) is attached to the surface of the EVOH resin, the amount of the lubricant (C) added can be considered as the content. When the lubricant (C) is contained in the present composition (4), if the lubricant (C) is, for example, a higher fatty acid amide, the total amount of nitrogen in the present composition (4) can be measured using a total nitrogen trace analyzer and converted into the lubricant (C) content, thereby measuring the content of the lubricant (C) in the present composition (4).

[0217] The mass ratio of the content of the lubricant (C) to the content of the titanium compound in terms of metal [content of lubricant (C) / content of titanium compound in terms of metal] is usually 500 to 280,000, preferably 600 to 250,000, more preferably 800 to 230,000, and particularly preferably 1,000 to 200,000. When this value is equal to or less than the upper limit, coloration tends to be easily suppressed, and when it is equal to or greater than the lower limit, the effect of suppressing thermal degradation tends to be obtained.

[0218] It is generally known that EVOH resins become discolored due to thermal degradation. This is thought to be because EVOH resins deteriorate due to heat, generating radicals, which cause dehydration reactions in the hydroxyl groups of the EVOH resin, resulting in the formation of double bond structures in the main chain of the EVOH resin. These sites then become reaction initiation sites, which further induce dehydration reactions and the like, resulting in the formation of polyene structures in the main chain of the EVOH resin.

[0219] In contrast, the present composition (4) contains a specific trace amount of a titanium compound, which suppresses discoloration of the EVOH resin due to thermal degradation and has excellent long-run properties. Normally, when a titanium compound is contained in composition (4), it is thought that titanium ions will cause discoloration of composition (4), and therefore it is common technical knowledge for a person skilled in the art to avoid using a titanium compound.

[0220] However, in the present embodiment, contrary to such common technical knowledge, it has been found that a composition (4) in which color change due to thermal degradation is suppressed can be obtained when the composition contains a specific trace amount of a titanium compound and a lubricant (C) and further when these two types are used in a specific mass ratio.

[0221] Titanium is stable as a tetravalent ion and stabilizes the EVOH resin by coordinating to the double bonds in the main chain and forming a chelate, which is thought to inhibit the formation of a polyene structure in the main chain of the EVOH resin. Furthermore, the coexistence of lubricant (C) with the titanium compound is thought to inhibit the reaction between lubricant (C) and composition (4), thereby suppressing the tendency for thickening and improving thermal stability. On the other hand, it is thought that when the content of the titanium compound is within a specific range, deterioration of the EVOH resin due to thermal decomposition caused by the titanium compound can be inhibited.

[0222] [Other Thermoplastic Resins] The present composition (4) may contain a thermoplastic resin other than the EVOH resin within a range that does not impair the effects of the present invention (for example, usually 50% by mass or less of the present composition (4), preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The lower limit is 0% by mass, for example, 0 to 50% by mass). As the other thermoplastic resin, the same ones as those described in the first embodiment of the present invention as [Other Thermoplastic Resins] can be used.

[0223] [Other Compounding Agents] Composition (4) may also contain compounding agents generally compounded with EVOH resins (however, the term "compounding agent" as used herein means excluding titanium compounds and lubricant (C)) within a range that does not impair the effects of the present invention (for example, 5% by mass or less, preferably 3% by mass or less, with a lower limit of 0% by mass, e.g., 0 to 5% by mass). Examples of the compounding agents include inorganic double salts (e.g., hydrotalcite, etc.), plasticizers (e.g., aliphatic polyhydric alcohols such as ethylene glycol, glycerin, and hexanediol, excluding those used as lubricant (C)), oxygen absorbers [e.g., inorganic oxygen absorbers such as aluminum powder and potassium sulfite; ascorbic acid, its fatty acid esters and metal salts, etc. (excluding those used as lubricant (C))], gallic acid, polyhydric phenols such as hydroxyl group-containing phenolaldehyde resins, terpene compounds, blends of tertiary hydrogen-containing resins and transition metals (e.g., a combination of polypropylene and cobalt), carbon-carbon Polymeric oxygen absorbers such as blends of unsaturated bond-containing resins and transition metals (e.g., a combination of polybutadiene and cobalt), photooxidatively degradable resins (e.g., polyketones), anthraquinone polymers (e.g., polyvinyl anthraquinone), and combinations thereof to which photoinitiators (e.g., benzophenone) or antioxidants or deodorizers (e.g., activated carbon) other than those mentioned above may also be added, heat stabilizers (boric acid, phosphoric acid), light stabilizers, ultraviolet absorbers, colorants, antistatic agents, surfactants (excluding those used as lubricants (C)), antibacterial agents, antiblocking agents, fillers (e.g., aluminum, inorganic fillers), etc. These compounds may be used alone or in combination of two or more.

[0224] [Method for Producing Composition] The composition (4) can be produced, for example, by mixing the EVOH resin, titanium compound, and lubricant (C) by a known method such as a dry blending method, a melt mixing method, a solution mixing method, an impregnation method, etc. Among these, a method including a step of mixing the EVOH resin and the titanium compound is preferred. These production methods can also be used in any combination.

[0225] The dry blending method may be, for example, (i) a method in which pelletized EVOH resin and a titanium compound and / or a lubricant (C) are dry blended using a tumbler or the like.

[0226] Examples of the melt-mixing method include (ii) a method in which a pellet-shaped EVOH resin is dry-blended with a titanium compound and / or a lubricant (C), and the resulting dry blend is melt-kneaded; and (iii) a method in which a titanium compound and / or a lubricant (C) is added to a molten EVOH resin, and the resulting mixture is melt-kneaded.

[0227] Examples of the solution mixing method include (iv) a method in which a solution is prepared using a commercially available EVOH resin, a titanium compound and / or a lubricant (C) is blended therein, the mixture is coagulated and molded, and then the mixture is subjected to solid-liquid separation by known means and dried; and (v) a method in which a titanium compound and / or a lubricant (C) is added to an ethylene-vinyl ester copolymer solution before saponification or a homogeneous solution of EVOH resin (such as a water / alcohol solution) during the production of EVOH resin, the mixture is coagulated and molded, and then the mixture is subjected to solid-liquid separation by known means and dried.

[0228] The impregnation method includes, for example, (vi) a method in which pellets of EVOH resin are brought into contact with an aqueous solution containing a titanium compound and / or a lubricant (C) to incorporate the titanium compound and / or the lubricant (C) into the EVOH resin, followed by drying. The aqueous solution containing a titanium compound may be an aqueous solution of a titanium compound or a titanium compound immersed in water containing various chemicals to elute titanium ions.

[0229] In the impregnation method, the content of the titanium compound (in terms of metal) can be controlled by the concentration of the titanium compound in the aqueous solution in which the EVOH resin is immersed, the immersion temperature, the immersion time, etc. The immersion temperature and the immersion time are usually 0.5 to 48 hours, preferably 1 to 36 hours, and the immersion temperature is usually 10 to 40°C, preferably 20 to 35°C.

[0230] As the drying method in each of the above-mentioned production methods, various drying methods can be used, and either static drying or fluidized drying may be used, or these may be used in combination.

[0231] As described above, in this embodiment, the above-mentioned different methods can be combined. Among them, the melt mixing method is preferred, and method (ii) is particularly preferred, in terms of productivity and the fact that a resin composition with more pronounced effects of the present invention can be obtained. Furthermore, when using the other thermoplastic resins and other compounding agents, they may be compounded by a conventional method according to the above-mentioned manufacturing method.

[0232] The shape of the present composition (4) obtained by each of the above-mentioned production methods may be any shape, but is preferably pellets. The pellets may be, for example, spherical, oval, cylindrical, die-shaped, or rectangular. They are typically oval or cylindrical. From the viewpoint of convenience when subsequently used as a molding material, the size of the pellets is such that, in the case of an oval shape, the minor axis is typically 1 to 10 mm, preferably 2 to 6 mm, and more preferably 2.5 to 5.5 mm, and the major axis is typically 1.5 to 30 mm, preferably 3 to 20 mm, and more preferably 3.5 to 10 mm. In the case of a cylindrical shape, the diameter of the base is typically 1 to 6 mm, preferably 2 to 5 mm, and the length is typically 1 to 6 mm, preferably 2 to 5 mm. In the case of a die-shaped shape, the length of one side is typically 1 to 6 mm, preferably 2 to 5 mm. The shape and size of the pelletized EVOH resin used in each of the above-mentioned production methods are also preferably similar.

[0233] The water content of the composition (4) is not particularly limited, but is usually 0.01 to 0.5% by mass, preferably 0.05 to 0.35% by mass, and particularly preferably 0.1 to 0.3% by mass.

[0234] The water content of the composition (4) is measured and calculated by the following method. １ ) was weighed on an electronic balance, dried in a hot air dryer at 150°C for 5 hours, and allowed to cool in a desiccator for 30 minutes, after which the mass (W ２ ) is weighed and calculated using the following formula: [Formula] Water content (mass%) = [(W１ -W ２ ) / W １ ]×100

[0235] When the composition (4) is in the form of pellets, it is also preferable to apply a known lubricant (C) to the surface of the pellets in order to stabilize the feedability during melt molding. Examples of the lubricant (C) include higher fatty acids having 12 or more carbon atoms (e.g., lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc.), higher fatty acid esters (methyl esters, isopropyl esters, butyl esters, octyl esters of higher fatty acids, etc.), higher fatty acid amides (e.g., saturated higher fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, and behenic acid amide; unsaturated higher fatty acid amides such as oleic acid amide and erucic acid amide; bis-higher fatty acid amides such as ethylene bisstearic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, and ethylene bislauric acid amide), low-molecular-weight polyolefins (e.g., low-molecular-weight polyethylene or low-molecular-weight polypropylene having a molecular weight of about 500 to 10,000, or acid-modified products thereof), higher alcohols having 6 or more carbon atoms, ester oligomers, and fluorinated ethylene resins. These compounds can be used alone or in combination of two or more. The content of the lubricant (C) is usually 5% by mass or less, preferably 1% by mass or less, of the composition (4). The lower limit is usually 0% by mass, for example, 0 to 5% by mass.

[0236] The composition (4) thus obtained has excellent thermal stability, and the composition (4) was analyzed by a visual analyzer IRIS VA400 (Alpha). The ratio ("1363" + "1364" + "1365") / ("1636" + "1637" + "1638") of the sum of color numbers "1363" (R: 88, G: 88, B: 56), "1364" (R: 88, G: 88, B: 72), and "1365" (R: 88, G: 88, B: 88) to the sum of color numbers "1636" (R: 104, G: 104, B: 72), "1637" (R: 104, G: 104, B: 88), and "1638" (R: 104, G: 104, B: 104) measured using a color temperature chart measurement system manufactured by MOS Co., Ltd., is usually 1.8 or less, preferably 1.4 or less, and more preferably 1 or less. The lower limit is usually 0, for example, usually 0 to 1.8. The smaller the ratio, the more suppressed is the coloration due to thermal degradation, and the thermal stability tends to be higher. Note that a difference of 0.05 in the ratio is very significant, as it appears as a large difference in yield in actual production.

[0237] <Molding material> The present composition (4) thus obtained is prepared into various forms such as pellets, powder, or liquid, and is provided as a molding material for various molded products. In particular, in this embodiment, when it is provided as a material for melt molding, the effects of the present invention tend to be more efficiently obtained, which is preferable.

[0238] Examples of the molded article include a monolayer film molded from the present composition (4), as well as a multilayer structure having a layer made of the present composition (4).

[0239] <Multilayer structure> The multilayer structure according to the fourth aspect of the present invention (hereinafter referred to as "the present multilayer structure (4)") contains the present composition (4) and has at least one layer made of the present composition (4). The layer made of the present composition (4) in the present multilayer structure (4) (hereinafter simply referred to as "the present composition layer (4)") may be a single layer or multiple layers. Furthermore, the present composition layer (4) can be laminated with another substrate (hereinafter, the resin used for the substrate may be abbreviated as "substrate resin") containing a thermoplastic resin other than EVOH resin as a main component to impart further strength, protect the present composition layer (4) from the effects of moisture, etc., or impart other functions.

[0240] Examples of the base resin include polyethylene-based resins such as linear low-density polyethylene, low-density polyethylene, very low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-propylene (block and random) copolymers, and ethylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymers; polypropylene-based resins such as polypropylene and propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymers; (unmodified) polyolefin-based resins such as polybutene, polypentene, and polycyclic olefin-based resins (polymers having a cyclic olefin structure in at least one of the main chain and side chain); and polyolefins obtained by dissolving these polyolefins in an unsaturated carboxylic acid or Examples include polyolefin resins in the broad sense, including modified olefin resins such as unsaturated carboxylic acid-modified polyolefin resins graft-modified with an ester thereof, ionomers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, polyester resins, polyamide resins (including copolymerized polyamides), polyvinyl chloride, polyvinylidene chloride, acrylic resins, polystyrene resins, vinyl ester resins, polyester elastomers, polyurethane elastomers, polystyrene elastomers, halogenated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, aromatic or aliphatic polyketones, etc. These may be used alone or in combination of two or more.

[0241] Of these, hydrophobic resins such as polyamide-based resins, polyolefin-based resins, polyester-based resins, and polystyrene-based resins are preferred, and more preferred are polyolefin-based resins such as polyethylene-based resins, polypropylene-based resins, polycyclic olefin-based resins, and unsaturated carboxylic acid-modified polyolefin-based resins thereof.

[0242] The layer structure of the multilayer structure (4) can be any combination, such as a / b, b / a / b, a / b / a, a1 / a2 / b, a / b1 / b2, b2 / b1 / a / b1 / b2, or b2 / b1 / a / b1 / a / b1 / b2, where a denotes the composition layer (4) and b denotes the base resin layer (b1, b2, etc.). Furthermore, when R denotes a recycled layer containing a mixture of the composition (4) and a thermoplastic resin other than EVOH resin, obtained by remelting and molding edges or defective products generated during the manufacturing process of the multilayer structure (4), b / R / a, b / R / a / b, b / R / a / R / b, b / a / R / a / b, b / R / a / R / a / R / b, or b / R / a / R / a / R / b, etc. The total number of layers in the multilayer structure (4) is usually 2 to 15, preferably 3 to 10. In the above layer structure, an adhesive resin layer containing an adhesive resin may be interposed between the respective layers, if necessary.

[0243] Known adhesive resins can be used, and may be selected appropriately depending on the type of thermoplastic resin used in the base resin layer "b." Representative examples include modified polyolefin polymers containing carboxy groups, which are obtained by chemically bonding an unsaturated carboxylic acid or its anhydride to a polyolefin resin via addition reaction, graft reaction, or the like. Examples of modified polyolefin polymers containing carboxy groups include maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, maleic anhydride-grafted ethylene-propylene (block and random) copolymers, maleic anhydride-grafted ethylene-ethyl acrylate copolymers, maleic anhydride-grafted ethylene-vinyl acetate copolymers, maleic anhydride-grafted polycyclic olefin resins, and maleic anhydride-grafted polyolefin resins. These may be used alone or in combination of two or more.

[0244] In the present multilayer structure (4), when an adhesive resin layer is used between the present composition layer (4) and the base resin layer, since the adhesive resin layers are located on both sides of the present composition layer (4), it is preferable to use an adhesive resin with excellent hydrophobicity.

[0245] The base resin and adhesive resin may contain conventionally known plasticizers, fillers, clay (montmorillonite, etc.), colorants, antioxidants, antistatic agents, lubricants, nucleating agents, antiblocking agents, waxes, etc., within a range that does not impair the spirit of the present invention (for example, usually 30% by mass or less, preferably 10% by mass or less, with the lower limit being 0% by mass, e.g., 0 to 30% by mass, based on the total resin). These may be used alone or in combination of two or more.

[0246] The lamination of the composition layer (4) and the substrate resin layer (including the case where an adhesive resin layer is interposed) can be carried out by a known method. For example, there can be mentioned a method of melt-extrusion laminating the substrate resin onto a film, sheet, etc. of the composition (4), a method of melt-extrusion laminating the composition (4) onto a substrate resin layer, a method of co-extruding the composition (4) and the substrate resin, a method of dry-laminating the composition (4) (composition layer (4)) and the substrate resin (substrate resin layer) using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, a polyurethane compound, etc., a method of applying a solution of the composition (4) onto the substrate resin and then removing the solvent, etc. Among these, in consideration of cost and environmental considerations, it is preferable to produce the layer including the composition layer (4) by a step of melt-molding the layer, and specifically, a co-extrusion method is preferred.

[0247] The multilayer structure (4) may be subjected to a (heat) stretching treatment, if necessary. The stretching treatment may be either uniaxial stretching or biaxial stretching, and in the case of biaxial stretching, it may be simultaneous stretching or sequential stretching. Furthermore, the stretching method may be a roll stretching method, tenter stretching method, tubular stretching method, stretch-blow method, vacuum pressure forming, or the like, whichever provides a higher stretch ratio. The stretching temperature is a temperature near the melting point of the multilayer structure (4), and is usually selected from the range of 40 to 170°C, preferably about 60 to 160°C. When the stretching temperature is equal to or higher than the lower limit, the stretchability tends to be excellent, and when the stretching temperature is equal to or lower than the upper limit, a stable stretched state tends to be easily maintained.

[0248] The stretched multilayer structure (4) may be heat-set to provide dimensional stability. Heat-setting can be performed by known means, for example, by subjecting the stretched multilayer structure (4) to heat treatment while maintaining tension, typically at 80 to 180°C, preferably 100 to 165°C, for typically 2 to 600 seconds.

[0249] When the stretched multilayer structure (4) is used as a shrink film, in order to impart heat shrinkability, the above-mentioned heat setting is not carried out, but rather a treatment such as cooling and setting the stretched multilayer structure (4) by applying cold air thereto may be carried out.

[0250] The thickness of the present multilayer structure (4) (including a stretched one), and further the thickness of the present composition layer (4), base resin layer, and adhesive resin layer constituting the multilayer structure (4) cannot be generally determined depending on the layer configuration, type of base resin, type of adhesive resin, intended use, packaging form, required physical properties, etc., but the thickness of the present multilayer structure (4) (including a stretched one) is usually 10 to 5,000 μm, preferably 30 to 3,000 μm, and particularly preferably 50 to 2,000 μm. The present composition layer (4) is usually 1 to 500 μm, preferably 3 to 300 μm, and particularly preferably 5 to 200 μm; the base resin layer is usually 5 to 3,000 μm, preferably 10 to 2,000 μm, and particularly preferably 20 to 1,000 μm; and the adhesive resin layer is usually 0.5 to 250 μm, preferably 1 to 150 μm, and particularly preferably 3 to 100 μm.

[0251] Furthermore, the thickness ratio of the present composition layer (4) to the base resin layer in the present multilayer structure (4) (present composition layer (4) / base resin layer), expressed as the ratio between the thickest layers when there are multiple layers of each, is usually 1 / 99 to 50 / 50, preferably 5 / 95 to 45 / 55, and particularly preferably 10 / 90 to 40 / 60. Furthermore, the thickness ratio of the present composition layer (4) to the adhesive resin layer in the present multilayer structure (4) (present composition layer (4) / adhesive resin layer), expressed as the ratio between the thickest layers when there are multiple layers of each, is usually 10 / 90 to 99 / 1, preferably 20 / 80 to 95 / 5, and particularly preferably 50 / 50 to 90 / 10.

[0252] <Molded Article> It is also possible to obtain a molded article in the shape of a cup or tray using the present multilayer structure (4). In this case, a drawing method is usually employed, specifically vacuum forming, pressure forming, vacuum pressure forming, plug-assisted vacuum pressure forming, etc. Furthermore, when a tube- or bottle-shaped multilayer container (laminate structure) is obtained from a multilayer parison (a hollow tubular preform before blowing), a blow molding method is employed. Specific examples include extrusion blow molding (two-head type, mold moving type, parison shift type, rotary type, accumulator type, horizontal parison type, etc.), cold parison blow molding, injection blow molding, and biaxial stretch blow molding (extrusion type cold parison biaxial stretch blow molding, injection type cold parison biaxial stretch blow molding, injection molding in-line biaxial stretch blow molding, etc.). The resulting laminate may be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making, deep drawing, box processing, tube processing, splitting processing, etc. as required.

[0253] <Packaging> Packaging such as a single layer film formed from the present composition (4) or a container or lid material formed from a bag, cup, tray, tube, bottle, etc., made from the present multilayer structure (4) is useful as a variety of packaging material containers (e.g., food packaging, drug packaging, cosmetic packaging) for general foods as well as seasonings such as mayonnaise and dressing, fermented foods such as miso, oily foods such as salad oil, beverages, cosmetics, pharmaceuticals, etc.

[0254] <<Fifth Aspect>> The fifth aspect includes the following aspects [V-1] to [V-13]. [V-1] A composition containing an EVOH resin, a titanium compound, and a polyamide-based resin (D), wherein at least a portion of the EVOH resin is derived from biomass, and the content of the titanium compound in terms of metal is 0.0001 ppm or more and less than 1 ppm relative to the mass of the composition. [V-2] The composition according to [V-1], wherein the content of the titanium compound in terms of metal is 0.0001 ppm or more and 0.8 ppm or less relative to the mass of the composition. [V-3] The composition according to [V-1] or [V-2], wherein the content of the polyamide-based resin (D) is 1 to 40 mass% relative to the total mass of the composition. [V-4] The composition according to any one of [V-1] to [V-3], wherein the mass content ratio of the EVOH resin to the polyamide resin (D) [EVOH resin / (D)] is 1 / 99 to 99 / 1. [V-5] The composition according to any one of [V-1] to [V-4], wherein the EVOH resin has a biobased content of 0.01 to 99%. [V-6] The composition according to any one of [V-1] to [V-5], wherein the EVOH resin has a biobased content of 1 to 99%. [V-7] A molding material comprising the composition according to any one of [V-1] to [V-6]. [V-8] A multilayer structure having a layer comprising the composition according to any one of [V-1] to [V-6]. [V-9] The multilayer structure according to [V-8], further comprising an adhesive resin layer. [V-10] A molded article comprising the multilayer structure according to [V-8] or [V-9]. [V-11] A food package comprising the multilayer structure according to [V-8] or [V-9]. [V-12] A method for producing the composition according to any one of [V-1] to [V-6], comprising a step of mixing the EVOH resin and the titanium compound. [V-13] A method for producing the multilayer structure according to [V-8] or [V-9], comprising a step of melt-molding a layer comprising the composition.

[0255] The fifth aspect will be described below based on examples of embodiments for carrying out the fifth aspect, although the present invention is not limited to the embodiments described below.

[0256] <Composition> The composition according to the fifth aspect of the present invention (hereinafter, sometimes referred to as "the composition (5)") contains an EVOH resin as an essential component, a specific trace amount of a titanium compound, and a polyamide resin (D). Each component will be described below.

[0257] [EVOH Resin] The EVOH resin used in this embodiment is at least partly biomass-derived, and may be the same as the [EVOH Resin] described in the first embodiment. In addition, "the present composition (1)" in the description of the [EVOH Resin] in the first embodiment may be read as "the present composition (5)."

[0258] The content of the EVOH resin in the composition is usually 1% by mass or more, preferably 10% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, particularly preferably 70% by mass or more, especially preferably 75% by mass or more, and especially preferably 80% by mass or more. The upper limit of the EVOH resin content is usually 99% by mass or less, preferably 95% by mass or less, and even more preferably 93% by mass or less. When the value is within the above range, the effects of the present invention tend to be more effectively obtained.

[0259] [Titanium Compound] The titanium compound used in this embodiment may be the same as the [titanium compound] described in the first embodiment. In addition, "the present composition (1)" in the description of the [titanium compound] in the first embodiment may be read as "the present composition (5)."

[0260] [Polyamide Resin (D)] The polyamide resin (D) used in this embodiment is a water-insoluble thermoplastic resin, and any known polyamide resin can be used.

[0261] Examples of the polyamide resin (D) include homopolymers such as polycapramide (nylon 6), poly-ω-aminoheptanoic acid (nylon 7), poly-ω-aminononanoic acid (nylon 9), polyundecaneamide (nylon 11), and polylauryllactam (nylon 12). Examples of copolymer polyamide resins include polyethylene diamine adipamide (nylon 26), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyoctamethylene adipamide (nylon 86), polydecamethylene adipamide (nylon 108), caprolactam / lauryllactam copolymer (nylon 6 / 12), caprolactam / ω-aminononanoic acid copolymer (nylon 6 / 9), caprolactam / hexamethylenediammonium adipate copolymer (nylon 6 / 66), lauryllactam / hexamethylenediammonium adipate copolymer (nylon 12 / 66), ethylenediamine adipamide / hexamethylenediammonium adipate copolymer (nylon 26 / 66), caprolactam / hexamethylenediammonium adipate copolymer (nylon 12 / 66), Examples of the polyamide resin include aliphatic polyamides such as ethylene ammonium adipate / hexamethylene diammonium adipate copolymer (nylon 66 / 610) and ethylene ammonium adipate / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer (nylon 6 / 66 / 610), aromatic polyamides such as polyhexamethylene isophthalamide, polyhexamethylene terephthalamide, polymetaxylylene adipamide, hexamethylene isophthalamide / terephthalamide copolymer, poly-p-phenylene terephthalamide, and poly-p-phenylene-3,4'-diphenyl ether terephthalamide, amorphous polyamides, and polyamide resins modified with aromatic amines such as methylenebenzylamine and metaxylylene diamine, metaxylylene diammonium adipate, and terminal-modified polyamide resins thereof. Of these, terminal-modified polyamide resins are preferred. These polyamide resins (D) can be used alone or in combination of two or more.

[0262] The polyamide resin (D) tends to have a high bonding strength with a resin containing a polar group, such as an EVOH resin, and therefore the resin composition (5) containing the EVOH resin and the polyamide resin (D) is preferably used to improve the moisture resistance of a multilayer structure in which a layer made of the resin composition (5) is laminated with a layer made of another thermoplastic resin.

[0263] The proportion of amide bonds in the amide monomer units constituting the polyamide resin (D), calculated as a proportion of the molecular weight of the amide monomer units (for example, the amide bond (-CONH-) in [-CH-CONH-] in the case of nylon 6), is preferably 20 to 60%, more preferably 30 to 50%, and particularly preferably 35 to 45%. When the proportion of amide bonds is equal to or greater than the lower limit, the bonding strength at the interface with polar resins such as EVOH resin tends to be excellent. Conversely, when the proportion is equal to or less than the upper limit, the appropriate reactivity with polar resins such as EVOH resin during melt molding tends to suppress the occurrence of poor appearance due to roughness at the adhesive interface during co-extrusion.

[0264] The melting point of the polyamide-based resin (D) is preferably 160 to 270°C, more preferably 175 to 250°C, and even more preferably 190 to 230°C. When the melting point of the polyamide-based resin (D) is equal to or higher than the lower limit, the resulting multilayer structure tends to have excellent heat resistance. On the other hand, when the melting point of the polyamide-based resin (D) is equal to or lower than the upper limit, the difference in melting point between the polyamide-based resin (D) and the resin used in the other layer is small in the case of a multilayer structure containing other resin layers. This tends to suppress deterioration in appearance that occurs when layers are disrupted at the time of merging during coextrusion molding with other resins. Furthermore, when coextrusion molding with an EVOH resin, it tends to suppress thermal degradation of the EVOH resin caused by the die temperature.

[0265] From the above viewpoints, the preferred polyamide resin (D) has a melting point of usually 160 to 270°C, preferably 175 to 250°C, and more preferably 190 to 230°C. The proportion of amide bonds is usually 20 to 60%, preferably 30 to 50%, and more preferably 35 to 45%. Specifically, for example, nylon 6 (melting point: about 225°C, proportion of amide bonds: 38%) and nylon 6 / 66 (melting point: about 195°C, proportion of amide bonds: 38%) are preferred.

[0266] The degree of polymerization of the polyamide resin (D) can generally be expressed by its relative viscosity, which is usually preferably 1.5 to 6.0, more preferably 2.0 to 6.0, and even more preferably 2.5 to 5.0. When the relative viscosity is below the upper limit, the extruder tends to avoid a high torque state during molding, facilitating extrusion processing. When the relative viscosity is above the lower limit, the thickness precision of the resulting film or sheet tends to be excellent. The relative viscosity can be measured in accordance with JIS K 6933 by completely dissolving 1 g of polyamide resin in 100 mL of 96% by weight concentrated sulfuric acid and using a capillary viscometer at 25°C.

[0267] The content of the polyamide resin (D) is usually 1 to 40% by mass, preferably 5 to 35% by mass, and more preferably 15 to 30% by mass, based on the total mass of the composition (5). When the content is equal to or less than the upper limit, coloration tends to be easily suppressed, and when the content is equal to or more than the lower limit, the effect of suppressing thermal degradation tends to be obtained.

[0268] In the present composition (5), the mass ratio of the EVOH resin to the polyamide resin (D) [EVOH resin / (D)] is usually preferably 1 / 99 to 99 / 1, more preferably 10 / 90 to 99 / 1, even more preferably 50 / 50 to 98 / 2, particularly preferably 60 / 40 to 95 / 5, particularly preferably 70 / 30 to 95 / 5, and especially preferably 75 / 25 to 95 / 5. When the mass ratio of the polyamide resin (D) is equal to or greater than the lower limit, the resulting molded article tends to maintain the effects of the polyamide resin (D) in the composition (e.g., hot water sterilization resistance). Conversely, when the mass ratio is equal to or less than the upper limit, the resulting molded article tends to have excellent gas barrier properties.

[0269] The total content of the EVOH resin and the polyamide-based resin (D) in the composition (5) is usually 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more. The upper limit of the total content of the EVOH resin and the polyamide-based resin (D) is the total mass of the resin composition (5) excluding the content of the titanium compound.

[0270] It is generally known that EVOH resins deteriorate due to heat, and that blending EVOH resins with polyamide resins makes them more susceptible to thermal degradation and also tends to increase their viscosity when heated. Although the mechanism is unclear, it is presumed that the viscosity increase is due to the reaction of the blended polyamide resin with composition (5). It is also believed that the thermal degradation progresses because a double bond structure is formed in the main chain of the EVOH resin during the reaction, and this site acts as a reaction starting point, further inducing a dehydration reaction, resulting in the formation of a polyene structure in the main chain of the EVOH resin.

[0271] On the other hand, if a titanium compound is contained in composition (5), it is believed that titanium ions will cause coloration of composition (5), and therefore it is common technical knowledge for a person skilled in the art to avoid the use of titanium compounds.

[0272] However, in this embodiment, contrary to such common technical knowledge, it has been discovered that a composition (5) having excellent thermal stability can be obtained by combining a polyamide resin (D) with a specific trace amount of a titanium compound.

[0273] Titanium is stable as a tetravalent ion and stabilizes the EVOH resin by coordinating to the double bonds in the main chain and forming a chelate, which is thought to inhibit the formation of a polyene structure in the main chain of the EVOH resin. Furthermore, the coexistence of the polyamide resin (D) with the titanium compound is thought to inhibit the reaction between the polyamide resin (D) and composition (5), thereby suppressing the tendency for thickening and improving thermal stability. On the other hand, it is thought that when the content of the titanium compound is within a specific range, deterioration of the EVOH resin due to thermal decomposition caused by the titanium compound can be inhibited.

[0274] [Other Thermoplastic Resins] The present composition (5) may contain thermoplastic resins other than the EVOH resin and the polyamide-based resin (D) within a range that does not impair the effects of the present invention (for example, usually 50% by mass or less of the present composition (5), preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The lower limit is 0% by mass, for example, 0 to 50% by mass). As the other thermoplastic resin, the same ones as those described in the first embodiment of the present invention as [Other Thermoplastic Resins] can be used.

[0275] [Other Compounding Agents] Composition (5) may also contain compounding agents generally compounded with EVOH resins (however, the term "compounding agent" as used herein excludes titanium compounds) within a range that does not impair the effects of the present invention (for example, 5% by mass or less, preferably 3% by mass or less, with a lower limit of 0% by mass, e.g., 0 to 5% by mass). Examples of the compounding agents include inorganic double salts (e.g., hydrotalcite, etc.), plasticizers (e.g., aliphatic polyhydric alcohols such as ethylene glycol, glycerin, and hexanediol), oxygen absorbers [e.g., inorganic oxygen absorbers such as aluminum powder and potassium sulfite; ascorbic acid, its fatty acid esters and metal salts, etc.; gallic acid; polyhydric phenols such as hydroxyl group-containing phenolaldehyde resins; terpene compounds; blends of tertiary hydrogen-containing resins and transition metals (e.g., a combination of polypropylene and cobalt); blends of carbon-carbon unsaturated bond-containing resins and transition metals; Polymeric oxygen absorbers such as polymeric oxygen absorbers, such as polymeric compounds (e.g., a combination of polybutadiene and cobalt), photooxidatively degradable resins (e.g., polyketones), anthraquinone polymers (e.g., polyvinyl anthraquinone), and combinations thereof to which photoinitiators (e.g., benzophenone), antioxidants other than those mentioned above, and deodorants (e.g., activated carbon), heat stabilizers (boric acid, phosphoric acid), light stabilizers, ultraviolet absorbers, colorants, antistatic agents, surfactants (excluding those used as lubricants), antibacterial agents, antiblocking agents, and fillers (e.g., aluminum, inorganic fillers). These compounds may be used alone or in combination of two or more.

[0276] [Method for Producing the Composition] The composition (5) can be produced, for example, by mixing the EVOH resin, titanium compound, and polyamide-based resin (D) by a known method such as a dry blending method, a melt mixing method, a solution mixing method, an impregnation method, etc. Among these, it is preferable to produce the composition by a method including a step of mixing the EVOH resin and the titanium compound. Furthermore, these production methods can be used in any combination.

[0277] The dry blending method may, for example, be (I) a method in which pellets containing a pellet-shaped EVOH resin and / or a polyamide resin (D) are dry-blended with a titanium compound using a tumbler or the like.

[0278] Examples of the melt mixing method include (II) a method in which a dry blend of pellets containing EVOH resin and / or polyamide-based resin (D) and a titanium compound is melt-kneaded to obtain pellets or other molded products; (III) a method in which a titanium compound is added to a melt of EVOH resin and / or polyamide-based resin (D) in a molten state, followed by melt-kneading to obtain pellets or other molded products; and a method in which a titanium compound is incorporated into EVOH resin and / or polyamide-based resin (D), and pellets having a core-sheath structure in which the EVOH resin is the core and the polyamide-based resin (D) is the sheath are prepared using the EVOH resin and / or polyamide-based resin (D), and then the pellets are melt-molded.

[0279] Examples of the solution mixing method include (IV) a method in which a solution is prepared using commercially available pellets containing EVOH resin and / or polyamide-based resin (D), a titanium compound is blended therein, the solution is coagulated and molded to form pellets, and the pellets are subjected to solid-liquid separation and drying; and (v) a method in which, in the production process of EVOH resin, a solution of polyamide-based resin (D) and / or a titanium compound is added to an ethylene-vinyl ester copolymer solution before saponification or a homogeneous solution of EVOH resin (such as a water / alcohol solution), the solution is coagulated and molded to form pellets, and the pellets are subjected to solid-liquid separation and drying.

[0280] The impregnation method may be exemplified by a method in which pellets containing (VI) EVOH resin and / or polyamide resin (D) are brought into contact with an aqueous solution containing a titanium compound to impregnate the pellets with the titanium compound, followed by drying. The aqueous solution containing a titanium compound may be an aqueous solution of a titanium compound or a titanium compound immersed in water containing various chemicals to elute titanium ions.

[0281] In the impregnation method, the content of the titanium compound (in terms of metal) can be controlled by the concentration of the titanium compound in the aqueous solution in which the EVOH resin is immersed, the immersion temperature, the immersion time, etc. The immersion temperature and the immersion time are usually 0.5 to 48 hours, preferably 1 to 36 hours, and the immersion temperature is usually 10 to 40°C, preferably 20 to 35°C.

[0282] In each of the above-mentioned methods, it is also possible to prepare a composition (5) (master patch) having a high concentration of the titanium compound by blending the EVOH resin and / or polyamide-based resin (D) with a predetermined ratio in advance, and then blend this composition (5) (master patch) with the EVOH resin or polyamide-based resin (D) to obtain a resin composition (5) of a desired concentration.

[0283] As the drying method in each of the above-mentioned production methods, various drying methods can be used, and either static drying or fluidized drying may be used, or these may be used in combination.

[0284] As described above, in this embodiment, the above-mentioned different methods can be combined. Among them, the melt mixing method is preferred, and method (II) is particularly preferred, in terms of productivity and the ability to obtain a resin composition (5) that exhibits the effects of the present invention more significantly. Furthermore, when using the other thermoplastic resins and other compounding agents, they may be compounded by a conventional method according to the above-mentioned production method.

[0285] The shape of the present composition (5) obtained by each of the above-mentioned production methods may be any shape, but is preferably pellets. The pellets may be, for example, spherical, oval, cylindrical, die-shaped, or rectangular, but are typically oval or cylindrical. From the viewpoint of convenience when subsequently used as a molding material, the size of the pellets is such that, in the case of an oval shape, the minor axis is typically 1 to 10 mm, preferably 2 to 6 mm, and more preferably 2.5 to 5.5 mm, and the major axis is typically 1.5 to 30 mm, preferably 3 to 20 mm, and more preferably 3.5 to 10 mm. In the case of a cylindrical shape, the diameter of the base is typically 1 to 6 mm, preferably 2 to 5 mm, and the length is typically 1 to 6 mm, preferably 2 to 5 mm. In the case of a die-shaped shape, the length of one side is typically 1 to 6 mm, preferably 2 to 5 mm. The shape and size of the pelletized EVOH resin used in each of the above-mentioned production methods are also preferably similar.

[0286] The water content of the composition (5) is not particularly limited, but is usually 0.01 to 0.5% by mass, preferably 0.05 to 0.35% by mass, and particularly preferably 0.1 to 0.3% by mass.

[0287] The water content of the composition (5) is measured and calculated by the following method. １ ) was weighed on an electronic balance, dried in a hot air dryer at 150°C for 5 hours, and allowed to cool in a desiccator for 30 minutes, after which the mass (W ２ ) is weighed and calculated using the following formula: [Formula] Water content (mass%) = [(W １ -W ２ ) / W １ ]×100

[0288] When the composition (5) is in the form of pellets, it is also preferable to apply a known lubricant to the surface of the pellets in order to stabilize the feedability during melt molding. Examples of lubricants include higher fatty acids having 12 or more carbon atoms (e.g., lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc.), higher fatty acid esters (methyl esters, isopropyl esters, butyl esters, octyl esters of higher fatty acids, etc.), higher fatty acid amides (e.g., saturated higher fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, etc.; unsaturated higher fatty acid amides such as oleic acid amide, erucic acid amide, etc.; bis-higher fatty acid amides such as ethylene bisstearic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, ethylene bislauric acid amide, etc.), low-molecular-weight polyolefins (e.g., low-molecular-weight polyethylene or low-molecular-weight polypropylene having a molecular weight of about 500 to 10,000, or low-molecular-weight polypropylene, or acid-modified products thereof), higher alcohols having 6 or more carbon atoms, ester oligomers, and fluorinated ethylene resins. These compounds can be used alone or in combination of two or more. The content of such lubricants is usually 5% by mass or less, preferably 1% by mass or less, of the present composition (5). The lower limit is usually 0% by mass, for example, 0 to 5% by mass.

[0289] The composition (5) thus obtained has excellent thermal stability. When the composition (5) is measured using a visual analyzer IRIS VA400 (manufactured by Alphamos), the ratio of the sum of color numbers "1091" (R: 72, G: 72, B: 56), "1092" (R: 72, G: 72, B: 72), and "1093" (R: 72, G: 72, B: 88) to the sum of color numbers "1620" (R: 104, G: 88, B: 72) and "1621" (R: 104, G: 88, B: 88), i.e., ("1091" + "1092" + "1093") / ("1620" + "1621"), is usually 2.5 or less, preferably 2 or less, and more preferably 1.5 or less. The lower limit is usually 0, for example, usually 0 to 2.5. The smaller the ratio, the more suppressed is the coloration due to thermal degradation, and the higher the thermal stability tends to be. Note that a difference of 0.5 in the ratio is very significant, as it appears as a large difference in yield in actual production.

[0290] <Molding material> The present composition (5) thus obtained is prepared into various forms such as pellets, powder, or liquid, and is provided as a molding material for various molded products. In particular, in this embodiment, when it is provided as a material for melt molding, the effects of the present invention tend to be more efficiently obtained, which is preferable.

[0291] Examples of the molded article include a monolayer film molded from the present composition (5), as well as a multilayer structure having a layer made of the present composition (5).

[0292] <Multilayer structure> The multilayer structure according to the fifth aspect of the present invention (hereinafter referred to as "the present multilayer structure (5)") contains the present composition (5) and has at least one layer made of the present composition (5). The layer made of the present composition (5) in the present multilayer structure (5) (hereinafter simply referred to as "the present composition layer (5)") may be a single layer or multiple layers. Furthermore, the present composition layer (5) can be laminated with another substrate (hereinafter, the resin used for the substrate may be abbreviated as "substrate resin") containing a thermoplastic resin other than EVOH resin as a main component to impart further strength, protect the present composition layer (5) from the effects of moisture, etc., or impart other functions.

[0293] Examples of the base resin include polyethylene-based resins such as linear low-density polyethylene, low-density polyethylene, very low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-propylene (block and random) copolymers, and ethylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymers; polypropylene-based resins such as polypropylene and propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymers; (unmodified) polyolefin-based resins such as polybutene, polypentene, and polycyclic olefin-based resins (polymers having a cyclic olefin structure in at least one of the main chain and side chain); and polyolefins obtained by dissolving these polyolefins in an unsaturated carboxylic acid or Examples include polyolefin resins in the broad sense, including modified olefin resins such as unsaturated carboxylic acid-modified polyolefin resins graft-modified with an ester thereof, ionomers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, polyester resins, polyamide resins (including copolymerized polyamides), polyvinyl chloride, polyvinylidene chloride, acrylic resins, polystyrene resins, vinyl ester resins, polyester elastomers, polyurethane elastomers, polystyrene elastomers, halogenated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, aromatic or aliphatic polyketones, etc. These may be used alone or in combination of two or more.

[0294] Of these, hydrophobic resins such as polyamide-based resins, polyolefin-based resins, polyester-based resins, and polystyrene-based resins are preferred, and more preferred are polyolefin-based resins such as polyethylene-based resins, polypropylene-based resins, polycyclic olefin-based resins, and unsaturated carboxylic acid-modified polyolefin-based resins thereof.

[0295] The layer structure of the multilayer structure (5) can be any combination, such as a / b, b / a / b, a / b / a, a1 / a2 / b, a / b1 / b2, b2 / b1 / a / b1 / b2, or b2 / b1 / a / b1 / a / b1 / b2, where a denotes the composition layer (5) and b denotes the base resin layer (b1, b2, etc.). Furthermore, when R denotes a recycled layer containing a mixture of the composition (5) and a thermoplastic resin other than EVOH resin, obtained by remelting and molding edges or defective products generated during the manufacturing process of the multilayer structure (5), b / R / a, b / R / a / b, b / R / a / R / b, b / a / R / a / b, b / R / a / R / a / R / b, or b / R / a / R / a / R / b, etc. The total number of layers in the multilayer structure (5) is usually 2 to 15, and preferably 3 to 10. In the above layer structure, an adhesive resin layer containing an adhesive resin may be interposed between the respective layers, if necessary.

[0296] Known adhesive resins can be used, and may be selected appropriately depending on the type of thermoplastic resin used in the base resin layer "b." Representative examples include modified polyolefin polymers containing carboxy groups, which are obtained by chemically bonding an unsaturated carboxylic acid or its anhydride to a polyolefin resin via addition reaction, graft reaction, or the like. Examples of modified polyolefin polymers containing carboxy groups include maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, maleic anhydride-grafted ethylene-propylene (block and random) copolymers, maleic anhydride-grafted ethylene-ethyl acrylate copolymers, maleic anhydride-grafted ethylene-vinyl acetate copolymers, maleic anhydride-grafted polycyclic olefin resins, and maleic anhydride-grafted polyolefin resins. These may be used alone or in combination of two or more.

[0297] In the present multilayer structure (5), when an adhesive resin layer is used between the present composition layer (5) and the base resin layer, it is preferable to use an adhesive resin with excellent hydrophobicity, since the adhesive resin layers are located on both sides of the present composition layer (5).

[0298] The base resin and adhesive resin may contain conventionally known plasticizers, fillers, clay (montmorillonite, etc.), colorants, antioxidants, antistatic agents, lubricants, nucleating agents, antiblocking agents, waxes, etc., within a range that does not impair the spirit of the present invention (for example, usually 30% by mass or less, preferably 10% by mass or less, with the lower limit being 0% by mass, e.g., 0 to 30% by mass, based on the total resin). These may be used alone or in combination of two or more.

[0299] The lamination of the present composition layer (5) and the above-mentioned base resin layer (including the case where an adhesive resin layer is interposed) can be carried out by a known method. For example, there can be mentioned a method of melt-extrusion laminating a base resin onto a film, sheet, etc. of the present composition (5), a method of melt-extrusion laminating the present composition (5) onto a base resin layer, a method of co-extruding the present composition (5) and a base resin, a method of dry-laminating the present composition (5) (the present composition layer (5)) and a base resin (base resin layer) using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, a polyurethane compound, etc., a method of applying a solution of the present composition (5) onto a base resin and then removing the solvent, etc. Among these, in consideration of cost and environmental considerations, it is preferable to produce the layer by including a step of melt-molding a layer containing the present composition layer (5), and specifically, a co-extrusion method is preferred.

[0300] The multilayer structure (5) may be subjected to a (heat) stretching treatment, if necessary. The stretching treatment may be either uniaxial stretching or biaxial stretching, and in the case of biaxial stretching, it may be simultaneous stretching or sequential stretching. Furthermore, the stretching method may be a roll stretching method, tenter stretching method, tubular stretching method, stretch-blow method, vacuum pressure forming, or the like, whichever provides a higher stretch ratio. The stretching temperature is a temperature near the melting point of the multilayer structure (5), and is usually selected from the range of 40 to 170°C, preferably about 60 to 160°C. When the stretching temperature is equal to or higher than the lower limit, the stretchability tends to be excellent, and when the stretching temperature is equal to or lower than the upper limit, a stable stretched state tends to be easily maintained.

[0301] The stretched multilayer structure (5) may be heat-set to provide dimensional stability. Heat-setting can be performed by known means, for example, by subjecting the stretched multilayer structure (5) to heat treatment while maintaining tension, typically at 80 to 180°C, preferably 100 to 165°C, for typically 2 to 600 seconds.

[0302] When the stretched multilayer structure (5) is used as a shrink film, in order to impart heat shrinkability, the above-mentioned heat setting is not carried out, but rather a treatment such as cooling and setting the stretched multilayer structure (5) by applying cold air thereto may be carried out.

[0303] The thickness of the present multilayer structure (5) (including a stretched one), as well as the thickness of the present composition layer (5), base resin layer, and adhesive resin layer constituting the multilayer structure (5), cannot be generally determined depending on the layer configuration, type of base resin, type of adhesive resin, intended use, packaging form, required physical properties, etc., but the thickness of the present multilayer structure (5) (including a stretched one) is usually 10 to 5,000 μm, preferably 30 to 3,000 μm, and particularly preferably 50 to 2,000 μm. The present composition layer (5) is usually 1 to 500 μm, preferably 3 to 300 μm, and particularly preferably 5 to 200 μm; the base resin layer is usually 5 to 3,000 μm, preferably 10 to 2,000 μm, and particularly preferably 20 to 1,000 μm; and the adhesive resin layer is usually 0.5 to 250 μm, preferably 1 to 150 μm, and particularly preferably 3 to 100 μm.

[0304] Furthermore, the thickness ratio of the present composition layer (5) to the base resin layer in the present multilayer structure (5) (present composition layer (5) / base resin layer), expressed as the ratio between the thickest layers when there are multiple layers of each, is usually 1 / 99 to 50 / 50, preferably 5 / 95 to 45 / 55, and particularly preferably 10 / 90 to 40 / 60. Furthermore, the thickness ratio of the present composition layer (5) to the adhesive resin layer in the present multilayer structure (5) (present composition layer (5) / adhesive resin layer), expressed as the ratio between the thickest layers when there are multiple layers of each, is usually 10 / 90 to 99 / 1, preferably 20 / 80 to 95 / 5, and particularly preferably 50 / 50 to 90 / 10.

[0305] <Molded Article> It is also possible to obtain a cup- or tray-shaped molded article using the present multilayer structure (5). In this case, a drawing method is usually employed, specifically vacuum forming, pressure forming, vacuum-pressure forming, plug-assisted vacuum-pressure forming, etc. Furthermore, when a tube- or bottle-shaped multilayer container (laminate structure) is obtained from a multilayer parison (a hollow tubular preform before blowing), a blow molding method is employed. Specific examples include extrusion blow molding (two-head type, mold-moving type, parison-shift type, rotary type, accumulator type, horizontal parison type, etc.), cold parison blow molding, injection blow molding, and biaxial stretch blow molding (extrusion-type cold parison biaxial stretch blow molding, injection-type cold parison biaxial stretch blow molding, injection-molding in-line biaxial stretch blow molding, etc.). The resulting laminate may be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making, deep drawing, box processing, tube processing, splitting processing, etc. as required.

[0306] <Packaging> Packaging such as a single layer film formed from the present composition (5) or a container or lid material formed from a bag, cup, tray, tube, bottle, etc., made from the present multilayer structure (5) is useful as a variety of packaging material containers (e.g., food packaging, drug packaging, cosmetic packaging) for general foods as well as seasonings such as mayonnaise and dressing, fermented foods such as miso, oily foods such as salad oil, beverages, cosmetics, pharmaceuticals, etc.

[0307] <<Sixth Aspect>> The sixth aspect includes the following aspects [VI-1] to [VI-13]. [VI-1] A composition containing an EVOH resin, a titanium compound, and a polyolefin-based resin (E), wherein at least a portion of the EVOH resin is derived from biomass, and the content of the titanium compound in terms of metal is 0.0001 ppm or more and less than 1 ppm relative to the mass of the composition. [VI-2] The composition according to [VI-1], wherein the content of the titanium compound in terms of metal is 0.0001 ppm or more and 0.8 ppm or less relative to the mass of the composition. [VI-3] The composition according to [VI-1] or [VI-2], wherein the content of the polyolefin-based resin (E) is 60 to 95 mass% relative to the total mass of the composition. [VI-4] The composition according to any one of [VI-1] to [VI-3], wherein the mass ratio of the EVOH resin to the polyolefin resin (E) [EVOH resin / (E)] is 1 / 99 to 99 / 1. [VI-5] The composition according to any one of [VI-1] to [VI-4], wherein the EVOH resin has a biobased content of 0.01 to 99%. [VI-6] The composition according to any one of [VI-1] to [VI-5], wherein the EVOH resin has a biobased content of 1 to 99%. [VI-7] A molding material comprising the composition according to any one of [VI-1] to [VI-6]. [VI-8] A multilayer structure having a layer comprising the composition according to any one of [VI-1] to [VI-6]. [VI-9] The multilayer structure according to [VI-8], further comprising an adhesive resin layer. [VI-10] A molded article comprising the multilayer structure according to [VI-8] or [VI-9]. [VI-11] A food package comprising the multilayer structure according to [VI-8] or [VI-9]. [VI-12] A method for producing the composition according to any one of [VI-1] to [VI-6], comprising a step of mixing the EVOH resin and the titanium compound. [VI-13] A method for producing the multilayer structure according to [VI-8] or [VI-9], comprising a step of melt-molding a layer containing the composition.

[0308] The sixth aspect will be described below based on examples of embodiments for carrying out the sixth aspect, although the present invention is not limited to the following embodiments.

[0309] <Composition> The composition according to the sixth aspect of the present invention (hereinafter, sometimes referred to as "the composition (6)") contains an EVOH resin as an essential component, a specific trace amount of a titanium compound, and a polyolefin resin (E). Each component will be described below.

[0310] [EVOH Resin] The EVOH resin used in this embodiment is at least partly biomass-derived, and may be the same as the [EVOH Resin] described in the first embodiment. In addition, "the present composition (1)" in the description of the [EVOH Resin] in the first embodiment may be read as "the present composition (6)."

[0311] The content of the EVOH resin in the composition is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5 to 40% by mass, even more preferably 5 to 30% by mass, particularly preferably 5 to 25% by mass or more, and especially preferably 5 to 20% by mass. When the content is within the above range, the effects of the present invention tend to be more effectively obtained.

[0312] [Titanium Compound] The titanium compound used in this embodiment may be the same as the [titanium compound] described in the first embodiment. In addition, "the present composition (1)" in the description of the [titanium compound] in the first embodiment may be read as "the present composition (6)."

[0313] [Polyolefin Resin (E)] The polyolefin resin (E) used in this embodiment is not particularly limited, but preferably contains 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more, of the monomer units constituting the polyolefin resin (E) in the greatest amount. Examples of the polyolefin resin (E) include linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), very low-density polyethylene (VLDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), ionomers, ethylene-propylene (block or random) copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, polypropylene (PP), propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymers, polybutene, polypentene, polymethylpentene, and other olefin homo- or copolymers, or olefin homo- or copolymers graft-modified with an unsaturated carboxylic acid or an ester thereof, in the broad sense of the term. These may be used alone or in combination of two or more kinds, and among them, polypropylene (PP), polyethylene (MDPE, HDPE), and blends thereof are preferred in order to obtain molded articles excellent in mechanical strength. In particular, polypropylene is most suitable in terms of effectiveness.

[0314] The polyolefin resin (E) used in this embodiment usually has a density of 0.89 g / cm 3 or more, preferably 0.90 g / cm 3 0.98g / cm or more 3 For example, when a molded article obtained using the composition (6) is reused, it may be used to reinforce the mechanical strength of the composition (6), and when such an application is intended, it is preferable to use a polyolefin resin (E) having a relatively high density in order to obtain a resin composition having a higher density and excellent mechanical strength.

[0315] The content of the polyolefin resin (E) is usually 60 to 99% by mass, preferably 70 to 99% by mass, and more preferably 85 to 98% by mass, based on the total mass of the composition (6). When the content is equal to or greater than the lower limit, coloration tends to be easily suppressed, and when the content is equal to or greater than the lower limit, the effect of suppressing thermal degradation tends to be obtained.

[0316] In the present composition (6), the mass content ratio of the EVOH resin to the polyolefin-based resin (E) [EVOH resin / (E)] is preferably 1 / 99 to 99 / 1, more preferably 2 / 98 to 75 / 25, even more preferably 3 / 97 to 50 / 50, particularly preferably 4 / 96 to 25 / 75, and especially preferably 5 / 95 to 10 / 90. When the mass content ratio of the EVOH resin to the olefin-based resin (E) is within the above range, the thermal degradation suppression effect becomes even more excellent.

[0317] The total content of the EVOH resin and the polyolefin resin (E) in the composition (6) is usually 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more. The upper limit of the total content of the EVOH resin and the polyolefin resin (E) is the total mass of the resin composition (6) excluding the titanium compound.

[0318] It is generally known that EVOH resin deteriorates due to heat. Although the mechanism is not clear, it is thought that the thermal deterioration progresses because double bond structures are formed in the main chain of the EVOH resin during the reaction, and these sites act as reaction initiation sites, which further induce dehydration reactions, resulting in the formation of polyene structures in the main chain of the EVOH resin.

[0319] On the other hand, if a titanium compound is contained in composition (6), it is believed that titanium ions will cause coloration of composition (6), and therefore it is common technical knowledge for a person skilled in the art to avoid the use of titanium compounds.

[0320] However, in this embodiment, contrary to such common technical knowledge, it has been found that a composition (6) having excellent thermal stability can be obtained by combining a polyolefin resin (E) with a specific trace amount of a titanium compound.

[0321] Titanium is stable as a tetravalent ion and stabilizes the EVOH resin by coordinating to the double bonds in the main chain and forming a chelate, which is thought to suppress the formation of a polyene structure in the main chain of the EVOH resin. Furthermore, the coexistence of the polyolefin resin (E) with the titanium compound results in a large number of double bond sites being distributed in the resin composition (6), which is thought to suppress the formation of additional double bonds and further improve thermal stability. On the other hand, it is thought that when the content of the titanium compound is within a specific range, deterioration of the EVOH resin due to thermal decomposition caused by the titanium compound tends to be suppressed.

[0322] [Other Thermoplastic Resins] The present composition (6) may contain thermoplastic resins other than the EVOH resin and the polyolefin-based resin (E) within a range that does not impair the effects of the present invention (for example, usually 50% by mass or less of the present composition (6), preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less; the lower limit is 0% by mass, for example, 0 to 50% by mass). As the other thermoplastic resin, the same ones as those described in the first embodiment of the present invention as [Other Thermoplastic Resins] can be used.

[0323] [Other Compounding Agents] Composition (6) may also contain compounding agents generally compounded with EVOH resins (however, the term "compounding agent" as used herein excludes titanium compounds) within a range that does not impair the effects of the present invention (for example, 5% by mass or less, preferably 3% by mass or less, with a lower limit of 0% by mass, e.g., 0 to 5% by mass). Examples of the compounding agents include inorganic double salts (e.g., hydrotalcite, etc.), plasticizers (e.g., aliphatic polyhydric alcohols such as ethylene glycol, glycerin, and hexanediol), oxygen absorbers [e.g., inorganic oxygen absorbers such as aluminum powder and potassium sulfite; ascorbic acid, its fatty acid esters and metal salts, etc.; gallic acid; polyhydric phenols such as hydroxyl group-containing phenolaldehyde resins; terpene compounds; blends of tertiary hydrogen-containing resins and transition metals (e.g., a combination of polypropylene and cobalt); blends of carbon-carbon unsaturated bond-containing resins and transition metals; Polymeric oxygen absorbers such as polymeric oxygen absorbers, such as polymeric compounds (e.g., a combination of polybutadiene and cobalt), photooxidatively degradable resins (e.g., polyketones), anthraquinone polymers (e.g., polyvinyl anthraquinone), and combinations thereof to which photoinitiators (e.g., benzophenone), antioxidants other than those mentioned above, and deodorants (e.g., activated carbon), heat stabilizers (boric acid, phosphoric acid), light stabilizers, ultraviolet absorbers, colorants, antistatic agents, surfactants (excluding those used as lubricants), antibacterial agents, antiblocking agents, and fillers (e.g., aluminum, inorganic fillers). These compounds may be used alone or in combination of two or more.

[0324] [Method for Producing Composition] The composition (6) can be produced, for example, by mixing the EVOH resin, titanium compound, and polyolefin resin (E) by a known method such as a dry blending method, a melt mixing method, a solution mixing method, an impregnation method, etc. Among these, it is preferable to produce the composition by a method including a step of mixing the EVOH resin and the titanium compound. Furthermore, these production methods can be used in any combination.

[0325] The dry blending method may, for example, be (I) a method in which pellets containing a pellet-shaped EVOH resin and / or a polyolefin resin (E) are dry-blended with a titanium compound using a tumbler or the like.

[0326] Examples of the melt mixing method include (II) a method in which a dry blend of pellets containing an EVOH resin and / or a polyolefin resin (E) and a titanium compound is melt-kneaded to obtain pellets or other molded products; (III) a method in which a titanium compound is added to a melt of a molten EVOH resin and / or a polyolefin resin (E), followed by melt-kneading to obtain pellets or other molded products; and a method in which a titanium compound is incorporated into an EVOH resin and / or a polyolefin resin (E), and the EVOH resin and / or the polyolefin resin (E) is used to prepare pellets having a core-sheath structure in which the EVOH resin is the core and the polyolefin resin (E) is the sheath, and the pellets are melt-molded.

[0327] Examples of the solution mixing method include (IV) a method in which a solution is prepared using pellets containing commercially available EVOH resin and / or polyolefin resin (E), a titanium compound is blended therein, the solution is coagulated and molded to form pellets, and the resulting pellets are subjected to solid-liquid separation and drying; and (v) a method in which, in the production process of EVOH resin, a solution of polyolefin resin (E) and / or a titanium compound is added to an ethylene-vinyl ester copolymer solution before saponification or a homogeneous solution of EVOH resin (such as a water / alcohol solution), the solution is coagulated and molded to form pellets, and the resulting pellets are subjected to solid-liquid separation and drying.

[0328] The impregnation method may be exemplified by a method in which pellets containing (VI) EVOH resin and / or polyolefin resin (E) are brought into contact with an aqueous solution containing a titanium compound to impregnate the pellets with the titanium compound, followed by drying. The aqueous solution containing a titanium compound may be an aqueous solution of a titanium compound or a titanium compound immersed in water containing various chemicals to elute titanium ions.

[0329] In the impregnation method, the content of the titanium compound (in terms of metal) can be controlled by the concentration of the titanium compound in the aqueous solution in which the EVOH resin is immersed, the immersion temperature, the immersion time, etc. The immersion temperature and the immersion time are usually 0.5 to 48 hours, preferably 1 to 36 hours, and the immersion temperature is usually 10 to 40°C, preferably 20 to 35°C.

[0330] In each of the above-mentioned methods, it is also possible to prepare a composition (6) (master patch) having a high concentration of the titanium compound by blending the EVOH resin and / or polyolefin resin (E) with the titanium compound in a predetermined ratio in advance, and then blend this composition (6) (master patch) with the EVOH resin or polyolefin resin (E) to obtain a resin composition (6) having a desired concentration.

[0331] As the drying method in each of the above-mentioned production methods, various drying methods can be used, and either static drying or fluidized drying may be used, or these may be used in combination.

[0332] As described above, in this embodiment, the above-mentioned different methods can be combined. Among them, the melt mixing method is preferred, and method (II) is particularly preferred, in terms of productivity and the fact that a resin composition with more pronounced effects of the present invention can be obtained. Furthermore, when using the other thermoplastic resins and other compounding agents, they may be compounded by a conventional method according to the above-mentioned production method.

[0333] The shape of the present composition (6) obtained by each of the above-mentioned production methods may be any shape, but is preferably pellets. The pellets may be, for example, spherical, oval, cylindrical, die-shaped, or rectangular, but are typically oval or cylindrical. From the viewpoint of convenience when subsequently used as a molding material, the size of the pellets is such that, in the case of an oval shape, the minor axis is typically 1 to 10 mm, preferably 2 to 6 mm, and more preferably 2.5 to 5.5 mm, and the major axis is typically 1.5 to 30 mm, preferably 3 to 20 mm, and more preferably 3.5 to 10 mm. In the case of a cylindrical shape, the base diameter is typically 1 to 6 mm, preferably 2 to 5 mm, and the length is typically 1 to 6 mm, preferably 2 to 5 mm. In the case of a die-shaped shape, one side is typically 1 to 6 mm, preferably 2 to 5 mm. The shape and size of the pelletized EVOH resin used in each of the above-mentioned production methods are also preferably similar.

[0334] The water content of the composition (6) is not particularly limited, but is usually 0.01 to 0.5% by mass, preferably 0.05 to 0.35% by mass, and particularly preferably 0.1 to 0.3% by mass.

[0335] The water content of the composition (6) is measured and calculated by the following method. １ ) was weighed on an electronic balance, dried in a hot air dryer at 150°C for 5 hours, and allowed to cool in a desiccator for 30 minutes, after which the mass (W ２ ) is weighed and calculated using the following formula: [Formula] Water content (mass%) = [(W １ -W ２ ) / W １ ]×100

[0336] When the composition (6) is in the form of pellets, it is also preferable to apply a known lubricant to the surface of the pellets in order to stabilize the feedability during melt molding. Examples of lubricants include higher fatty acids having 12 or more carbon atoms (e.g., lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc.), higher fatty acid esters (methyl esters, isopropyl esters, butyl esters, octyl esters of higher fatty acids, etc.), higher fatty acid amides (e.g., saturated higher fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, etc.; unsaturated higher fatty acid amides such as oleic acid amide, erucic acid amide, etc.; bis-higher fatty acid amides such as ethylene bisstearic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, ethylene bislauric acid amide, etc.), low-molecular-weight polyolefins (e.g., low-molecular-weight polyethylene or low-molecular-weight polypropylene having a molecular weight of about 500 to 10,000, or acid-modified products thereof), higher alcohols having 6 or more carbon atoms, ester oligomers, and fluorinated ethylene resins. These compounds can be used alone or in combination of two or more. The content of such lubricants is usually 5% by mass or less, preferably 1% by mass or less, of the present composition (6). The lower limit is usually 0% by mass, for example, 0 to 5% by mass.

[0337] The composition (6) thus obtained has excellent thermal stability. The ratio of the sum of color numbers "1108" (R: 72, G: 88, B: 72) and "1109" (R: 72, G: 88, B: 88) to color number "1331" (R: 88, G: 56, B: 56), measured using a visual analyzer IRIS VA400 (manufactured by Alphamos), ("1108" + "1109" / "1331"), is typically less than 2, preferably 1.5 or less, and more preferably 1 or less. The lower limit is typically 0, for example, typically 0 or more but less than 2. The smaller the ratio, the more suppressed discoloration associated with thermal degradation and the higher the thermal stability. A difference of 0.5 in the ratio results in a significant difference in yield in actual production, and is therefore a very significant difference.

[0338] <Molding material> The present composition (6) thus obtained is prepared into various forms such as pellets, powder, or liquid, and is provided as a molding material for various molded products. In particular, in the present invention, when it is provided as a material for melt molding, the effects of the present invention tend to be more efficiently obtained, which is preferable.

[0339] Examples of the molded article include a monolayer film molded from the present composition (6), as well as a multilayer structure having a layer made of the present composition (6).

[0340] <Multilayer structure> The multilayer structure according to the sixth aspect of the present invention (hereinafter referred to as "the present multilayer structure (6)") contains the present composition (6) and has at least one layer made of the present composition (6). The layer made of the present composition (6) in the present multilayer structure (6) (hereinafter simply referred to as "the present composition layer (6)") may be a single layer or multiple layers. Furthermore, the present composition layer (6) can be laminated with another substrate (hereinafter, the resin used for the substrate may be abbreviated as "substrate resin") containing a thermoplastic resin other than EVOH resin as a main component to impart further strength, protect the present composition layer (6) from the effects of moisture, etc., or impart other functions.

[0341] Examples of the base resin include polyethylene-based resins such as linear low-density polyethylene, low-density polyethylene, very low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-propylene (block and random) copolymers, and ethylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymers; polypropylene-based resins such as polypropylene and propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymers; (unmodified) polyolefin-based resins such as polybutene, polypentene, and polycyclic olefin-based resins (polymers having a cyclic olefin structure in at least one of the main chain and side chain); and polyolefins obtained by dissolving these polyolefins in an unsaturated carboxylic acid or Examples include polyolefin resins in the broad sense, including modified olefin resins such as unsaturated carboxylic acid-modified polyolefin resins graft-modified with an ester thereof, ionomers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, polyester resins, polyamide resins (including copolymerized polyamides), polyvinyl chloride, polyvinylidene chloride, acrylic resins, polystyrene resins, vinyl ester resins, polyester elastomers, polyurethane elastomers, polystyrene elastomers, halogenated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, aromatic or aliphatic polyketones, etc. These may be used alone or in combination of two or more.

[0342] Of these, hydrophobic resins such as polyamide-based resins, polyolefin-based resins, polyester-based resins, and polystyrene-based resins are preferred, and more preferred are polyolefin-based resins such as polyethylene-based resins, polypropylene-based resins, polycyclic olefin-based resins, and unsaturated carboxylic acid-modified polyolefin-based resins thereof.

[0343] The layer structure of the multilayer structure (6) can be any combination, such as a / b, b / a / b, a / b / a, a1 / a2 / b, a / b1 / b2, b2 / b1 / a / b1 / b2, or b2 / b1 / a / b1 / a / b1 / b2, where a represents the composition layer (6) and b represents the base resin layer (b1, b2, etc.). Furthermore, when R represents a recycled layer containing a mixture of the composition (6) and a thermoplastic resin other than EVOH resin, obtained by remelting and molding edges or defective products generated during the manufacturing process of the multilayer structure (6), the layer structure can also be b / R / a, b / R / a / b, b / R / a / R / b, b / a / R / a / b, b / R / a / R / a / R / b, or b / R / a / R / a / R / b. The total number of layers in the multilayer structure (6) is usually 2 to 15, preferably 3 to 10. In the above layer structure, an adhesive resin layer containing an adhesive resin may be interposed between the respective layers, if necessary.

[0344] Known adhesive resins can be used, and may be selected appropriately depending on the type of thermoplastic resin used in the base resin layer "b." Representative examples include modified polyolefin polymers containing carboxy groups, which are obtained by chemically bonding an unsaturated carboxylic acid or its anhydride to a polyolefin resin via addition reaction, graft reaction, or the like. Examples of modified polyolefin polymers containing carboxy groups include maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, maleic anhydride-grafted ethylene-propylene (block and random) copolymers, maleic anhydride-grafted ethylene-ethyl acrylate copolymers, maleic anhydride-grafted ethylene-vinyl acetate copolymers, maleic anhydride-grafted polycyclic olefin resins, and maleic anhydride-grafted polyolefin resins. These may be used alone or in combination of two or more.

[0345] In the present multilayer structure (6), when an adhesive resin layer is used between the present composition layer (6) and the base resin layer, it is preferable to use an adhesive resin with excellent hydrophobicity, since the adhesive resin layers are located on both sides of the present composition layer (6).

[0346] The base resin and adhesive resin may contain conventionally known plasticizers, fillers, clay (montmorillonite, etc.), colorants, antioxidants, antistatic agents, lubricants, nucleating agents, antiblocking agents, waxes, etc., within a range that does not impair the spirit of the present invention (for example, usually 30% by mass or less, preferably 10% by mass or less, with the lower limit being 0% by mass, e.g., 0 to 30% by mass, based on the total resin). These may be used alone or in combination of two or more.

[0347] The lamination of the present composition layer (6) and the above-mentioned base resin layer (including the case where an adhesive resin layer is interposed) can be carried out by a known method. For example, there can be mentioned a method of melt-extrusion laminating a base resin onto a film, sheet, etc. of the present composition (6), a method of melt-extrusion laminating the present composition (6) onto a base resin layer, a method of co-extruding the present composition (6) and a base resin, a method of dry-laminating the present composition (6) (the present composition layer (6)) and a base resin (base resin layer) using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, a polyurethane compound, etc., a method of applying a solution of the present composition (6) onto a base resin and then removing the solvent, etc. Among these, in consideration of cost and environmental considerations, it is preferable to produce the layer including the present composition layer (6) by a step of melt-molding the layer, and specifically, a co-extrusion method is preferred.

[0348] The multilayer structure (6) may be subjected to a (heat) stretching treatment, if necessary. The stretching treatment may be either uniaxial stretching or biaxial stretching, and in the case of biaxial stretching, it may be simultaneous stretching or sequential stretching. Furthermore, the stretching method may be a roll stretching method, tenter stretching method, tubular stretching method, stretch-blow method, vacuum pressure forming, or the like, whichever provides a higher stretch ratio. The stretching temperature is a temperature near the melting point of the multilayer structure (6), and is usually selected from the range of 40 to 170°C, preferably about 60 to 160°C. When the stretching temperature is equal to or higher than the lower limit, the stretchability tends to be excellent, and when the stretching temperature is equal to or lower than the upper limit, a stable stretched state tends to be easily maintained.

[0349] The stretched multilayer structure (6) may be heat-set to provide dimensional stability. Heat-setting can be performed by known means, for example, by subjecting the stretched multilayer structure (6) to heat treatment while maintaining tension, typically at 80 to 180°C, preferably 100 to 165°C, for typically 2 to 600 seconds.

[0350] When the stretched multilayer structure (6) is used as a shrink film, in order to impart heat shrinkability, the above-mentioned heat setting is not carried out, but rather a treatment such as cooling and setting the stretched multilayer structure (6) by applying cold air thereto may be carried out.

[0351] The thickness of the present multilayer structure (6) (including a stretched one), as well as the thickness of the present composition layer (6), base resin layer, and adhesive resin layer constituting the multilayer structure (6), cannot be generally determined depending on the layer configuration, type of base resin, type of adhesive resin, intended use, packaging form, required physical properties, etc., but the thickness of the present multilayer structure (6) (including a stretched one) is usually 10 to 5,000 μm, preferably 30 to 3,000 μm, and particularly preferably 50 to 2,000 μm. The present composition layer (6) is usually 1 to 500 μm, preferably 3 to 300 μm, and particularly preferably 5 to 200 μm. The base resin layer is usually 5 to 3,000 μm, preferably 10 to 2,000 μm, and particularly preferably 20 to 1,000 μm. The adhesive resin layer is usually 0.5 to 250 μm, preferably 1 to 150 μm, and particularly preferably 3 to 100 μm.

[0352] Furthermore, the thickness ratio of the present composition layer (6) to the base resin layer in the present multilayer structure (6) (present composition layer (6) / base resin layer), expressed as the ratio between the thickest layers when there are multiple layers of each, is usually 1 / 99 to 50 / 50, preferably 5 / 95 to 45 / 55, and particularly preferably 10 / 90 to 40 / 60. Furthermore, the thickness ratio of the present composition layer (6) to the adhesive resin layer in the present multilayer structure (6) (present composition layer (6) / adhesive resin layer), expressed as the ratio between the thickest layers when there are multiple layers of each, is usually 10 / 90 to 99 / 1, preferably 20 / 80 to 95 / 5, and particularly preferably 50 / 50 to 90 / 10.

[0353] <Molded Article> It is also possible to obtain a cup- or tray-shaped molded article using the present multilayer structure (6). In this case, a drawing method is usually employed, specifically vacuum forming, pressure forming, vacuum-pressure forming, plug-assisted vacuum-pressure forming, etc. Furthermore, when a tube- or bottle-shaped multilayer container (laminate structure) is obtained from a multilayer parison (a hollow tubular preform before blowing), a blow molding method is employed. Specific examples include extrusion blow molding (two-head type, mold-moving type, parison-shift type, rotary type, accumulator type, horizontal parison type, etc.), cold parison blow molding, injection blow molding, and biaxial stretch blow molding (extrusion-type cold parison biaxial stretch blow molding, injection-type cold parison biaxial stretch blow molding, injection-molding in-line biaxial stretch blow molding, etc.). The resulting laminate may be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making, deep drawing, box processing, tube processing, splitting processing, etc. as required.

[0354] <Packaging> Packaging such as a single layer film formed from the present composition (6) or a container or lid material formed from a bag, cup, tray, tube, bottle, etc., made from the present multilayer structure (6) is useful as a variety of packaging material containers (e.g., food packaging, drug packaging, cosmetic packaging) for general foods as well as seasonings such as mayonnaise and dressing, fermented foods such as miso, oily foods such as salad oil, beverages, cosmetics, pharmaceuticals, etc.

[0355] <<Seventh Aspect>> The first aspect includes the following aspects [VII-1] to [VII-13]. [VII-1] A composition containing an EVOH resin, a titanium compound, and an olefin-based elastomer (F), wherein at least a portion of the EVOH resin is derived from biomass, and the content of the titanium compound, calculated as metal, is 0.0001 ppm or more and less than 1 ppm, based on the mass of the composition. [VII-2] The composition according to [VII-1], wherein the content of the titanium compound, calculated as metal, is 0.0001 ppm or more and less than 0.8 ppm, based on the mass of the composition. [VII-3] The composition according to [VII-1] or [VII-2], wherein the content of the olefin-based elastomer (F) is 1 to 40 mass%, based on the total mass of the composition. [VII-4] The composition according to any one of [VII-1] to [VII-3], wherein the mass content ratio of the EVOH resin to the olefinic elastomer (F) [EVOH resin / (F)] is 1 / 99 to 99 / 1. [VII-5] The composition according to any one of [VII-1] to [VII-4], wherein the EVOH resin has a biobased content of 0.01 to 99%. [VII-6] The composition according to any one of [VII-1] to [VII-5], wherein the EVOH resin has a biobased content of 1 to 99%. [VII-7] A molding material comprising the composition according to any one of [VII-1] to [VII-6]. [VII-8] A multilayer structure comprising a layer comprising the composition according to any one of [VII-1] to [VII-6]. [VII-9] The multilayer structure according to [VII-8], further comprising an adhesive resin layer. [VII-10] A molded article comprising the multilayer structure described in [VII-8] or [VII-9]. [VII-11] A food package comprising the multilayer structure described in [VII-8] or [VII-9]. [VII-12] A method for producing the composition described in any of [VII-1] to [VII-6], comprising a step of mixing the EVOH resin and the titanium compound. [VII-13] A method for producing the multilayer structure described in [VII-8] or [VII-9], comprising a step of melt-molding a layer containing the composition.

[0356] The seventh aspect will be described below based on examples of modes for carrying out the seventh aspect, although the present invention is not limited to the embodiments described below.

[0357] <Composition> The composition according to the seventh aspect of the present invention (hereinafter, sometimes referred to as "the composition (7)") contains an EVOH resin as an essential component, a specific trace amount of a titanium compound, and a polyamide resin (F). Each component will be described below.

[0358] [EVOH Resin] The EVOH resin used in this embodiment is at least partly biomass-derived, and may be the same as the [EVOH Resin] described in the first embodiment. In addition, "the present composition (1)" in the description of the [EVOH Resin] in the first embodiment may be read as "the present composition (7)."

[0359] The content of the EVOH resin in the composition is usually 1% by mass or more, preferably 10% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, particularly preferably 70% by mass or more, especially preferably 75% by mass or more, and especially preferably 80% by mass or more. The upper limit of the EVOH resin content is usually 99% by mass or less, preferably 95% by mass or less, and even more preferably 93% by mass or less. When the value is within the above range, the effects of the present invention tend to be more effectively obtained.

[0360] [Titanium Compound] The titanium compound used in this embodiment may be the same as the [titanium compound] described in the first embodiment. In addition, "the present composition (1)" in the description of the [titanium compound] in the first embodiment may be read as "the present composition (7)."

[0361] [Olefin-Based Elastomer (F)] The olefin-based elastomer (F) used in this embodiment refers to an elastomer having an olefin, which is an aliphatic hydrocarbon monomer containing a carbon-carbon double bond, as its main chain, and is typically a lipophilic elastomer, which is a polymer having a number-average molecular weight of 10,000 or more. Specifically, it is an aliphatic rubber and / or an ionomer (herein excluding aliphatic rubber), and among these, aliphatic rubber is preferred. Furthermore, the aliphatic rubber or ionomer may be used alone or in combination of two or more.

[0362] The aliphatic rubber used in this embodiment will be described in detail below.

[0363] A preferred aliphatic rubber is an ethylene-α-olefin copolymer rubber having ethylene units and α-olefin units.

[0364] The α-olefin unit used in the ethylene-α-olefin copolymer rubber preferably has 3 to 8 carbon atoms, and examples of α-olefins having 3 to 8 carbon atoms include 1-propylene, 1-butene, 2-methylpropylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Of these, α-olefins having 3 to 8 carbon atoms and having a carbon-carbon double bond at a terminal carbon atom, such as 1-propylene, 1-butene, 1-hexene, and 1-octene, are preferred. The ethylene-α-olefin copolymer rubber may be one type of α-olefin copolymerized with ethylene, or two or more types of α-olefins copolymerized with ethylene.

[0365] The ethylene-α-olefin copolymer rubber may contain, in addition to ethylene units and α-olefin units having 3 to 8 carbon atoms, other monomer units such as monomer units based on a non-conjugated diene (non-conjugated diene units). Examples of the non-conjugated dienes include linear non-conjugated dienes such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-1,6-octadiene; and cyclic non-conjugated dienes such as cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, and 6-chloromethyl-5-isopropenyl-2-norbornene. These may be used alone or in combination of two or more. Of these, 5-ethylidene-2-norbornene and dicyclopentadiene are preferred.

[0366] The ethylene unit content of the ethylene-α-olefin copolymer rubber is 50 to 80 mass%, preferably 55 to 77 mass%, more preferably 60 to 75 mass%, based on the total amount of the ethylene unit content and the α-olefin unit content.

[0367] The content of the α-olefin unit in the ethylene-α-olefin copolymer rubber is 20 to 50 mass%, preferably 22 to 45 mass%, more preferably 25 to 40 mass%, based on the total amount of the ethylene unit content and the α-olefin unit content.

[0368] The ethylene unit content and the α-olefin unit content in the ethylene-α-olefin copolymer rubber can each be determined by infrared spectroscopy. The non-conjugated diene unit content of the ethylene-α-olefin copolymer rubber is usually 0 to 10 mass%, preferably 0 to 5 mass%, based on the total mass of the ethylene-α-olefin copolymer rubber. The non-conjugated diene unit content can be determined by infrared spectroscopy.

[0369] Examples of the ethylene-α-olefin copolymer rubber include random copolymers and / or block copolymers of two or more kinds of olefin monomers, copolymers of olefin monomers and diene monomers, and / or hydrogenated products thereof.

[0370] Examples of block copolymers of olefin monomers (olefin block copolymers) include ethylene-α-olefin copolymers such as ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, and ethylene-octene copolymer; propylene-α-olefin copolymers such as propylene-ethylene copolymer and propylene-butene copolymer; and butene-α-olefin copolymers such as butene-ethylene copolymer and butene-propylene copolymer. Examples of random copolymers of olefin monomers (olefin random copolymers) include those obtained by randomly copolymerizing two or more of the olefin monomers. Olefin block copolymers and olefin random copolymers are commercially available, and examples include the Tafmer (registered trademark) series manufactured by Mitsui Chemicals, Inc. and the Engage (registered trademark) series manufactured by Dow Chemical Company.

[0371] Furthermore, examples of copolymers of olefin monomers and diene monomers and / or hydrogenated products thereof include ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), butadiene rubber (BR), and the like.

[0372] The ionomer is usually a metal salt of an ethylene-unsaturated carboxylic acid copolymer, and the carboxyl groups in the ionomer are neutralized with a metal.

[0373] The density of the olefin-based elastomer (F) is usually 0.890 g / cm 3 less than 0.820 g / cm 3 0.890g / cm or more 3 Examples of the olefinic elastomer (F) that satisfies these conditions include low-crystalline ethylene-α-olefin random copolymers, EPM, and EPDM.

[0374] Furthermore, the glass transition temperature of the olefinic elastomer (F) is typically −110 to 0°C, preferably −80 to −20°C, and more preferably −70 to −40°C. Because the glass transition temperature of the olefinic elastomer (F) is much lower than room temperature (25°C) and has low crystallinity, the resulting resin composition (7) exhibits excellent flexibility over a wide temperature range, from low to room temperature. Furthermore, blending the olefinic elastomer (F) with an EVOH resin can impart a high accumulated fatigue absorption effect. Here, the glass transition temperature refers to the temperature at which the amorphous portion of the olefinic elastomer (F) transitions from a glassy state to a rubbery state, and can usually be measured using a differential scanning calorimeter according to JIS K 7121.

[0375] The melt flow rate (MFR) of the olefin elastomer (F) is usually 0.01 to 150 g / 10 min, preferably 0.1 to 50 g / 10 min, more preferably 1 to 25 g / 10 min, and even more preferably 2 to 10 g / 10 min, under conditions of 190°C and a load of 2160 g.

[0376] The closer the melt viscosity of the EVOH resin and the melt viscosity of the olefin-based elastomer (F) are, the easier the melt-kneading becomes, and the easier it is to obtain a resin composition (7) in which the olefin-based elastomer (F) is uniformly dispersed in the EVOH resin, and thus the easier it is to obtain a resin composition (7) excellent in flex resistance and transparency. Specifically, the ratio of MFR values ​​(EVOH resin / olefin-based elastomer (F)) measured under conditions of 210°C and a load of 2,160 g is usually 0.1 to 10, preferably 0.3 to 4, and more preferably 0.5 to 3.

[0377] The olefin elastomer (F) has low crystallinity or rubbery properties, and when blended with a highly crystalline EVOH resin, it is possible to obtain a resin composition (7) imparted with flexibility, and thus to provide a composition (7) having excellent flex resistance.

[0378] The content of the olefinic elastomer (F) is usually 1 to 40% by mass, preferably 3 to 30% by mass, and more preferably 5 to 25% by mass, based on the total mass of the composition (7). When the content is equal to or less than the upper limit, coloration tends to be easily suppressed, while when the content is equal to or more than the lower limit, the effect of suppressing thermal degradation tends to be obtained.

[0379] In the present composition (7), the mass content ratio of the EVOH resin to the olefin-based elastomer (F) [EVOH resin / (F)] is preferably 1 / 99 to 99 / 1, more preferably 25 / 75 to 98 / 2, still more preferably 50 / 50 to 97 / 3, particularly preferably 65 / 35 to 96 / 4, and particularly preferably 75 / 25 to 95 / 5. When the mass content ratio of the EVOH resin to the olefin-based elastomer (F) is within the above range, the discoloration suppression effect becomes even more excellent.

[0380] The total content of the EVOH resin and the olefinic elastomer (F) in the composition (7) is usually 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more. The upper limit of the total content of the EVOH resin and the olefinic elastomer (F) is the total mass of the resin composition (7) excluding the titanium compound.

[0381] It is generally known that EVOH resin deteriorates due to heat. Although the mechanism is not clear, it is thought that the thermal deterioration progresses because double bond structures are formed in the main chain of the EVOH resin during the reaction, and these sites act as reaction initiation sites, which further induce dehydration reactions, resulting in the formation of polyene structures in the main chain of the EVOH resin.

[0382] On the other hand, if a titanium compound is contained in composition (7), it is believed that composition (7) will be colored by titanium ions, and therefore it is common technical knowledge for a person skilled in the art to avoid the use of a titanium compound.

[0383] However, in this embodiment, contrary to such common technical knowledge, it has been found that a composition (7) having excellent thermal stability can be obtained by combining an olefin-based elastomer (F) with a specific trace amount of a titanium compound.

[0384] Titanium is stable as a tetravalent ion and stabilizes the EVOH resin by coordinating to the double bonds in the main chain and forming a chelate, which is thought to inhibit the formation of a polyene structure in the main chain of the EVOH resin. Furthermore, the coexistence of the olefin-based elastomer with the titanium compound results in its distribution within the EVOH resin, which is thought to inhibit the formation of additional double bonds and further improve thermal stability. Meanwhile, it is thought that a titanium compound content within a specific range tends to inhibit deterioration of the EVOH resin due to thermal decomposition caused by the titanium compound.

[0385] [Other Thermoplastic Resins] The present composition (7) may contain thermoplastic resins other than the EVOH resin and the olefin-based elastomer (F) within a range that does not impair the effects of the present invention (for example, usually 50% by mass or less of the present composition (7), preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The lower limit is 0% by mass, for example, 0 to 50% by mass). As the other thermoplastic resin, the same ones as those described in the first embodiment of the present invention as [Other Thermoplastic Resins] can be used.

[0386] [Other Compounding Agents] Composition (7) may also contain compounding agents generally compounded with EVOH resins (however, the term "compounding agent" as used herein excludes titanium compounds) within a range that does not impair the effects of the present invention (for example, 5% by mass or less, preferably 3% by mass or less, with a lower limit of 0% by mass, e.g., 0 to 5% by mass). Examples of the compounding agents include inorganic double salts (e.g., hydrotalcite, etc.), plasticizers (e.g., aliphatic polyhydric alcohols such as ethylene glycol, glycerin, and hexanediol), oxygen absorbers [e.g., inorganic oxygen absorbers such as aluminum powder and potassium sulfite; ascorbic acid, its fatty acid esters and metal salts, etc.; gallic acid; polyhydric phenols such as hydroxyl group-containing phenolaldehyde resins; terpene compounds; blends of tertiary hydrogen-containing resins and transition metals (e.g., a combination of polypropylene and cobalt); blends of carbon-carbon unsaturated bond-containing resins and transition metals; Polymeric oxygen absorbers such as polymeric oxygen absorbers, such as polymeric compounds (e.g., a combination of polybutadiene and cobalt), photooxidatively degradable resins (e.g., polyketones), anthraquinone polymers (e.g., polyvinyl anthraquinone), and combinations thereof to which photoinitiators (e.g., benzophenone), antioxidants other than those mentioned above, and deodorants (e.g., activated carbon), heat stabilizers (boric acid, phosphoric acid), light stabilizers, ultraviolet absorbers, colorants, antistatic agents, surfactants (excluding those used as lubricants), antibacterial agents, antiblocking agents, and fillers (e.g., aluminum, inorganic fillers). These compounds may be used alone or in combination of two or more.

[0387] [Method for Producing Composition] The composition (7) can be produced, for example, by mixing the EVOH resin, titanium compound, and olefin-based elastomer (F) by a known method such as a dry blending method, a melt mixing method, a solution mixing method, an impregnation method, etc. Among these, a method including a step of mixing the EVOH resin and the titanium compound is preferred. These production methods can also be used in any combination.

[0388] The dry blending method may, for example, be (I) a method in which pellets containing a pellet-shaped EVOH resin and / or an olefin-based elastomer (F) are dry-blended with a titanium compound using a tumbler or the like.

[0389] Examples of the melt mixing method include (II) a method in which a dry blend of pellets containing EVOH resin and / or olefinic elastomer (F) and a titanium compound is melt-kneaded to obtain pellets or other molded products; (III) a method in which a titanium compound is added to a melt of EVOH resin and / or olefinic elastomer (F) in a molten state, followed by melt-kneading to obtain pellets or other molded products; and a method in which a titanium compound is incorporated into EVOH resin and / or olefinic elastomer (F), and pellets having a core-sheath structure in which the EVOH resin is the core and the olefinic elastomer (F) is the sheath are prepared using the EVOH resin and / or olefinic elastomer (F), and then the pellets are melt-molded.

[0390] Examples of the solution mixing method include (IV) a method in which a solution is prepared using pellets containing commercially available EVOH resin and / or olefinic elastomer (F), a titanium compound is blended therein, the solution is coagulated and molded to form pellets, and the pellets are subjected to solid-liquid separation and drying; and (V) a method in which, in the production process of EVOH resin, a solution of olefinic elastomer (F) and / or a titanium compound is added to an ethylene-vinyl ester copolymer solution before saponification or a homogeneous solution of EVOH resin (such as a water / alcohol solution), the solution is coagulated and molded to form pellets, and the pellets are subjected to solid-liquid separation and drying.

[0391] The impregnation method may be, for example, a method in which pellets containing (VI) EVOH resin and / or olefinic elastomer (F) are brought into contact with an aqueous solution containing a titanium compound to impregnate the pellets with the titanium compound, followed by drying. The aqueous solution containing a titanium compound may be an aqueous solution of a titanium compound or a titanium compound immersed in water containing various chemicals to elute titanium ions.

[0392] In the impregnation method, the content of the titanium compound (in terms of metal) can be controlled by the concentration of the titanium compound in the aqueous solution in which the EVOH resin is immersed, the immersion temperature, the immersion time, etc. The immersion temperature and the immersion time are usually 0.5 to 48 hours, preferably 1 to 36 hours, and the immersion temperature is usually 10 to 40°C, preferably 20 to 35°C.

[0393] In each of the above-mentioned methods, it is also possible to prepare a composition (7) (master patch) having a high concentration of the titanium compound by blending the EVOH resin and / or the olefinic elastomer (F) with the titanium compound in a predetermined ratio in advance, and then blend this composition (7) (master patch) with the EVOH resin or the olefinic elastomer (F) to obtain a resin composition (7) having a desired concentration.

[0394] As the drying method in each of the above-mentioned production methods, various drying methods can be used, and either static drying or fluidized drying may be used, or these may be used in combination.

[0395] As described above, in this embodiment, the above-mentioned different methods can be combined. Among them, the melt mixing method is preferred, and method (II) is particularly preferred, in terms of productivity and the fact that a resin composition with more pronounced effects of the present invention can be obtained. Furthermore, when using the other thermoplastic resins and other compounding agents, they may be compounded by a conventional method according to the above-mentioned production method.

[0396] The shape of the present composition (7) obtained by each of the above-mentioned production methods may be any shape, but is preferably pellets. The pellets may be, for example, spherical, oval, cylindrical, die-shaped, or rectangular. They are typically oval or cylindrical. From the viewpoint of convenience when subsequently used as a molding material, the size of the pellets is such that, in the case of an oval shape, the minor axis is typically 1 to 10 mm, preferably 2 to 6 mm, and more preferably 2.5 to 5.5 mm, and the major axis is typically 1.5 to 30 mm, preferably 3 to 20 mm, and more preferably 3.5 to 10 mm. In the case of a cylindrical shape, the diameter of the base is typically 1 to 6 mm, preferably 2 to 5 mm, and the length is typically 1 to 6 mm, preferably 2 to 5 mm. In the case of a die-shaped shape, the length of one side is typically 1 to 6 mm, preferably 2 to 5 mm. The shape and size of the pelletized EVOH resin used in each of the above-mentioned production methods are also preferably similar.

[0397] The water content of the composition (7) is not particularly limited, but is usually 0.01 to 0.5% by mass, preferably 0.05 to 0.35% by mass, and particularly preferably 0.1 to 0.3% by mass.

[0398] The water content of the composition (7) is measured and calculated by the following method. １ ) was weighed on an electronic balance, dried in a hot air dryer at 150°C for 5 hours, and allowed to cool in a desiccator for 30 minutes, after which the mass (W ２ ) is weighed and calculated using the following formula: [Formula] Water content (mass%) = [(W １ -W ２ ) / W １ ]×100

[0399] When the composition (7) is in the form of pellets, it is also preferable to apply a known lubricant to the surface of the pellets in order to stabilize the feedability during melt molding. Examples of lubricants include higher fatty acids having 12 or more carbon atoms (e.g., lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc.), higher fatty acid esters (methyl esters, isopropyl esters, butyl esters, octyl esters of higher fatty acids, etc.), higher fatty acid amides (e.g., saturated higher fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, etc.; unsaturated higher fatty acid amides such as oleic acid amide, erucic acid amide, etc.; bis-higher fatty acid amides such as ethylene bisstearic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, ethylene bislauric acid amide, etc.), low-molecular-weight polyolefins (e.g., low-molecular-weight polyethylene or low-molecular-weight polypropylene having a molecular weight of about 500 to 10,000, or acid-modified products thereof), higher alcohols having 6 or more carbon atoms, ester oligomers, and fluorinated ethylene resins. These compounds can be used alone or in combination of two or more. The content of such lubricants is usually 5% by mass or less, preferably 1% by mass or less, of the present composition (7). The lower limit is usually 0% by mass, for example, 0 to 5% by mass.

[0400] The composition (7) thus obtained has excellent thermal stability, and the composition (7) was analyzed by visual analyzer IRIS VA400 (Alpha). The ratio ("1363" + "1364" + "1365" + "1366") / ("1381" + "1382") of the sum of color numbers "1363" (R: 88, G: 88, B: 56), "1364" (R: 88, G: 88, B: 72), "1365" (R: 88, G: 88, B: 88), and "1366" (R: 88, G: 88, B: 104) to the sum of color numbers "1381" (R: 88, G: 104, B: 88) and "1382" (R: 88, G: 104, B: 104), measured using a chromatograph manufactured by MOS, is usually less than 5, preferably 4 or less, and more preferably 3 or less. The lower limit is usually 0, for example, usually 0 or more but less than 5. The smaller the ratio, the more the coloration due to thermal degradation is suppressed, and the higher the thermal stability tends to be. Note that a difference of 0.5 in the ratio is very significant, as it appears as a large difference in yield in actual production.

[0401] <Molding material> The present composition (7) thus obtained is prepared into various forms such as pellets, powder, or liquid, and is provided as a molding material for various molded products. In particular, in this embodiment, when it is provided as a material for melt molding, the effects of the present invention tend to be more efficiently obtained, which is preferable.

[0402] Examples of the molded article include a monolayer film molded from the present composition (7), as well as a multilayer structure having a layer made of the present composition (7).

[0403] <Multilayer structure> The multilayer structure according to the seventh aspect of the present invention (hereinafter referred to as "the present multilayer structure (7)") contains the present composition (7) and has at least one layer made of the present composition (7). The layer made of the present composition (7) in the present multilayer structure (7) (hereinafter simply referred to as "the present composition layer (7)") may be a single layer or multiple layers. Furthermore, the present composition layer (7) can be laminated with another substrate (hereinafter, the resin used for the substrate may be abbreviated as "substrate resin") containing a thermoplastic resin other than EVOH resin as a main component to impart further strength, protect the present composition layer (7) from the effects of moisture, etc., or impart other functions.

[0404] Examples of the base resin include polyethylene-based resins such as linear low-density polyethylene, low-density polyethylene, very low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-propylene (block and random) copolymers, and ethylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymers; polypropylene-based resins such as polypropylene and propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymers; (unmodified) polyolefin-based resins such as polybutene, polypentene, and polycyclic olefin-based resins (polymers having a cyclic olefin structure in at least one of the main chain and side chain); and polyolefins obtained by dissolving these polyolefins in an unsaturated carboxylic acid or Examples include polyolefin resins in the broad sense, including modified olefin resins such as unsaturated carboxylic acid-modified polyolefin resins graft-modified with an ester thereof, ionomers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, polyester resins, polyamide resins (including copolymerized polyamides), polyvinyl chloride, polyvinylidene chloride, acrylic resins, polystyrene resins, vinyl ester resins, polyester elastomers, polyurethane elastomers, polystyrene elastomers, halogenated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, aromatic or aliphatic polyketones, etc. These may be used alone or in combination of two or more.

[0405] Of these, hydrophobic resins such as polyamide-based resins, polyolefin-based resins, polyester-based resins, and polystyrene-based resins are preferred, and more preferred are polyolefin-based resins such as polyethylene-based resins, polypropylene-based resins, polycyclic olefin-based resins, and unsaturated carboxylic acid-modified polyolefin-based resins thereof.

[0406] The layer structure of the multilayer structure (7) can be any combination, such as a / b, b / a / b, a / b / a, a1 / a2 / b, a / b1 / b2, b2 / b1 / a / b1 / b2, or b2 / b1 / a / b1 / a / b1 / b2, where a denotes the composition layer (7) and b denotes the base resin layer (b1, b2, etc.). Furthermore, when R denotes a recycled layer containing a mixture of the composition (7) and a thermoplastic resin other than EVOH resin, obtained by remelting and molding edges or defective products generated during the manufacturing process of the multilayer structure (7), b / R / a, b / R / a / b, b / R / a / R / b, b / a / R / a / b, b / R / a / R / a / R / b, or b / R / a / R / a / R / b, etc. The total number of layers in the multilayer structure (7) is usually 2 to 15, and preferably 3 to 10. In the above layer structure, an adhesive resin layer containing an adhesive resin may be interposed between the respective layers, if necessary.

[0407] Known adhesive resins can be used, and may be selected appropriately depending on the type of thermoplastic resin used in the base resin layer "b." Representative examples include modified polyolefin polymers containing carboxy groups, which are obtained by chemically bonding an unsaturated carboxylic acid or its anhydride to a polyolefin resin via addition reaction, graft reaction, or the like. Examples of modified polyolefin polymers containing carboxy groups include maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, maleic anhydride-grafted ethylene-propylene (block and random) copolymers, maleic anhydride-grafted ethylene-ethyl acrylate copolymers, maleic anhydride-grafted ethylene-vinyl acetate copolymers, maleic anhydride-grafted polycyclic olefin resins, and maleic anhydride-grafted polyolefin resins. These may be used alone or in combination of two or more.

[0408] In the present multilayer structure (7), when an adhesive resin layer is used between the present composition layer (7) and the base resin layer, it is preferable to use an adhesive resin with excellent hydrophobicity, since the adhesive resin layers are located on both sides of the present composition layer (7).

[0409] The base resin and adhesive resin may contain conventionally known plasticizers, fillers, clay (montmorillonite, etc.), colorants, antioxidants, antistatic agents, lubricants, nucleating agents, antiblocking agents, waxes, etc., within a range that does not impair the spirit of the present invention (for example, usually 30% by mass or less, preferably 10% by mass or less, with the lower limit being 0% by mass, e.g., 0 to 30% by mass, based on the total resin). These may be used alone or in combination of two or more.

[0410] The lamination of the present composition layer (7) and the above-mentioned substrate resin layer (including the case where an adhesive resin layer is interposed) can be carried out by a known method. For example, there can be mentioned a method of melt-extrusion laminating a substrate resin onto a film, sheet, etc. of the present composition (7), a method of melt-extrusion laminating the present composition (7) onto a substrate resin layer, a method of co-extruding the present composition (7) and a substrate resin, a method of dry-laminating the present composition (7) (the present composition layer (7)) and a substrate resin (substrate resin layer) using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, a polyurethane compound, etc., a method of applying a solution of the present composition (7) onto a substrate resin and then removing the solvent, etc. Among these, in consideration of cost and environmental considerations, it is preferable to produce the layer including the present composition layer (7) by a step of melt-molding the layer, and specifically, a co-extrusion method is preferred.

[0411] The multilayer structure (7) may be subjected to a (heat) stretching treatment, if necessary. The stretching treatment may be either uniaxial stretching or biaxial stretching, and in the case of biaxial stretching, it may be simultaneous stretching or sequential stretching. Furthermore, the stretching method may be a roll stretching method, tenter stretching method, tubular stretching method, stretch-blow method, vacuum pressure forming, or the like, whichever provides a higher stretch ratio. The stretching temperature is a temperature near the melting point of the multilayer structure (7), and is usually selected from the range of 40 to 170°C, preferably about 60 to 160°C. When the stretching temperature is equal to or higher than the lower limit, the stretchability tends to be excellent, and when the stretching temperature is equal to or lower than the upper limit, a stable stretched state tends to be easily maintained.

[0412] The stretched multilayer structure (7) may be heat-set to provide dimensional stability. Heat-setting can be performed by known means, for example, by subjecting the stretched multilayer structure (7) to heat treatment while maintaining tension, typically at 80 to 180°C, preferably 100 to 165°C, for typically 2 to 600 seconds.

[0413] When the stretched multilayer structure (7) is used as a shrink film, in order to impart heat shrinkability, the above-mentioned heat setting is not carried out, but rather a treatment such as cooling and setting the stretched multilayer structure (7) by applying cold air thereto may be carried out.

[0414] The thickness of the present multilayer structure (7) (including a stretched one), and further the thickness of the present composition layer (7), base resin layer, and adhesive resin layer constituting the multilayer structure (7) cannot be generally determined depending on the layer configuration, type of base resin, type of adhesive resin, intended use, packaging form, required physical properties, etc., but the thickness of the present multilayer structure (7) (including a stretched one) is usually 10 to 5,000 μm, preferably 30 to 3,000 μm, and particularly preferably 50 to 2,000 μm. The present composition layer (7) is usually 1 to 500 μm, preferably 3 to 300 μm, and particularly preferably 5 to 200 μm; the base resin layer is usually 5 to 3,000 μm, preferably 10 to 2,000 μm, and particularly preferably 20 to 1,000 μm; and the adhesive resin layer is usually 0.5 to 250 μm, preferably 1 to 150 μm, and particularly preferably 3 to 100 μm.

[0415] Furthermore, the thickness ratio of the present composition layer (7) to the base resin layer in the present multilayer structure (7) (present composition layer (7) / base resin layer), expressed as the ratio between the thickest layers when there are multiple layers of each, is usually 1 / 99 to 50 / 50, preferably 5 / 95 to 45 / 55, and particularly preferably 10 / 90 to 40 / 60. Furthermore, the thickness ratio of the present composition layer (7) to the adhesive resin layer in the present multilayer structure (7) (present composition layer (7) / adhesive resin layer), expressed as the ratio between the thickest layers when there are multiple layers of each, is usually 10 / 90 to 99 / 1, preferably 20 / 80 to 95 / 5, and particularly preferably 50 / 50 to 90 / 10.

[0416] <Molded Article> It is also possible to obtain a cup- or tray-shaped molded article using the present multilayer structure (7). In this case, a drawing method is usually employed, specifically vacuum forming, pressure forming, vacuum pressure forming, plug-assisted vacuum pressure forming, etc. Furthermore, when a tube- or bottle-shaped multilayer container (laminate structure) is obtained from a multilayer parison (a hollow tubular preform before blowing), a blow molding method is employed. Specific examples include extrusion blow molding (two-head type, mold moving type, parison shift type, rotary type, accumulator type, horizontal parison type, etc.), cold parison blow molding, injection blow molding, and biaxial stretch blow molding (extrusion type cold parison biaxial stretch blow molding, injection type cold parison biaxial stretch blow molding, injection molding in-line biaxial stretch blow molding, etc.). The resulting laminate may be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making, deep drawing, box processing, tube processing, splitting processing, etc. as required.

[0417] <Packaging> Packaging such as a single layer film formed from the present composition (7) or a container or lid material formed from a bag, cup, tray, tube, bottle, etc., made from the present multilayer structure (7) is useful as a variety of packaging material containers (e.g., food packaging, drug packaging, cosmetic packaging) for general foods as well as seasonings such as mayonnaise and dressing, fermented foods such as miso, oily foods such as salad oil, beverages, cosmetics, pharmaceuticals, etc.

[0418] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention. In the examples, "parts" and "%" are based on mass.

[0419] Prior to the examples, the following EVOH resin was prepared and manufactured. (Production of Ethylene-Vinyl Acetate Copolymer) A polymerization vessel was charged with 100 parts of vinyl acetate, the carbon in the vinyl group moiety of which was derived from biomass, and 16 parts of methanol. The system was first purged with nitriding gas, and then with ethylene, which was then introduced under pressure until the ethylene pressure reached 4.12 MPa. Under ethylene pressure, the temperature was raised to 67°C with stirring, and a peroxyester was added at a rate of 0.05 part / hr for 4 hours while the reaction was carried out for a total of 6 hours, yielding an ethylene-vinyl acetate copolymer. The polymerization rate of the resulting ethylene-vinyl acetate copolymer was 56%.

[0420] (Production of EVOH Resin) 70 parts of a methanol solution containing 0.02 equivalents of sodium hydroxide relative to the residual vinyl acetate groups in the copolymer was added to 100 parts of a methanol solution containing 50% of the above-mentioned ethylene-vinyl acetate copolymer, and a saponification reaction was carried out at 80°C for 80 minutes. Next, 100 parts of a methanol solution with a water content of 50% was added to the methanol solution of the EVOH resin under azeotropic conditions, and the methanol was distilled off until the resin concentration in the methanol / water solution of the EVOH resin reached 40%, yielding a completely transparent methanol / water homogeneous solution of the EVOH resin. The resulting methanol / water solution of the EVOH resin was then solidified into a thin plate and cut with a knife to obtain diced pellets with a side length of 3 mm. The resulting diced pellets were washed for 30 minutes with 250 parts of treated water containing 5 parts of acetic acid per 100 parts of pellets. The treated water was replaced and the washing was repeated three times. The resulting diced pellets were then washed for 30 minutes with 250 parts of water per 100 parts of pellets. The resulting pellets were washed twice with new water. The resulting die-shaped pellets were then dried at 118°C for 8 hours in a nitrogen gas stream with an oxygen concentration of 0.5% by volume or less to obtain pellets of EVOH resin (ethylene structural unit content: 32 mol%, saponification degree: 99.7 mol%, bio-based degree: 64% (content of biovinyl alcohol structural units in all vinyl alcohol structural units: 94%)).

[0421] <<First Aspect>> <Example I-1> (Production of Titanium Compound-Containing Composition Pellets) The obtained EVOH resin pellets and rutile-type titanium(IV) oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a titanium compound having an average particle size of 5 μm or less were melt-kneaded in a benchtop kneader "Xplore-HTMC15HT (15 mL capacity)" (manufactured by LeoLabo) under the following kneading conditions so that the metal-equivalent content was 0.1 ppm relative to the mass of the composition, and the extruded and discharged strand was cooled and solidified by air cooling to obtain pellets of the composition. [Kneading Conditions] - Small kneader temperature: 200°C - Screw shape: twin-screw conical type - Screw rotation: same direction - Kneading time: 10 minutes

[0422] Example I-2, Comparative Examples I-1 to I-3 Pellets of the composition were obtained in the same manner as in Example I-1, except that the content of titanium oxide was changed as shown in Table I-1 below.

[0423] The pellets of the compositions of Examples I-1 and I-2 and Comparative Examples I-1 to I-3 were subjected to the following thermal stability evaluations, and the results are shown in Table I-1.

[0424] [Evaluation of Thermal Stability] Using 5 mg of pellets of the obtained composition, the temperature difference (°C) from the temperature at which the mass decreased by 5% to the temperature at which the mass decreased by 10% was calculated using a thermogravimetric analyzer (Pyris 1 TGA, manufactured by Perkin Elmer) under conditions of a nitride atmosphere, an air flow rate of 20 mL / min, a heating rate of 10°C / min, and a temperature range of 30 to 550°C. A larger temperature difference (°C) from the temperature at which the mass decreased by 5% to the temperature at which the mass decreased by 10% means that thermal decomposition is slower and thermal stability is better.

[0425]

[0426] The results in Table I-1 above show that the compositions of Examples I-1 and I-2, which contain a specific trace amount of titanium compound, have a larger temperature difference (°C) between the temperature at which the mass is reduced by 5% and the temperature at which the mass is reduced by 10% compared to the composition of Comparative Example I-1, which does not contain a titanium compound, and the compositions of Comparative Examples I-2 and I-3, which contain a titanium compound in excess of the specific range (for example, Example I-1 has an improvement of about 1.23 times that of Comparative Example I-1, about 1.31 times that of Comparative Example I-2, and about 1.38 times that of Comparative Example I-3), and therefore have excellent thermal stability. Furthermore, multilayer structures having layers made of the compositions of Examples I-1 and I-2 also have excellent thermal stability, and molded articles and food packages containing such multilayer structures also have excellent thermal stability.

[0427] <<Second Aspect>> <Example II-1> (Production of Pellets of Composition Containing Titanium Compound and Alkaline Earth Metal Compound (A)) The obtained EVOH resin pellets, rutile-type titanium oxide (IV) (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) having an average particle size of 5 μm or less as the titanium compound, and magnesium oxide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as the alkaline earth metal compound (A) were used. The EVOH resin pellets were melt-kneaded in a benchtop kneader "Xplore-HTMC15HT (15 mL capacity)" (manufactured by RheoLabo) under the following kneading conditions so that the titanium oxide content in terms of metal was 0.04 ppm and the magnesium oxide content in terms of metal was 1,200 ppm, relative to the mass of the composition. The extruded and discharged strands were cooled and solidified by air cooling to obtain pellets of the composition. [Mixing conditions] Small mixer temperature: 200°C Screw shape: twin conical type Screw rotation: same direction Mixing time: 10 minutes

[0428] Example II-2 A composition was obtained in the same manner as in Example II-1, except that the content of magnesium oxide in terms of metal was changed to 40 ppm relative to the mass of the composition.

[0429] Example II-3 A composition was obtained in the same manner as in Example II-1, except that the content of titanium oxide in terms of metal was changed to 0.1 ppm relative to the mass of the composition, and the content of magnesium oxide in terms of metal was changed to 200 ppm relative to the mass of the composition.

[0430] Comparative Example II-1 A composition was obtained in the same manner as in Example II-1, except that the content of titanium oxide in terms of metal was changed to 3 ppm relative to the mass of the composition, and the content of magnesium oxide in terms of metal was changed to 0 ppm relative to the mass of the composition.

[0431] The compositions obtained in Examples II-1 to II-3 and Comparative Example II-1 were subjected to the following thermal stability evaluations, and the results are shown in Table II-1 below.

[0432] [Evaluation of Thermal Stability] The resulting composition was cut with nippers and pulverized to prepare a sample. Using a visual analyzer IRIS VA400 (manufactured by Alphamos), the ratio ("1381" + "1382") / ("1636" + "1637" + "1638") of the sum of color numbers "1381" (R: 88, G: 104, B: 88) and "1382" (R: 88, G: 104, B: 104) to the sum of color numbers "1636" (R: 104, G: 104, B: 72), "1637" (R: 104, G: 104, B: 88), and "1638" (R: 104, G: 104, B: 104) was evaluated. Color numbers 1636, 1637, and 1638 are light yellow colors, while color numbers 1381 and 1382 are deep yellow colors. The smaller this ratio, the more suppressed yellowing due to thermal degradation is, indicating higher thermal stability.

[0433]

[0434] The results in Table II-1 above show that the compositions of Examples II-1 to II-3, which contain a specific trace amount of titanium compound and the alkaline earth metal compound (A) and titanium compound in a specific mass ratio, have a lower proportion of deep yellowish color and are superior in thermal stability compared to the composition of Comparative Example II-1, which does not contain a specific trace amount of titanium compound and the alkaline earth metal compound (A) and titanium compound in the specific mass ratio. Furthermore, multilayer structures having layers made of the compositions of Examples II-1 to II-3 also have excellent thermal stability, and molded articles and food packages containing such multilayer structures also have excellent thermal stability.

[0435] <<Third Aspect>> <Example III-1> (Production of Composition Pellets Containing a Titanium Compound and a Metal Compound (B) Belonging to a Specific Periodic d Block) The obtained EVOH resin pellets were used along with rutile-type titanium(IV) oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) having an average particle size of 5 μm or less as the titanium compound, and zinc caprylate "Z-08N" (manufactured by Nitto Kasei Kogyo Co., Ltd.) as the metal compound (B) belonging to a specific periodic d block. The EVOH resin pellets were melt-kneaded in a benchtop kneader "Xplore-HTMC15HT (15 mL capacity)" (manufactured by LeoLabo) under the following kneading conditions so that the titanium oxide content in terms of metal was 0.04 ppm and the zinc caprylate content in terms of metal was 800 ppm, relative to the mass of the composition. The extruded and discharged strands were cooled and solidified by air cooling to obtain pellets of the composition. [Mixing conditions] Small mixer temperature: 200°C Screw shape: twin conical type Screw rotation: same direction Mixing time: 10 minutes

[0436] Example III-2 A composition was obtained in the same manner as in Example III-1, except that the content of zinc caprylate in terms of metal was changed to 0.1 ppm relative to the mass of the composition.

[0437] Example III-3 A composition was obtained in the same manner as in Example III-1, except that the content of titanium oxide in terms of metal relative to the mass of the composition was changed to 0.1 ppm and the content of zinc caprylate in terms of metal relative to the mass of the composition was changed to 200 ppm.

[0438] Comparative Example III-1 A composition was obtained in the same manner as in Example III-1, except that the content of titanium oxide in terms of metal was changed to 3 ppm relative to the mass of the composition, and the content of zinc caprylate in terms of metal was changed to 0 ppm relative to the mass of the composition.

[0439] The compositions of Examples III-1 to III-3 and Comparative Example III-1 were subjected to the following thermal stability evaluations, and the results are shown in Table III-1.

[0440] [Evaluation of Thermal Stability] The resulting composition was cut with nippers and pulverized to prepare a sample. Using a visual analyzer IRIS VA400 (manufactured by Alphamos), the ratio ("1347" + "1348" + "1349") / ("1381" + "1382") of the sum of color numbers "1347" (R: 88, G: 72, B: 56), "1348" (R: 88, G: 72, B: 72), and "1349" (R: 88, G: 72, B: 88) to the sum of color numbers "1381" (R: 88, G: 104, B: 88) and "1382" (R: 88, G: 104, B: 104) was evaluated. Color numbers 1381 and 1382 are colors with a light yellow tint, and color numbers 1347, 1348, and 1349 are colors with a deep yellow tint. The smaller this ratio, the more suppressed yellowing due to thermal degradation is, indicating higher thermal stability.

[0441]

[0442] The results in Table III-1 show that the compositions of Examples III-1 to III-3, which contain a specific trace amount of titanium compound and the metal compound belonging to the specific periodic d block and titanium compound in a specific mass ratio, have a lower proportion of deep yellowish color and are superior in thermal stability compared to the composition of Comparative Example III-1, which does not contain a specific trace amount of titanium compound and the metal compound belonging to the specific periodic d block and titanium compound in the specific mass ratio. Furthermore, multilayer structures having layers made of the compositions of Examples III-1 to III-3 also have excellent thermal stability, and molded articles and food packages containing such multilayer structures also have excellent thermal stability.

[0443] <<Fourth Aspect>> <Example IV-1> (Production of Pellets of Composition Containing Titanium Compound and Lubricant (C)) The obtained EVOH resin pellets, rutile-type titanium oxide (IV) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) having an average particle size of 5 μm or less as the titanium compound, and lubricant "Alflo H50-FP" (manufactured by NOF Corporation) were used. The EVOH resin pellets were melt-kneaded in a benchtop kneader "Xplore-HTMC15HT (15 mL capacity)" (manufactured by LeoLabo) under the following kneading conditions so that the titanium oxide content in terms of metal was 0.04 ppm relative to the mass of the composition and the lubricant (C) content was 8000 ppm relative to the mass of the composition. The extruded and discharged strands were cooled and solidified by air cooling to obtain pellets of the composition. [Mixing conditions] Small mixer temperature: 200°C Screw shape: twin conical type Screw rotation: same direction Mixing time: 10 minutes

[0444] Example IV-2 A composition was obtained in the same manner as in Example IV-1, except that the content of the lubricant (C) was changed to 40 ppm based on the mass of the composition.

[0445] Example IV-3 A composition was obtained in the same manner as in Example IV-1, except that the content of titanium oxide in terms of metal was changed to 0.1 ppm relative to the mass of the composition, and the content of lubricant (C) was changed to 200 ppm relative to the mass of the composition.

[0446] Comparative Example IV-1 A composition was obtained in the same manner as in Example IV-1, except that the content of titanium oxide in terms of metal was changed to 3 ppm relative to the mass of the composition, and the content of lubricant (C) was changed to 0 ppm relative to the mass of the composition.

[0447] The compositions of Examples IV-1 to IV-3 and Comparative Example IV-1 were subjected to the following thermal stability evaluations, and the results are shown in Table IV-1.

[0448] [Evaluation of Thermal Stability] The obtained composition was cut with nippers and crushed to prepare a sample. The sample was analyzed by a visual analyzer IRIS VA400 (Alpha Using a color grading scale manufactured by MOS, the ratio ("1363" + "1364" + "1365") / ("1636" + "1637" + "1638") of the sum of color numbers "1636" (R: 104, G: 104, B: 72), "1637" (R: 104, G: 104, B: 88), and "1638" (R: 104, G: 104, B: 104) to the sum of color numbers "1363" (R: 88, G: 88, B: 56), "1364" (R: 88, G: 88, B: 72), and "1365" (R: 88, G: 88, B: 88) was evaluated. Color numbers 1636, 1637, and 1638 are colors with a light yellow tint, while color numbers 1363, 1364, and 1365 are colors with a deep yellow tint. The smaller this ratio, the more suppressed the yellow coloring is, which means higher thermal stability.

[0449]

[0450] The results in Table IV-1 above show that the compositions of Examples IV-1 to IV-3, which contain a specific trace amount of titanium compound and the lubricant (C) and titanium compound in a specific mass ratio, have a lower proportion of deep yellowish color and are superior in thermal stability compared to the composition of Comparative Example IV-1, which does not contain a specific trace amount of titanium compound and the lubricant (C) and titanium compound in a specific mass ratio. Furthermore, multilayer structures having layers made of the compositions of Examples IV-1 to IV-3 also have excellent thermal stability, and molded articles and food packages containing such multilayer structures also have excellent thermal stability.

[0451] <<Fifth Aspect>> <Example V-1> (Production of Pellets of a Composition Containing a Titanium Compound and a Polyamide-Based Resin (D)) The obtained EVOH resin pellets were used, along with rutile-type titanium oxide (IV) having an average particle size of 5 μm or less (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as the titanium compound, and "1028EN" (manufactured by DSM) as the polyamide-based resin (D). The EVOH resin pellets were dry-blended so that the content of the polyamide-based resin was 20% relative to the total composition, and the mixture was melt-kneaded in a benchtop kneader "Xplore-HTMC15HT (15 mL capacity)" (manufactured by LeoLabo) under the following kneading conditions so that the content of the titanium oxide in terms of metal was 0.1 ppm relative to the mass of the composition. The extruded and discharged strands were cooled and solidified by air cooling to obtain pellets of the composition. [Mixing conditions] Small mixer temperature: 200°C Screw shape: twin conical type Screw rotation: same direction Mixing time: 10 minutes

[0452] Example V-2 A composition was obtained in the same manner as in Example V-1, except that the content of titanium oxide in terms of metal was changed to 0.5 ppm relative to the mass of the composition.

[0453] Comparative Example V-1 A composition was obtained in the same manner as in Example V-1, except that titanium oxide was not used.

[0454] Comparative Example V-2 A composition was obtained in the same manner as in Example V-1, except that the content of titanium oxide in terms of metal was changed to 3 ppm relative to the mass of the composition.

[0455] The compositions of Examples V-1 and V-2 and Comparative Examples V-1 and V-2 were evaluated for extrusion processability, and the following thermal stability was also evaluated using the compositions obtained. The results are shown in Table V-1 below.

[0456] [Evaluation of Extrusion Processability] The mixture was melt-kneaded using a tabletop kneader "Xplore-HTMC15HT (15 mL capacity)" (manufactured by LeoLabo), and the extruded and discharged strands were cooled and solidified by air cooling to determine whether or not a mixture could be obtained as extrusion processability. If a strand could be obtained, the result was rated as "Good (◯)", and if not, the result was rated as "Bad (×)".

[0457] [Evaluation of Thermal Stability] The obtained composition was cut with nippers and pulverized to prepare a sample. Using a visual analyzer IRIS VA400 (manufactured by Alphamos), the ratio ("1091" + "1092" + "1093") / ("1620" + "1621") of the sum of color numbers "1091" (R: 72, G: 72, B: 56), "1092" (R: 72, G: 72, B: 72), and "1093" (R: 72, G: 72, B: 88) to the sum of color numbers "1620" (R: 104, G: 88, B: 72) and "1621" (R: 104, G: 88, B: 88) was evaluated. Color numbers 1620 and 1621 are colors with a light yellow tint, while color numbers 1091, 1092, and 1093 are colors with a deep yellow tint. The smaller this ratio, the more suppressed yellowing due to thermal degradation is, indicating higher thermal stability.

[0458]

[0459] The results of Table V-1 above show that the compositions of Examples V-1 and V-2, which contain a polyamide resin (D) and a specific trace amount of a titanium compound, have a lower proportion of deep yellowness (for example, about 33% to 66% lower in Examples V-1 and V-2 than in Comparative Examples V-1 and V-2), and are excellent in thermal stability, compared to the compositions of Comparative Examples V-1 and V-2, which do not contain a specific trace amount of a titanium compound. Furthermore, multilayer structures having layers made of the compositions of Examples V-1 and V-2 also have excellent thermal stability, and molded articles and food packages containing such multilayer structures also have excellent thermal stability.

[0460] <<Sixth Aspect>> <Example VI-1> (Production of Pellets of a Composition Containing a Titanium Compound and a Polyolefin Resin (E)) The obtained EVOH resin pellets were used, along with rutile-type titanium oxide (IV) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) having an average particle size of 5 μm or less as the titanium compound, and "Novatec PP (EA9)" (manufactured by DSM) as the polyolefin resin (E). The EVOH resin pellets were dry-blended so that the content of the polyolefin resin was 95% based on the total composition, and the mixture was melt-kneaded in a benchtop kneader "Xplore-HTMC15HT (15 mL capacity)" (manufactured by LeoLabo) under the following kneading conditions so that the titanium oxide content, calculated as metal, was 0.1 ppm based on the mass of the composition. The extruded and discharged strands were cooled and solidified by air cooling to obtain pellets of the composition. [Mixing conditions] Small mixer temperature: 200°C Screw shape: twin conical type Screw rotation: same direction Mixing time: 10 minutes

[0461] Example VI-2 A composition was obtained in the same manner as in Example VI-1, except that the content of titanium oxide was changed to 0.5 ppm in terms of metal relative to the mass of the composition.

[0462] Comparative Example VI-1 A composition was obtained in the same manner as in Example VI-1, except that titanium oxide was not used.

[0463] Comparative Example VI-2 A composition was obtained in the same manner as in Example VI-1, except that the content of titanium oxide was changed to 3 ppm in terms of metal relative to the mass of the composition.

[0464] Comparative Example VI-3 A composition was obtained without using EVOH resin, and containing titanium oxide in an amount of 0.1 ppm in terms of metal relative to the mass of the polyolefin resin composition.

[0465] The resulting Examples VI-1 and VI-2 and Comparative Examples VI-1 to VI-3 were evaluated for coloration, and the results are shown in Table VI-1 below.

[0466] [Coloration Evaluation] The obtained composition was cut with nippers and crushed to prepare a sample. Using a visual analyzer IRIS VA400 (manufactured by Alphamos), the ratio of the sum of color numbers "1108" (R: 72, G: 88, B: 72) and "1109" (R: 72, G: 88, B: 88) to color number "1331" (R: 88, G: 56, B: 56) ("1108" + "1109" / "1331") was evaluated. Color number "1331" is a color with a light yellowish tint, and color numbers "1108" and "1109" are colors with a deep yellowish tint. The smaller this ratio, the more suppressed yellowish coloration due to thermal degradation is, indicating higher thermal stability.

[0467]

[0468] The results of Table VI-1 above show that the compositions of Examples VI-1 and VI-2, which contain a polyolefin resin (E) and a specific trace amount of a titanium compound, have a lower proportion of deep yellowness (for example, a 50% decrease in the proportion of Examples VI-1 and VI-2 compared to Comparative Examples VI-1 and VI-2) and are superior in thermal stability compared to the compositions of Comparative Examples VI-1 and VI-2, which do not contain a specific trace amount of a titanium compound, and the composition of Comparative Example VI-3, which does not contain an EVOH resin. Furthermore, multilayer structures having layers made of the compositions of Examples VI-1 and VI-2 also have excellent thermal stability, and molded articles and food packages containing such multilayer structures also have excellent thermal stability.

[0469] <<Seventh Aspect>> <Example VII-1> (Production of Pellets of a Composition Containing a Titanium Compound and an Olefin-Based Elastomer (F)) The obtained EVOH resin pellets were used, along with rutile-type titanium oxide (IV) having an average particle size of 5 μm or less (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as the titanium compound, and "Tafmer: A4085S (random copolymer)" (manufactured by Mitsui Chemicals, Inc.) as the olefin-based elastomer (F). The EVOH resin pellets were dry-blended with the olefin-based elastomer so that the content of the olefin-based elastomer was 20% based on the total composition, and the mixture was melt-kneaded in a benchtop kneader "Xplore-HTMC15HT (15 mL capacity)" (manufactured by LeoLabo) under the following kneading conditions so that the titanium oxide content, calculated as metal, was 0.1 ppm based on the mass of the composition. The extruded and discharged strands were cooled and solidified by air cooling to obtain pellets of the composition. [Mixing conditions] Small mixer temperature: 200°C Screw shape: twin conical type Screw rotation: same direction Mixing time: 10 minutes

[0470] Example VII-2 A composition was obtained in the same manner as in Example VII-1, except that the content of titanium oxide in terms of metal was changed to 0.5 ppm relative to the mass of the composition.

[0471] Comparative Example VII-1: A composition was obtained in the same manner as in Example VII-1, except that titanium oxide was not used. Comparative Example VII-2: A composition was obtained in the same manner as in Example VII-1, except that the content of titanium oxide in terms of metal was changed to 3 ppm relative to the mass of the composition.

[0472] The resulting Examples VII-1 and 2 and Comparative Examples VII-1 and 2 were evaluated for coloration, and the results are shown in Table VII-1 below.

[0473] [Evaluation of Coloring] The obtained composition was cut with nippers and crushed to prepare a sample. The sample was analyzed by a visual analyzer IRIS VA400 (Alpha Using a color grading scale manufactured by MOS, the ratio of the sum of color numbers "1363" (R: 88, G: 88, B: 56), color number "1364" (R: 88, G: 88, B: 72), color number "1365" (R: 88, G: 88, B: 88), and color number "1366" (R: 88, G: 88, B: 104) to the sum of color numbers "1381" (R: 88, G: 104, B: 88) and "1382" (R: 88, G: 104, B: 104) ("1363" + "1364" + "1365" + "1366") / ("1381" + "1382") was evaluated. Color numbers 1381 and 1382 are colors with a light yellow tint, and color numbers 1363, 1364, 1365, and 1366 are colors with a deep yellow tint. The smaller this ratio, the more suppressed yellowing due to thermal degradation is, indicating higher thermal stability.

[0474]

[0475] The results in Table VII-1 above show that the compositions of Examples VII-1 and VII-2, which contain an olefinic elastomer (F) and a specific trace amount of a titanium compound, have a lower proportion of deep yellowness than the compositions of Comparative Examples VII-1 and VII-2, which do not contain a specific trace amount of a titanium compound (for example, Example VII-1 has a lower proportion of deep yellowness than Comparative Example VII-1, and a lower proportion of deep yellowness than Comparative Example VII-2), and are therefore excellent in thermal stability. Furthermore, multilayer structures having layers made of the compositions of Examples VII-1 and VII-2 also have excellent thermal stability, and molded articles and food packages containing such multilayer structures also have excellent thermal stability.

[0476] Although the above examples show specific embodiments of the present invention, the examples are merely illustrative and should not be construed as limiting. Various modifications that are obvious to those skilled in the art are intended to fall within the scope of the present invention.

[0477] Because the present composition has excellent thermal stability, it is useful as a packaging material for various foods, as well as seasonings such as mayonnaise and dressings, fermented foods such as miso, oily foods such as salad oil, beverages, cosmetics, pharmaceuticals, etc.

Claims

1. A composition containing an ethylene-vinyl alcohol copolymer and a titanium compound, wherein at least a portion of the ethylene-vinyl alcohol copolymer is derived from biomass, and the titanium compound has a metal-equivalent content of 0.0001 ppm or more and less than 1 ppm based on the mass of the composition.

2. The composition according to claim 1, wherein the content of said titanium compound in terms of metal is 0.0001 ppm or more and 0.8 ppm or less based on the mass of said composition.

3. The composition according to claim 1 or 2, further comprising an alkaline earth metal compound (A), and the mass ratio of the content of the alkaline earth metal compound (A) in terms of the metal to the content of the titanium compound in terms of the metal is 500 to 55,000.

4. The composition according to any one of claims 1 to 3, further comprising a metal compound (B) belonging to d block, Period 4 of the long form periodic table other than the titanium compound, and the mass ratio of the metal-equivalent content of the metal compound (B) belonging to d block, Period 4 of the long form periodic table to the metal-equivalent content of the titanium compound is 2 to 45,000.

5. The composition according to any one of claims 1 to 4, further comprising a lubricant (C) other than the alkaline earth metal compound (A), and the mass ratio of the content of the lubricant (C) to the content of the titanium compound in terms of metal is 500 to 280,000.

6. The composition according to any one of claims 1 to 5, further comprising a polyamide resin (D).

7. The composition according to any one of claims 1 to 6, further comprising a polyolefin resin (E) in the composition.

8. The composition according to any one of claims 1 to 7, further comprising an olefin-based elastomer (F) in the composition.

9. The composition of any one of claims 1 to 8, wherein the ethylene-vinyl alcohol copolymer has a bio-based content of 0.01 to 99%.

10. The composition of any one of claims 1 to 8, wherein the ethylene-vinyl alcohol copolymer has a bio-based content of 1 to 99%.

11. A molding material comprising the composition according to any one of claims 1 to 10.

12. A multilayer structure having a layer comprising the composition according to any one of claims 1 to 10.

13. The multilayer structure of claim 12, further comprising an adhesive resin layer.

14. A molded article comprising the multilayer structure according to claim 12 or 13.

15. A food package comprising the multi-layer structure of claim 12 or 13.

16. A method for producing the composition according to any one of claims 1 to 10, comprising the step of mixing said ethylene-vinyl alcohol copolymer and said titanium compound.

17. A method for producing a multi-layer structure according to claim 12 or 13, comprising the step of melt-molding a layer containing said composition.

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