Modifiers for resin compositions, molded articles, and polyolefin resin / starch composite compositions

Abstract

To provide a polyolefin resin / starch composite composition that is suppressed from contaminating a production apparatus and has excellent moldability.SOLUTION: Provided is a resin composition comprising a polyolefin resin (A), a thermoplastic starch (B), and at least one resin (C) selected from the group consisting of a rosin-based resin, a petroleum resin, and a terpene resin.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition, a molded article, and a modifier for a polyolefin resin / starch composite composition.

Background Art

[0002] Since polyolefin resins have excellent mechanical properties, they are processed into injection molded products, hollow molded products, films, sheets, fibers, etc. and are widely used in various applications.

[0003] In recent years, there has been an increasing concern about the global environment, and there is a growing trend to use materials that are as environmentally friendly as possible for plastic molded articles. As such materials, polyolefin resin / starch composite compositions in which a starch-based material and a polyolefin resin are compounded are known as typical examples.

[0004] However, conventional polyolefin resin / starch composite compositions have a problem that it is difficult to obtain a molded article with good mechanical properties because the affinity between the polyolefin resin and the starch-based material is poor and it is difficult to form a uniform composite.

[0005] In response to the above problem, Patent Document 1 proposes that by using maleic anhydride-modified polyolefin as a compatibilizer in a polyolefin resin / starch composite composition, the compatibility between the polyolefin resin and the starch-based material can be improved, and a molded article with good mechanical properties can be obtained.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0008] The present invention has been made in view of the above circumstances, and aims to provide a polyolefin resin / starch composite composition that suppresses contamination of manufacturing equipment and has excellent moldability.

[0009] Furthermore, the present invention aims to provide a novel modifier that can suppress contamination of manufacturing equipment in the production of polyolefin resin / starch composite compositions and improve the moldability of polyolefin resin / starch composite compositions. [Means for solving the problem]

[0010] As a result of diligent research, the inventors have found that the above problems can be solved by using a specific resin in a resin composition containing polyolefin resin and thermoplastic starch. Furthermore, the inventors have found that the above problems can be solved by a modifier containing a specific resin. In other words, the present invention relates to the following resin composition, molded article, and modifier.

[0011] 1. Polyolefin resin (A), thermoplastic starch (B) and A resin composition comprising at least one resin (C) selected from the group consisting of rosin resins, petroleum resins, and terpene resins.

[0012] 2. The resin composition according to item 1 above, wherein component (A) is at least one selected from the group consisting of polyethylene and polypropylene.

[0013] 3. The resin composition according to item 1 or 2 above, wherein component (C) is a rosin-based resin.

[0014] 4. A molded article obtained from any one of the resin compositions described in items 1 to 3 above.

[0015] 5. A modifier for polyolefin resin / starch composite compositions comprising at least one resin (C) selected from the group consisting of rosin resins, petroleum resins, and terpene resins.

[0016] 6. The modifier for polyolefin resin / starch composite composition according to item 5, wherein the polyolefin resin is at least one selected from the group consisting of polyethylene and polypropylene.

[0017] 7. A modifier for polyolefin resin / starch composite compositions according to item 5 or 6 above, wherein component (C) is a rosin-based resin. [Effects of the Invention]

[0018] The resin composition of the present invention exhibits excellent fluidity during melting, resulting in superior moldability. Furthermore, contamination of manufacturing equipment is suppressed during the production of the resin composition.

[0019] The modifier of the present invention, when used in a polyolefin resin / starch composite composition, improves the fluidity of the composite composition during melting, thereby improving its moldability. Furthermore, the modifier can suppress contamination of manufacturing equipment during the production of the polyolefin resin / starch composite composition. [Best Mode for Carrying Out the Invention]

[0020] [Resin composition] The resin composition of the present invention comprises a polyolefin resin (A) (hereinafter also referred to as component (A)), thermoplastic starch (B) (hereinafter also referred to as component (B)), and resin (C) (hereinafter also referred to as component (C)).

[0021] <Polyolefin resin (A)> (A) component is not particularly limited, and various known ones can be used. (A) component may be used alone or in combination of two or more.

[0022] (A) component includes, for example, homopolymers of α-olefins having about 2 to 8 carbon atoms such as ethylene, propylene, 1-butene; binary or ternary (co)polymers of the above α-olefins; binary or ternary (co)polymers of the above α-olefins and α-olefins having about 9 to 18 carbon atoms, unsaturated carboxylic acids, (meth)acrylic acid esters, vinyl acetate, etc.

[0023] The above α-olefins having about 2 to 18 carbon atoms include, for example, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, 1-decene, 1-octadecene, etc. The above unsaturated carboxylic acids include, for example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, etc. The above (meth)acrylic acid esters include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, isooctyl (meth)acrylate, etc.

[0024] (A) component includes, for example, ethylene-based resins such as polyethylene, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-heptene copolymer, ethylene-1-octene copolymer; propylene-based resins such as polypropylene, propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-4-methyl-1-pentene copolymer, propylene-ethylene-1-hexene copolymer; 1-butene-based resins such as 1-butene homopolymer, 1-butene-ethylene copolymer, 1-butene-propylene copolymer; 4-methyl-1-pentene-based resins such as 4-methyl-1-pentene homopolymer, 4-methyl-1-pentene-ethylene copolymer, etc.

[0025] (A) component is preferably a homopolymer of α-olefins having about 2 to 8 carbon atoms such as ethylene, propylene, 1-butene, etc. from the viewpoint of excellent molding processability; a binary or ternary (co)polymer of the above α-olefins; a binary or ternary (co)polymer of the above α-olefins and α-olefins having about 9 to 18 carbon atoms such as 1-decene, 1-octadecene, etc. From the same viewpoint, at least one selected from the group consisting of polyethylene and polypropylene is more preferable.

[0026] <Thermoplastic starch (B)> (B) component is not particularly limited as long as it is thermoplastic starch (TPS), and various known ones can be used. (B) component may be used alone or in combination of two or more.

[0027] (B) component can be obtained, for example, by heating and kneading starch together with a plasticizer.

[0028] The above starch is not particularly limited, and various known ones can be used. The above starch includes, for example, unprocessed starch (raw starch), processed starch, etc. The above starch may be used alone or in combination of two or more.

[0029] Examples of the above-mentioned unprocessed starches (raw starches) include corn starch, bean starch, tapioca starch, potato starch, wheat starch, rice starch, cassava starch, water chestnut starch, lotus starch, sago starch, bracken starch, and kudzu starch.

[0030] Examples of the modified starches mentioned above include physically treated starches and chemically treated starches. Examples of physically treated starches include pregelatinized starches, moist heat-treated starches, and oil-processed starches.

[0031] Examples of the chemically treated starches mentioned above include oxidized starch, acetoacetic acid esterified starch, acetate esterified starch, hydroxymethyl etherified starch, hydroxypropyl etherified starch, carboxymethyl etherified starch, allyl etherified starch, methyl etherified starch, succinate esterified starch, xanthogene acetate esterified starch, nitrate esterified starch, urea phosphate esterified starch, phosphate esterified starch, phosphate cross-linked starch, formaldehyde cross-linked starch, acrolein cross-linked starch, epichlorohydrin cross-linked starch, and cationized starch.

[0032] The plasticizer described above is not particularly limited, and various known plasticizers can be used. Examples of such plasticizers include polyhydric alcohols, hydrogen-bonding organic compounds that do not have hydroxyl groups, anhydrides of sugar alcohols, animal proteins, plant proteins, aliphatic acids, and ester compounds. Examples of polyhydric alcohols include glycerin, diglycerin, polyglycerin, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, glucose, fructose, sorbitol, sucrose, trehalose, and maltose. Examples of aliphatic acids include ethylene acrylic acid, ethylene maleic acid, butadiene acrylic acid, butadiene maleic acid, propylene acrylic acid, propylene maleic acid, and other hydrocarbon base acids. Examples of the ester compounds include phthalates, succinates, glyceryl acetate (mono, di, and tri forms), glyceryl propionate (mono, di, and tri forms), butanoates, lactic acids, citrates, adipic acids, stearates, and oleates. The plasticizers may be used individually or in combination of two or more.

[0033] (B) Component can be obtained by various known means. Specifically, for example, it can be produced by kneading the above starch and the above plasticizer at 80°C to 230°C.

[0034] <Resin (C)> Component (C) is not particularly limited as long as it is at least one resin selected from the group consisting of rosin resins, petroleum resins, and terpene resins, and various known resins can be used. Component (C) may be used alone or in combination of two or more.

[0035] The resin composition of the present invention, by using component (C), has improved fluidity during melting, making it easier to mold and resulting in excellent moldability. Furthermore, by using component (C) in the resin composition of the present invention, components (A) and (B) mix more easily during manufacturing, thus suppressing contamination of manufacturing equipment.

[0036] (Rosin-based resin) Examples of the rosin-based resins mentioned above include natural rosin (gum rosin, tall oil rosin, wood rosin) derived from species such as Pinus massoniana, Pinus elliottii, Pinus merkusii, Pinus caribaea, Pinus kesiya, Pinus taeda, and Pinus palustris; refined rosin (hereinafter, natural rosin and refined rosin are collectively referred to as unmodified rosin); hydrogenated rosin; disproportionated rosin; polymerized rosin; α,β-unsaturated carboxylic acid-modified rosin; esterified products of these rosins (hereinafter also referred to as rosin esters); rosinphenol resins; and rosin diols.

[0037] (Refined rosin) The purified rosin described above can be obtained using various known methods. Specifically, it can be obtained using various known purification methods such as distillation, extraction, recrystallization, and adsorption. Distillation methods include, for example, distilling the natural rosin at a temperature of approximately 200-300°C and under reduced pressure of approximately 0.01-3 kPa. Extraction methods include, for example, making an alkaline aqueous solution of the natural rosin, extracting the insoluble unsaponifiable matter with various organic solvents, and then neutralizing the aqueous layer. Recrystallization methods include, for example, dissolving the natural rosin in an organic solvent as a good solvent, then distilling off the solvent to obtain a concentrated solution, and then adding an organic solvent as a poor solvent. Examples of good solvents include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; chlorinated hydrocarbon solvents such as chloroform; lower alcohols; ketones such as acetone; and acetic acid esters such as ethyl acetate. Examples of poor solvents include n-hexane, n-heptane, cyclohexane, and isooctane. Adsorption methods include, for example, contacting a porous adsorbent with the above-mentioned natural rosin in a molten state or in a solution form dissolved in an organic solvent. Examples of porous adsorbents include activated carbon, metal oxides such as alumina, zirconia, silica, molecular sieves, zeolites, and porous clay with micropores.

[0038] Furthermore, the purified rosin may be subjected to the disproportionation and hydrogenation operations described later, either individually or in combination of two or more, as described below.

[0039] (Disproportionated rosin) The above-mentioned disproportionated rosin can be obtained by various known means. Specifically, for example, it can be obtained by heating the above-mentioned unmodified rosin in the presence of a disproportionation catalyst (disproportionation). As the disproportionation catalyst, various known supported catalysts such as palladium-carbon, rhodium-carbon, and platinum-carbon; metal powders such as nickel and platinum; and various known iodides such as iodine and iron iodide can be used. The amount of catalyst used is usually about 0.01 to 5 parts by mass, preferably about 0.01 to 1 part by mass, per 100 parts by mass of unmodified rosin. The reaction temperature is about 100 to 300°C, preferably about 150 to 290°C.

[0040] Furthermore, the disproportionated rosin may be subjected to the purification, disproportionation, and hydrogenation operations described later, either individually or in combination of two or more.

[0041] (Hydrogenated rosin) The above-mentioned hydrogenated rosin can be obtained using various known methods. Specifically, for example, it can be obtained by hydrogenating the above-mentioned unmodified rosin using known hydrogenation conditions. Examples of hydrogenation conditions include heating the above-mentioned unmodified rosin to about 100 to 300°C at a hydrogen pressure of about 2 to 20 MPa in the presence of a hydrogenation catalyst. It is also preferable that the hydrogen pressure be about 5 to 20 MPa and the reaction temperature be about 150 to 300°C. Various known hydrogenation catalysts such as supported catalysts and metal powders can be used. Examples of supported catalysts include palladium-carbon, rhodium-carbon, ruthenium-carbon, and platinum-carbon. Examples of metal powders include nickel and platinum. Among these, palladium, rhodium, ruthenium, and platinum-based catalysts are preferred because they increase the hydrogenation rate of the above-mentioned unmodified rosin and shorten the hydrogenation time. The amount of hydrogenation catalyst used is typically about 0.01 to 5 parts by mass, preferably about 0.01 to 2 parts by mass, per 100 parts by mass of the unmodified rosin.

[0042] The above hydrogenation may be carried out with the unmodified rosin dissolved in a solvent, if necessary. The solvent used is not particularly limited, but any solvent that is inert to the reaction and readily dissolves the raw materials and products is acceptable. Specifically, for example, one or more of the following can be used: cyclohexane, n-hexane, n-heptane, decalin, tetrahydrofuran, dioxane, etc. The amount of solvent used is not particularly limited, but it is usually sufficient to use such a solvent that the solid content relative to the unmodified rosin is 10% by mass or more, preferably in the range of 10 to 70% by mass.

[0043] Furthermore, the hydrogenated rosin obtained may be subjected to the purification, hydrogenation, and disproportionation operations individually or in combination of two or more.

[0044] Furthermore, to improve the color tone, the purified rosin, hydrogenated rosin, and disproportionated rosin may be subjected to further dehydrogenation treatment. The dehydrogenation treatment is not particularly limited, and ordinary conditions can be used. For example, the dehydrogenation treatment is carried out in a sealed container in the presence of a dehydrogenation catalyst, using the purified rosin, hydrogenated rosin, and disproportionated rosin, with an initial hydrogen pressure of less than 10 kg / cm2, preferably less than 5 kg / cm2, and a reaction temperature of about 100 to 300°C, preferably in the range of a lower limit of 200°C and an upper limit of 280°C. Various known dehydrogenation catalysts can be used without particular limitations, but preferably palladium-based, rhodium-based, and platinum-based catalysts can be exemplified, and they are usually used supported on a carrier such as silica or carbon. The amount of catalyst used is usually about 0.01 to 5% by weight, preferably a lower limit of 0.05% by weight and an upper limit of 3% by weight, relative to the purified rosin, hydrogenated rosin, or disproportionated rosin.

[0045] (Polymerized rosin) The polymerized rosin described above can be obtained by various known means. Specifically, for example, one method involves reacting the unmodified rosin described above as a raw material in a solvent such as toluene or xylene containing a catalyst such as sulfuric acid, hydrogen fluoride, aluminum chloride, or titanium tetrachloride, at a reaction temperature of about 40 to 160°C for about 1 to 5 hours.

[0046] Specific examples of polymerized rosin include gum-based polymerized rosin using gum rosin as a raw material (e.g., product name "Polymerized Rosin B-140," manufactured by Xinzhou (Wuping) Forestry Co., Ltd.), tall oil-based polymerized rosin using tall oil rosin (e.g., product name "Silbatac 140," manufactured by Arizona Chemical Corporation), and wood-based polymerized rosin using wood rosin (e.g., product name "Dymarex," manufactured by Eastman Chemical Corporation).

[0047] Furthermore, the polymerized rosin may be one which has been subjected to various treatments, including purification, hydrogenation, disproportionation, and α,β-unsaturated carboxylic acid modification such as acrylication, maleation, and fumaration, as described later. These treatments may be performed individually or in combination of two or more.

[0048] (α,β-unsaturated carboxylic acid modified rosin) The above-mentioned α,β-unsaturated carboxylic acid-modified rosin is obtained by adding an α,β-unsaturated carboxylic acid to the above-mentioned unmodified rosin.

[0049] The α,β-unsaturated carboxylic acid mentioned above is not particularly limited, and various known types can be used. Specifically, examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, muconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, muconic anhydride, maleic acid half-ester, fumaric acid half-ester, itaconic acid half-ester, etc. Among these, acrylic acid, maleic acid, maleic anhydride, and fumaric acid are preferred. The amount of α,β-unsaturated carboxylic acid used is usually about 1 to 20 parts by mass, preferably about 1 to 3 parts by mass, per 100 parts by mass of the unmodified rosin, in order to have excellent fluidity when melted and excellent moldability.

[0050] The above-mentioned α,β-unsaturated carboxylic acid-modified rosin can be obtained by various known means. Specifically, for example, the above-mentioned α,β-unsaturated carboxylic acid can be added to the above-mentioned unmodified rosin that has been melted under heating, and the reaction can be carried out at a temperature of about 180 to 240°C for about 1 to 9 hours. Alternatively, the above reaction may be carried out while blowing an inert gas such as nitrogen into a sealed reaction system. Furthermore, in the reaction, known catalysts such as Lewis acids such as zinc chloride, iron chloride, and tin chloride, or Brønsted acids such as p-toluenesulfonic acid and methanesulfonic acid may be used. The amount of these catalysts used is usually about 0.01 to 10% by mass relative to the above-mentioned unmodified rosin.

[0051] The obtained α,β-unsaturated carboxylic acid-modified rosin may contain resin acids derived from the unmodified rosin, the amount of which is less than 10% by mass.

[0052] Furthermore, as the α,β-unsaturated carboxylic acid modified rosin mentioned above, the obtained α,β-unsaturated carboxylic acid modified rosin may be further subjected to the hydrogenation process described above.

[0053] (Rosin esters) Examples of the rosin esters mentioned above include reaction products of unmodified rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, and α,β-unsaturated carboxylic acid-modified rosin (hereinafter collectively referred to as rosins) with alcohol. In this specification, the esterified products of unmodified rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, and α,β-unsaturated carboxylic acid-modified rosin are referred to as unmodified rosin ester, purified rosin ester, hydrogenated rosin ester, disproportionated rosin ester, polymerized rosin ester, and α,β-unsaturated carboxylic acid-modified rosin ester, respectively.

[0054] The above alcohols are not particularly limited and various known alcohols can be used. Examples of the above alcohols include monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, cyclohexanol, benzyl alcohol, borneol, etc.; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, neopentyl glycol, trimethylene glycol, etc. Examples include dihydric alcohols such as chlorohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4'-isopropylidenedicyclohexanol, and 4,8-bis(hydroxymethyl)tricyclo[5.2.1.02,6]decane; trihydric alcohols such as glycerin, trimethylolethane, and trimethylolpropane; tetrahydric alcohols such as pentaerythritol, diglycerin, and di(trimethylolpropane); pentahydric alcohols such as triglycerin; and hexahydric alcohols such as dipentaerythritol. Note that glycidyl ethers or glycidol, which react with carboxylic acids to form esters, may also be used. The above alcohols may be used individually or in combination of two or more.

[0055] The above alcohols are preferably trivalent to hexavalent alcohols, and more preferably glycerin, pentaerythritol, diglycerin, and dipentaerythritol, due to their excellent fluidity during the melting of the resin composition and their excellent moldability.

[0056] The above-mentioned rosin esters can be obtained by various known means. Specifically, for example, the rosin and the alcohol can be reacted at a temperature of about 150 to 300°C for about 1 to 24 hours. The amounts of rosin and alcohol used are not particularly limited, but are usually determined so that the ratio of OH groups of alcohol to COOH groups of rosin (equivalent ratio) is in the range of about 0.8 to 8, preferably 1.1 to 1.3.

[0057] In the above method for producing rosin esters, the esterification reaction can be carried out in the presence of a catalyst in order to shorten the reaction time. Examples of catalysts include acid catalysts such as p-toluenesulfonic acid, acetic acid, methanesulfonic acid, hypophosphorous acid, and sulfuric acid; metal hydroxides such as calcium hydroxide and magnesium hydroxide; metal oxides such as calcium oxide and magnesium oxide; and metal salts such as iron chloride and calcium formate. One catalyst may be used alone, or two or more catalysts may be used in combination. Also, since water is produced as a result of the esterification reaction, the reaction can be carried out while removing the produced water from the system. Considering the color of the resulting rosin ester, it is desirable to carry out the reaction under an inert gas stream. Furthermore, the reaction can be carried out under pressure if necessary.

[0058] In the above method for producing rosin esters, the rosins may be reacted with an organic solvent that is non-reactive to alcohol. Examples of such organic solvents include hexane, cyclohexane, toluene, and xylene. When an organic solvent is used, the organic solvent or unreacted raw materials may be removed by vacuum distillation as needed.

[0059] In the above method for producing rosin esters, the obtained rosin esters may be further subjected to various treatments such as purification, hydrogenation, disproportionation, and α,β-unsaturated carboxylic acid modification. Furthermore, these treatments may be performed individually or in combination of two or more.

[0060] Furthermore, the method for producing hydrogenated rosin esters, disproportionated rosin esters, polymerized rosin esters, and α,β-unsaturated carboxylic acid-modified rosin esters may also involve performing hydrogenation, disproportionation, polymerization, and modification reactions with α,β-unsaturated carboxylic acids on the reaction product of the unmodified rosin and the alcohol, respectively.

[0061] (Rosinphenol resin) The above-mentioned rosin-phenol resin is obtained by reacting the above-mentioned unmodified rosin with phenols.

[0062] The phenols mentioned above are not particularly limited, and various known phenols can be used. Specifically, examples include cresol, butylphenol, octylphenol, nonylphenol and other alkylphenols, phenols, bisphenols, naphthols, etc. These may be used individually or in mixtures of two or more. From the standpoint of emulsification, the amount of phenol to be used is usually about 0.8 to 1.5 moles per mole of the above raw material rosin.

[0063] The method for producing the above-mentioned rosinphenol resin is not particularly limited, but for example, it is a method in which the above-mentioned unmodified rosin and phenols are heated and reacted in the presence of an acid catalyst as needed. The reaction temperature is usually 180 to 350°C for about 6 to 18 hours. The acid catalyst that can be used in this reaction is not particularly limited, but for example, inorganic acid catalysts such as sulfuric acid, hydrogen chloride, and boron trifluoride, or organic acid catalysts such as p-toluenesulfonic acid and methanesulfonic acid can be used. When using an acid catalyst, it is sufficient to use about 0.01 to 1.0 part by mass per 100 parts by mass of the above-mentioned unmodified rosin. The rosinphenol resin may also be obtained by further reacting the resin obtained in the above reaction with an alcohol to esterify it. The alcohol used in this case is the same as above.

[0064] (Rosindiol) Rosin diol is a compound that has at least two rosin skeletons and at least two hydroxyl groups within its molecule.

[0065] Examples of the rosin diols mentioned above include reaction products of unmodified rosin, hydrogenated rosin, or disproportionated rosin with epoxy resin (see Japanese Patent Publication No. 5-155972).

[0066] Examples of the epoxy resins mentioned above include bisphenol-type epoxy resins, novolac-type epoxy resins, resorcinol-type epoxy resins, phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, aliphatic polyepoxy compounds, alicyclic epoxy compounds, glycidylamine-type epoxy compounds, glycidyl ester-type epoxy compounds, monoepoxy compounds, naphthalene-type epoxy compounds, biphenyl-type epoxy compounds, epoxidized polybutadiene, epoxidized styrene-butadiene-styrene block copolymers, epoxy group-containing polyester resins, epoxy group-containing polyurethane resins, epoxy group-containing acrylic resins, stilbene-type epoxy compounds, triazine-type epoxy compounds, fluorene-type epoxy compounds, triphenolmethane-type epoxy compounds, alkyl-modified triphenolmethane-type epoxy compounds, dicyclopentadiene-type epoxy compounds, and arylalkylene-type epoxy compounds.

[0067] Examples of the bisphenol-type epoxy resins mentioned above include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol AD ​​type epoxy resin, and tetrabromobisphenol A type epoxy resin.

[0068] Examples of the above-mentioned novolac-type epoxy resins include cresol novolac-type epoxy resin, phenol novolac-type epoxy resin, α-naphthol novolac-type epoxy resin, bisphenol A-type novolac-type epoxy resin, and brominated phenol novolac-type epoxy resin.

[0069] Examples of the above aliphatic polyepoxy compounds include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, diglycerol triglycidyl ether, sorbitol tetraglycidyl ether, and diglycidyl ether.

[0070] Examples of the above-mentioned alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meth-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadienediepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl)ether, ethylenebis(3,4-epoxycyclohexanecarboxylate), and lactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate.

[0071] Examples of the glycidylamine-type epoxy compounds mentioned above include tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmethaminophenol, and tetraglycidylmetaxylylenediamine.

[0072] Examples of the glycidyl ester-type epoxy compounds mentioned above include diglycidyl phthalate, diglycidyl hexahydrophthalate, and diglycidyl tetrahydrophthalate.

[0073] The method for producing the above-mentioned rosin diol is not particularly limited, but one example is a method in which the above-mentioned unmodified rosin, hydrogenated rosin, or disproportionated rosin and epoxy resin are subjected to a ring-opening addition reaction at 120 to 200°C in the presence of a catalyst.

[0074] Examples of catalysts that can be used include amine-based catalysts such as trimethylamine, triethylamine, tributylamine, benzyldimethylamine, pyridine, and 2-methylimidazole; quaternary ammonium salts such as benzyltrimethylammonium chloride; Lewis acids; boric acid esters; organometallic compounds; and organometallic salts.

[0075] (Petroleum resin) The above-mentioned petroleum resin is not particularly limited, and various known types can be used. Examples of the above-mentioned petroleum resin include aliphatic petroleum resin, alicyclic petroleum resin, aromatic petroleum resin, aliphatic-aromatic petroleum resin, hydroxyl group-containing petroleum resin, or hydrides thereof (hereinafter, these hydrides will be referred to as hydrogenated petroleum resins). The above-mentioned petroleum resin may be used individually or in combination of two or more types.

[0076] (Aliphatic petroleum resin) Examples of the aliphatic petroleum resins mentioned above include C5 petroleum resins obtained from the C5 petroleum fraction of naphtha.

[0077] Examples of C5 petroleum fractions include conjugated diolefinic unsaturated hydrocarbons with 4 to 6 carbon atoms, such as isoprene, trans-1,3-pentadiene, cis-1,3-pentadiene, cyclopentadiene, and methylcyclopentadiene; monoolefinic unsaturated hydrocarbons with 4 to 6 carbon atoms, such as butene, 2-methyl-1-butene, 2-methyl-2-butene, 1-pentene, 2-pentene, and cyclopentene; aliphatic saturated hydrocarbons such as cyclopentane, 2-methylpentane, 3-methylpentane, and n-hexane; and mixtures thereof.

[0078] (Alicyclic petroleum resin) Examples of the alicyclic petroleum resins mentioned above include dicyclopentadiene petroleum resins obtained from the cyclopentadiene petroleum fraction of naphtha. Examples of cyclopentadiene petroleum fractions include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, and their dimers, trimers, copolymers, and mixtures thereof. Examples of such dimers include dicyclopentadiene.

[0079] (Aromatic petroleum resin) Examples of the aromatic petroleum resins mentioned above include C9 petroleum resins obtained from the C9 petroleum fraction of naphtha, and copolymers obtained by polymerizing the C9 petroleum resin alone or in combination with other C9 petroleum resins. Examples of C9 petroleum fractions include C8 aromatic compounds such as styrene; C9 aromatic compounds such as α-methylstyrene, β-methylstyrene, vinyltoluene, and indene; C10 aromatic compounds such as 1-methylindene, 2-methylindene, and 3-methylindene; C11 aromatic compounds such as 2,3-dimethylindene and 2,5-dimethylindene; and mixtures thereof.

[0080] (Aliphatic / aromatic petroleum resin) Examples of the above-mentioned aliphatic-aromatic petroleum resins include C5 / C9 copolymer petroleum resins obtained from the above-mentioned C5 petroleum fraction and C9 petroleum fraction.

[0081] (Hydroxygroup-containing petroleum resin) The hydroxyl group-containing petroleum resin described above is not particularly limited and any known petroleum resin having at least two hydroxyl groups in its molecule can be used. One type of hydroxyl group-containing petroleum resin may be used alone, or two or more types may be used in combination.

[0082] Examples of the hydroxyl group-containing petroleum resins mentioned above include hydroxyl group-containing C5 petroleum resins, hydroxyl group-containing dicyclopentadiene petroleum resins, hydroxyl group-containing C9 petroleum resins, hydroxyl group-containing C5-C9 petroleum resins, and hydroxyl group-containing dicyclopentadiene-C9 petroleum resins.

[0083] Examples of the hydroxyl group-containing C5 petroleum resins mentioned above include reaction products of the above-mentioned C5 petroleum fraction and hydroxyl group-containing compounds.

[0084] Examples of the hydroxyl group-containing compounds mentioned above include phenolic compounds and hydroxyl group-containing olefin compounds. Examples of phenolic compounds include phenol, cresol, xylenol, amylphenol, bisphenol A, vinylphenol, and alkylphenols such as butylphenol, octylphenol, nonylphenol, and dodecylphenol. Examples of hydroxyl group-containing olefin compounds include allyl alcohol compounds and hydroxyl group-containing mono(meth)acrylates.

[0085] The above allyl alcohol compounds include, for example, allyl alcohol, 2-methyl-2-propen-1-ol, 3-methyl-2-propen-1-ol, 2-buten-1-ol, 2-penten-1-ol, 2-hexen-1-ol, 5-methyl-2-hexen-1-ol, 4-cyclohexyl-2-buten-1-ol, 2,5-hexadiene-1-ol, 2,5-heptadiene-1-ol, 2,6- Heptadiene-1-ol, 2,5-octadiene-1-ol, 2,6-octadiene-1-ol, 2,7-octadiene-1-ol, 4-(1-cyclohexenyl)-2-buten-1-ol, 4-phenyl-2-buten-1-ol, 4-naphthyl-2-buten-1-ol, 3,7-dimethyl-2,7-octadiene-1-ol, 3,7-dimethyl-2,6-octadiene-1-ol, 3,7 ,11-trimethyl-2,6,10-dodecatriene-1-ol, 1-penten-3-ol, 1-hexen-3-ol, 5-methyl-1-hexen-3-ol, 4-cyclohexyl-1-buten-3-ol, 1,5-hexadiene-3-ol, 1,5-heptadiene-3-ol, 1,6-heptadiene-3-ol, 1,5-octadiene-3-ol, 1,6-octadiene-3-ol, 1 Examples include 7-octadiene-3-ol, 4-(1-cyclohexenyl)-1-buten-3-ol, cinnamyl alcohol, 4-phenyl-1-buten-3-ol, 4-naphthyl-1-buten-3-ol, 3,7-dimethyl-2,7-octadiene-1-ol, 3,7-dimethyl-1,6-octadiene-3-ol, and 3,7,11-trimethyl-1,6,10-dodecatriene-3-ol.

[0086] Examples of the hydroxyl group-containing mono(meth)acrylates mentioned above include 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate, and hydroxycyclohexyl(meth)acrylate.

[0087] Examples of the hydroxyl group-containing dicyclopentadiene-based petroleum resins mentioned above include reaction products of the cyclopentadiene-based petroleum fraction and the hydroxyl group-containing compound.

[0088] Examples of the hydroxyl group-containing C9 petroleum resins mentioned above include reaction products of the C9 petroleum fraction and the hydroxyl group-containing compound.

[0089] Examples of the hydroxyl group-containing C5-C9 petroleum resins mentioned above include the reaction products of the C5 petroleum fraction, the C9 petroleum fraction, and the hydroxyl group-containing compound.

[0090] Examples of the hydroxyl group-containing dicyclopentadiene·C9 petroleum resins mentioned above include the reaction products of the cyclopentazine petroleum fraction, the C9 petroleum fraction, and the hydroxyl group-containing compound.

[0091] The method for producing the above-mentioned hydroxyl group-containing petroleum resin is not particularly limited, and various known methods can be employed. Specifically, examples include a method of cationic polymerization using a Friedel-Craft catalyst such as aluminum chloride or boron trifluoride in the presence of various petroleum fractions and the above-mentioned hydroxyl group-containing compound; and a method of thermal polymerization in an autoclave in the presence of various petroleum fractions and the above-mentioned hydroxyl group-containing compound.

[0092] (Hydrogenated petroleum resin) The above-mentioned hydrogenated petroleum resins can be obtained by various known means. Specifically, for example, they can be obtained by hydrogenating the above-mentioned various petroleum resins (aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, aliphatic-aromatic petroleum resins, hydroxyl group-containing petroleum resins) using known hydrogenation conditions.

[0093] Hydrogenation conditions include, for example, heating the petroleum resin to a temperature of approximately 200 to 350°C at a hydrogen partial pressure of approximately 0.2 to 30 MPa in the presence of a hydrogenation catalyst. Examples of hydrogenation catalysts include metals such as nickel, palladium, cobalt, ruthenium, platinum, and rhodium, as well as oxides of these metals. The amount of hydrogenation catalyst used is usually preferably about 0.01 to 10 parts by mass per 100 parts by mass of the raw material resin.

[0094] The above hydrogenation is carried out by melting the various petroleum resins (aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, aliphatic-aromatic petroleum resins, hydroxyl group-containing petroleum resins) or by dissolving them in a solvent. The solvent used to dissolve the petroleum resin is not particularly limited, but any solvent that is inert to the reaction and readily dissolves the raw materials and products is acceptable. For example, one or more of cyclohexane, n-hexane, n-heptane, decalin, tetrahydrofuran, dioxane, etc., can be used. The amount of solvent used is not particularly limited, but usually the solid content is 10% by mass or more relative to the petroleum resin, preferably in the range of 10 to 70% by mass. The above hydrogenation conditions are described for a batch reaction, but a flow reaction (fixed bed, fluidized bed, etc.) can also be used.

[0095] The above hydrogenation conditions are described for a batch reaction, but a flow reaction (fixed bed, fluidized bed, etc.) can also be used.

[0096] (Terpene resin) The above-mentioned terpene resin is not particularly limited, and various known resins can be used. Examples of such terpene resins include resins obtained by copolymerizing known terpenes with phenols. The terpene resin may also be hydrogenated. The above-mentioned terpene resin may be used individually or in combination of two or more types.

[0097] Component (C) is preferably a rosin-based resin because it suppresses contamination of the manufacturing equipment and the resin composition has excellent moldability. More preferably, it is at least one selected from the group consisting of natural rosin, purified rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, α,β-unsaturated carboxylic acid modified rosin, rosin esters, and rosinphenol. Particularly preferred is at least one selected from the group consisting of natural rosin, purified rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, and α,β-unsaturated carboxylic acid modified rosin, from the standpoint of having particularly excellent moldability of the resin composition.

[0098] (Physical properties of resin (C)) The physical properties of component (C) are not particularly limited. The acid value of component (C) is preferably about 130 to 350 mgKOH / g, and more preferably about 140 to 330 mgKOH / g, from the viewpoint of superior moldability of the resin composition. In this specification, the acid value is the value measured according to JIS K0070.

[0099] The softening point of component (C) is preferably around 80 to 180°C, and more preferably around 100 to 160°C, from the viewpoint of superior moldability of the resin composition. In this specification, the softening point is the value measured by the ring-ball method of JIS K 5902.

[0100] The color tone of component (C) is preferably 8 Gardner or less, more preferably 10 to 400 Hazen, and particularly preferably 10 to 200 Hazen, in order to suppress discoloration in the resin composition. In this specification, the color tone is measured in Hazen units in accordance with JIS K 0071-1 and in Gardner units in accordance with JIS K 0071-2.

[0101] Component (C) may include various known additives as needed, insofar as they do not impair the effects of the present invention. Examples of additives include dehydrating agents, weathering agents, antioxidants, ultraviolet absorbers, heat stabilizers, light stabilizers, and the like. The above additives may be used individually or in combination of two or more.

[0102] (Additives) The above resin composition may contain additives as needed, provided that the effects of the present invention are not impaired. Examples of additives include flame retardants (e.g., phosphorus-containing epoxy resins, red phosphorus, phosphazene compounds, phosphates, phosphate esters, etc.), silicone oil, wetting and dispersing agents, defoaming agents, defoaming agents, natural waxes, synthetic waxes, release agents such as metal salts of linear fatty acids, fatty acid amides, esters, and paraffins, crystalline silica, fused silica, calcium silicate, alumina, calcium carbonate, talc, inorganic pigments, organic pigments, dehydrating agents, nucleating agents, plasticizers, fluidity improvers other than component (B), weathering agents, antioxidants, ultraviolet absorbers, heat stabilizers, light stabilizers, etc.

[0103] Examples of the inorganic pigments mentioned above include cadmium red, cadmium lemon yellow, cadmium yellow orange, titanium dioxide, carbon black, black iron oxide, and black complex inorganic pigments.

[0104] Examples of the above-mentioned organic pigments include aniline black, perylene black, anthraquinone black, benzidine-based yellow pigment, phthalocyanine blue, and phthalocyanine green.

[0105] (Content of each component) The content of component (A) in the above resin composition is not particularly limited, but from the viewpoint of excellent mechanical properties of the resin composition, it is preferably 60 to 90 parts by mass per 100 parts by mass of the total of components (A) and (B).

[0106] The content of component (B) in the above resin composition is not particularly limited, but from the viewpoint of excellent mechanical properties of the resin composition, it is preferably 10 to 40 parts by mass per 100 parts by mass of the total of components (A) and (B).

[0107] The content ratio ((A) / (B)) of component (A) to component (B) in the above resin composition is preferably 60 / 40 to 90 / 10, in order to obtain excellent mechanical properties of the resin composition.

[0108] The content of component (C) in the above resin composition is not particularly limited, but is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total of components (A) and (B).

[0109] If the content of component (C) is 0.1 parts by mass or more per 100 parts by mass of the total of components (A) and (B), the resin composition will have superior moldability. If the content of component (C) is 5 parts by mass or less per 100 parts by mass of the total of components (A) and (B), the resin composition will have superior moldability.

[0110] The content of component (C) in the above resin composition is more preferably 0.5 to 2 parts by mass per 100 parts by mass of the total of components (A) and (B), in order to suppress contamination of the manufacturing equipment and to improve the moldability of the resin composition.

[0111] The content of the additive in the above resin composition is not particularly limited, but is usually 0.001 parts by mass or more, preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and usually 100 parts by mass or less, preferably 50 parts by mass or less, per 100 parts by mass of the above resin composition.

[0112] (Method for manufacturing resin compositions) The method for producing the above resin composition is not particularly limited, and various known methods can be employed. For example, one method for producing the above resin composition is to pre-mix components (A), (B), and (C), and optionally the above additives, using various mixers such as a tumbler mixer or a Henschel mixer, and then melt-knead them using a mixer such as a Banbury mixer, roll mixer, Brabender, single-screw extruder, twin-screw extruder, or kneader. The temperature of the melt-kneading is not particularly limited, but is usually in the range of 170 to 230°C.

[0113] [Molded body] The molded articles of the present invention are obtained by molding the above-mentioned resin composition using various known molding methods. There are no particular restrictions on the shape of the molded articles, and they can be appropriately selected according to the application and purpose of the molded articles. Examples include plate-shaped, rod-shaped, sheet-shaped, film-shaped, cylindrical, annular, circular, elliptical, polygonal, irregularly shaped, hollow, frame-shaped, box-shaped, and panel-shaped articles.

[0114] The method for forming the above-mentioned molded article is not particularly limited, and conventionally known molding methods can be employed. Specifically, examples include injection molding, injection compression molding, extrusion molding, stretch film molding, inflation molding, shape extrusion, transfer molding, hollow molding, gas-assisted hollow molding, blow molding, extrusion blow molding, IMC (in-mold coating) molding, press molding, rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding, and pressure molding. Among these, molding is preferably carried out by injection molding. Examples of injection molding machines include known injection molding machines such as ultra-high-speed injection molding machines and injection compression molding machines.

[0115] The above-mentioned molded articles are suitable for a wide range of applications, from household goods to industrial products, such as automotive materials including interior materials, exterior panels and bumpers, electrical and electronic equipment, home appliance components, office automation equipment, information terminal equipment, machine parts, packaging materials, building materials, civil engineering materials, fisheries materials, various containers, lighting equipment, films, sheets, fibers, and other industrial materials.

[0116] Examples of the above-mentioned electrical and electronic devices include car navigation systems, personal computers, game consoles, televisions, display devices such as e-paper, printers, copiers, fax machines, electronic organizers and PDAs, electronic desktop calculators, electronic dictionaries, cameras, video cameras, DVD players and other display devices, mobile phones, tablet-type portable devices, and touch-panel portable devices.

[0117] [Modifier] The modifier of the present invention contains component (C) described above. When used in a polyolefin resin / starch composite composition, the modifier of the present invention improves the fluidity of the composite composition during melting and improves its moldability. Furthermore, the modifier facilitates the mixing of the polyolefin resin and starch-based material during the production of the polyolefin resin / starch composite composition, thereby suppressing contamination of the production equipment. Note that the modifier of the present invention is different from the resin composition described above.

[0118] The above-mentioned modifier can be used with various known polyolefin resin / starch composite compositions. Examples of the above-mentioned polyolefin resin / starch composite compositions include compositions containing a polyolefin resin and a starch-based material. Examples of the polyolefin resin include component (A) described above. The polyolefin resin may be used alone or in combination of two or more types. Examples of the starch-based material include component (B) described above. The starch-based material may be used alone or in combination of two or more types.

[0119] The polyolefin resins in which the above-mentioned modifier is used are preferably homopolymers of α-olefins having about 2 to 8 carbon atoms, such as ethylene, propylene, and 1-butene; binary or ternary (co)polymers of the α-olefins; and binary or ternary (co)polymers of the α-olefins and α-olefins having about 9 to 18 carbon atoms, such as 1-decene and 1-octadecene, from the viewpoint of excellent moldability. Similarly, at least one selected from the group consisting of polyethylene and polypropylene is more preferred.

[0120] The (C) component in the above modifier is preferably a rosin-based resin, as it improves the moldability of the polyolefin resin / starch composite composition and suppresses contamination in the manufacturing equipment. More preferably, it is at least one selected from the group consisting of natural rosin, purified rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, α,β-unsaturated carboxylic acid modified rosin, rosin esters, and rosin phenol. Particularly preferred is at least one selected from the group consisting of natural rosin, purified rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, and α,β-unsaturated carboxylic acid modified rosin.

[0121] The acid value of component (C) in the above modifier is preferably about 130 to 350 mgKOH / g, and more preferably about 140 to 330 mgKOH / g, from the viewpoint of improving the moldability of the composite composition. In this specification, the acid value is the value measured according to JIS K0070.

[0122] The softening point of component (C) in the above modifier is preferably around 80 to 180°C, and more preferably around 100 to 160°C, from the viewpoint of improving the moldability of the composite composition. In this specification, the softening point is the value measured by the ring-and-ball method of JIS K 5902.

[0123] The color tone of component (C) in the above modifier is preferably 8 Gardner or less, more preferably 10 to 400 Hazen, and particularly preferably 10 to 200 Hazen, in order to suppress discoloration in the polyolefin resin / starch composite composition. In this specification, the color tone is measured in Hazen units in accordance with JIS K 0071-1 and in Gardner units in accordance with JIS K 0071-2.

[0124] The amount of the above-mentioned modifier used is not particularly limited, but it is preferably 0.1 to 5 parts by mass per 100 parts by mass of the total of the polyolefin resin and starch-based material.

[0125] If the amount of the above-mentioned modifier used is 0.1 parts by mass or more per 100 parts by mass of the total of the polyolefin resin and starch-based material, the moldability of the composite composition is further improved. If the amount of the above-mentioned modifier used is 5 parts by mass or less per 100 parts by mass of the total of the polyolefin resin and starch-based material, the moldability of the composite composition is further improved.

[0126] The amount of the above-mentioned modifier used is more preferably 0.5 to 2 parts by mass per 100 parts by mass of the total of the polyolefin resin and starch-based material, in order to improve the moldability of the composite composition and suppress contamination in the manufacturing equipment.

[0127] The modifier of the present invention may contain various known additives as needed, as long as they do not impair the effects of the present invention. Examples of additives include dehydrating agents, weathering agents, antioxidants, ultraviolet absorbers, heat stabilizers, and light stabilizers. The above additives may be used individually or in combination of two or more. The content of the above additives is not particularly limited, but is preferably 0.5 to 10 parts by mass per 100 parts by mass of the modifier.

[0128] The method of using the modifier of the present invention is not particularly limited. For example, one method of using the modifier is to add the modifier together with the polyolefin resin and starch-based material to a mixer and then melt-knead the mixture in the mixer. Examples of the mixer include a Banbury mixer, roll mixer, Brabender, single-screw extruder, twin-screw extruder, kneader, and the like. [Examples]

[0129] The present invention will be described in more detail below with reference to examples of the present invention, but the present invention is actually... This is not limited to the examples provided. Note that "part" and "%" in the examples refer to, respectively... This represents "parts by mass" and "mass %".

[0130] (Manufacturing of resin (C)) Manufacturing Example 1 In a reactor equipped with a thermometer, stirrer, nitrogen inlet tube, and vacuum device, 700 parts of Chinese gum rosin (acid value 170.0 mg KOH / g, softening point 78°C, color 6 Gardner), 700 parts of xylene, and 17.5 parts of zinc chloride as a catalyst were charged, and the polymerization reaction was carried out at 140°C for 7 hours under a nitrogen stream. After filtering off the catalyst from the reaction product, xylene was removed by distillation under conditions of a liquid temperature of less than 200°C and a vacuum of 1300 Pa. Then, rosin decomposition products and unreacted gum rosin were further removed by distillation under conditions of a liquid temperature of 200-275°C and a vacuum of 400 Pa to obtain polymerized rosin (hereinafter referred to as component (C1)) with an acid value of 145 mg KOH / g and a softening point of 140°C.

[0131] Manufacturing Example 2 In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 1000 parts of Chinese gum rosin (acid value 172 mg KOH / g, softening point 75°C) were added to 0.3 parts of 5% palladium carbon (water content 50%) as a disproportionation catalyst. The mixture was stirred at 280°C for 4 hours under a nitrogen seal to carry out the disproportionation reaction, yielding disproportionated rosin (hereinafter referred to as component (C2)) with an acid value of 160 mg KOH / g and a softening point of 80°C.

[0132] Manufacturing Example 3 In a reaction vessel equipped with a stirrer, reflux condenser with water divider, and thermometer, 1,000 parts of Chinese gum rosin were charged and heated to 180°C under a nitrogen atmosphere while stirring until melted. Then, 267 parts of fumaric acid were added, and the temperature was raised to 230°C while stirring. After holding the temperature for 1 hour, a fumaric acid-modified rosin (hereinafter referred to as component (C3)) with an acid value of 300 mg KOH / g and a softening point of 150°C was obtained.

[0133] Manufacturing Example 4 Chinese gum rosin (acid value 172 mgKOH / g, softening point 75°C, color 6 Gardner) was charged into a vacuum distillation vessel and distilled under reduced pressure of 0.4 kPa under a nitrogen seal to obtain purified rosin with an acid value of 177 mgKOH / g, softening point 80°C, and color 3 Gardner.

[0134] Next, 700 parts of the purified rosin and 140 parts of maleic anhydride were charged into another vacuum distillation vessel and reacted at 220°C for 4 hours while stirring under a nitrogen stream. After that, unreacted material was removed under reduced pressure of 4 kPa to obtain an addition reaction product with an acid value of 335 mg KOH / g, a softening point of 121°C, and a color of 8 Gardner.

[0135] Furthermore, 500 parts of the addition reaction product and 6.0 parts of 5% palladium carbon (50% water content) (catalyst amount 1.2%) were placed in a 1-liter rotary autoclave. After replacing the air in the system with hydrogen, the autoclave was pressurized to 10 MPa with hydrogen, the temperature was raised to 220°C, and the hydrogenation reaction was carried out at the same temperature for 5 hours. The catalyst was filtered off to obtain a hydride of maleic anhydride-modified rosin (hereinafter referred to as component (C4)) with an acid value of 330 mg KOH / g, a softening point of 120°C, and a color of 150 Hazen.

[0136] Manufacturing Example 5 1000 parts of Chinese gum rosin (acid value 172 mg KOH / g, softening point 75°C, color 6 Gardner) and 500 parts of xylene were placed in a corvene and heated until dissolved. Approximately 350 parts of xylene were removed by distillation, then 350 parts of cyclohexane were added, and the mixture was cooled to room temperature. When approximately 100 parts of crystals formed due to cooling, the supernatant was transferred to another corvene and recrystallized at room temperature. After removing the supernatant, the mixture was washed with 100 parts of cyclohexane, and the solvent was removed by distillation to obtain 700 parts of purified rosin.

[0137] Next, 660 parts of purified rosin and 100 parts of acrylic acid were charged into a reaction vessel, and the reaction was carried out at 220°C for 4 hours while stirring under a nitrogen atmosphere. Then, unreacted material was removed under reduced pressure to obtain 720 parts of the addition reaction product.

[0138] Furthermore, 500 parts of the above addition reaction product and 5.0 parts of 5% palladium carbon (50% water content) were charged into a 1-liter rotary autoclave. After removing oxygen from the system, the system was pressurized with hydrogen to 10 MPa and heated to 220°C. The hydrogenation reaction was carried out at the same temperature for 3 hours to obtain a hydride of acrylic acid-modified rosin (hereinafter referred to as component (C5)) with an acid value of 240 mg KOH / g, a softening point of 130°C, and a color of 100 Hazen.

[0139] Manufacturing Example 6 In a reactor equipped with a thermometer, stirrer, nitrogen inlet tube, and vacuum device, 1000 parts of Chinese gum rosin (acid value 172 mg KOH / g, softening point 75°C, color 6 Gardner) and 0.3 parts of palladium carbon (palladium loading 5%, water content 50%) as catalyst were charged. Under a nitrogen seal, the mixture was stirred at 280°C for 4 hours to carry out a disproportionation reaction, yielding disproportionated rosin with an acid value of 157 mg KOH / g, a softening point 77°C, and a color 7 Gardner. Next, the disproportionated rosin was distilled under a nitrogen seal under a reduced pressure of 3 mmHg, and the resulting main distillate was used as purified disproportionated rosin.

[0140] In a reactor equipped with a thermometer, stirrer, nitrogen inlet tube, and vacuum device, 500 parts of the above-mentioned purified disproportionated rosin (acid value 178 mg KOH / g, softening point 83°C, color 4 Gardner) were charged. The temperature was raised to 180°C under a nitrogen seal, and under melting and stirring, 60 parts of glycerin were added at 200°C. The temperature was then raised to 280°C, and the esterification reaction was carried out at the same temperature for 12 hours to obtain 515 parts of purified disproportionated rosin ester with an acid value of 4 mg KOH / g, softening point 90°C, and color 5 Gardner.

[0141] 1. In a shaking autoclave, 200 parts of the above-mentioned purified disproportionated rosin ester and 2 parts of palladium carbon are charged. After removing oxygen from the system, the system is purified with hydrogen at a rate of 100 kg / cm³. 2 The mixture was pressurized and heated to 255°C, and a hydrogenation reaction was carried out at the same temperature for 3 hours to obtain a hydrogenated rosin ester (hereinafter referred to as component (C6)) with an acid value of 13 mg KOH / g, a softening point of 90°C, and a color of 50 Hazen.

[0142] Manufacturing example 7 In a reaction vessel equipped with a stirrer, condenser, thermometer, and nitrogen and steam inlet tubes, 100.0 parts of gum rosin derived from Chinese mauve pine and 150.0 parts of phenol were charged, the temperature was raised to 100°C, 2.1 parts of 96% sulfuric acid were charged, and the mixture was reacted under a nitrogen gas stream for 4 hours. 3.0 parts of slaked lime and 0.1 parts of 4,4'-thiobis(6-t-butyl-3-methylphenol) (trade name "Lowinox TBM-6", manufactured by Addivant) were added, the temperature was raised to 280°C under reduced pressure of 10 kPa, and the mixture was reacted at the same temperature for 4 hours to obtain rosinphenol resin (hereinafter referred to as component (C7)).

[0143] (Acid value) The acid values ​​of components (C1) to (C7) were measured according to JIS K 0070.

[0144] (softening point) The softening points of components (C1) to (C7) were measured according to JIS K 5902.

[0145] (color tone) The color tones of components (C1) to (C7) were measured in Hazen units according to JIS K 0071-1 and in Gardner units according to JIS K 0071-2.

[0146] [Preparation of resin composition] Example 1 80 parts of polyethylene (manufactured by Rhombic Co., Ltd., product name "LLDPE RLL1BF") (hereinafter referred to as PE), 20 parts of thermoplastic starch pellets (manufactured by SMS Co., Ltd., product name "TAPIOPLAST TPS") (hereinafter referred to as TAPIOPLAST), and 2 parts of component (C1) were added to a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name "Laboplastmill Model 10C100"), and kneaded at a roller rotation speed of 40 rpm and a temperature of 200°C for 10 minutes. After that, the obtained resin (resin composition) was removed from the kneading device, hot-pressed at 180°C to form a sheet with a thickness of 1.0 mm, and cut into 5 mm x 5 mm pieces with a cutting machine to obtain pellets.

[0147] Example 2 In Example 1, the preparation was carried out in the same manner as in Example 1, except that 2 parts of component (C2) were used instead of component (C1), to obtain pellets.

[0148] Example 3 In Example 1, the preparation was carried out in the same manner as in Example 1, except that 2 parts of component (C3) were used instead of component (C1), to obtain pellets.

[0149] Example 4 In Example 1, the preparation was carried out in the same manner as in Example 1, except that 2 parts of component (C4) were used instead of component (C1), to obtain pellets.

[0150] Example 5 In Example 1, the preparation was carried out in the same manner as in Example 1, except that 2 parts of component (C5) were used instead of component (C1), to obtain pellets.

[0151] Example 6 In Example 1, the preparation was carried out in the same manner as in Example 1, except that 2 parts of component (C6) were used instead of component (C1), to obtain pellets.

[0152] Example 7 In Example 1, the preparation was carried out in the same manner as in Example 1, except that 2 parts of component (C7) were used instead of component (C1), to obtain pellets.

[0153] Comparative Example 1 80 parts of PE and 20 parts of TAPIOPLAST were placed in a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., device name "Laboplastmill Model 10C100") and kneaded for 10 minutes at a roller rotation speed of 40 rpm and a temperature of 200°C. After that, the resulting kneaded material was removed from the kneading device, hot-pressed at 180°C to form a sheet with a thickness of 1.0 mm, and then cut into 5 mm x 5 mm pieces using a cutting machine to obtain pellets.

[0154] Comparative Example 2 Except for using two parts of maleic anhydride-modified polypropylene (manufactured by Sanyo Chemical Industries, Ltd., trade name "Yumex 1010") (hereinafter referred to as component (c1)) instead of component (C1) in Example 1, the preparation was carried out in the same manner as in Example 1 to obtain pellets.

[0155] Comparative Example 3 Except for using two parts of maleic anhydride-modified polypropylene (manufactured by Sanyo Chemical Industries, Ltd., trade name "Yumex 1001") (hereinafter referred to as component (c2)) instead of component (C1) in Example 1, the preparation was carried out in the same manner as in Example 1 to obtain pellets.

[0156] Comparative Example 4 Except for using two parts of maleic anhydride-modified polypropylene (manufactured by Sanyo Chemical Industries, Ltd., trade name "Yumex 100TS") (hereinafter referred to as component (c3)) instead of component (C1) in Example 1, the preparation was carried out in the same manner as in Example 1 to obtain pellets.

[0157] Example 8 80 parts of polypropylene (manufactured by Nippon Polypropylene Co., Ltd., product name "Novatec PP MA3") (hereinafter referred to as PP), 20 parts of TAPIOPLAST, and 2 parts of component (C1) were added to a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., device name "Laboplastmill Model 10C100"), and kneaded for 10 minutes at a roller rotation speed of 40 rpm and a temperature of 180°C. After that, the resulting kneaded material was removed from the kneading device, hot-pressed at 200°C to form a sheet with a thickness of 1.0 mm, and then cut into 5 mm x 5 mm pieces with a cutting machine to obtain pellets.

[0158] Example 9 In Example 8, the preparation was carried out in the same manner as in Example 8, except that 2 parts of component (C2) were used instead of component (C1), to obtain pellets.

[0159] Example 10 In Example 8, the preparation was carried out in the same manner as in Example 8, except that 2 parts of component (C3) were used instead of component (C1), to obtain pellets.

[0160] Example 11 In Example 8, the preparation was carried out in the same manner as in Example 8, except that 2 parts of component (C4) were used instead of component (C1), to obtain pellets.

[0161] Example 12 In Example 8, the preparation was carried out in the same manner as in Example 8, except that 2 parts of component (C5) were used instead of component (C1), to obtain pellets.

[0162] Example 13 In Example 8, the preparation was carried out in the same manner as in Example 8, except that 2 parts of component (C6) were used instead of component (C1), to obtain pellets.

[0163] Example 14 In Example 8, the preparation was carried out in the same manner as in Example 8, except that 2 parts of component (C7) were used instead of component (C1), to obtain pellets.

[0164] Comparative Example 5 80 parts of PP and 20 parts of TAPIOPLAST were placed in a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., device name "Laboplastmill Model 10C100") and kneaded for 10 minutes at a roller rotation speed of 40 rpm and a temperature of 180°C. After that, the resulting kneaded material (resin composition) was removed from the kneading device, hot-pressed at 180°C to form a sheet with a thickness of 1.0 mm, and then cut into 5 mm x 5 mm pieces using a cutting machine to obtain pellets.

[0165] Comparative Example 6 In Example 8, the preparation was carried out in the same manner as in Example 8, except that 2 parts of component (c1) were used instead of component (C1), to obtain pellets.

[0166] Comparative Example 7 In Example 8, the preparation was carried out in the same manner as in Example 8, except that 2 parts of component (c2) were used instead of component (C1), to obtain pellets.

[0167] Comparative Example 8 In Example 8, the preparation was carried out in the same manner as in Example 8, except that 2 parts of component (c3) were used instead of component (C1), to obtain pellets.

[0168] (Evaluation of moldability) In accordance with JIS K 7210, the MFR of the pellets from Examples 1-7 and Comparative Examples 1-4 was measured at a temperature of 190°C and a load of 21.2 N (2.16 kg), while the MFR of the pellets from Examples 8-14 and Comparative Examples 5-8 was measured at a temperature of 230°C and a load of 21.2 N (2.16 kg). The results are shown in Tables 1 and 2.

[0169] (Evaluation of equipment contamination) In the preparation of pellets in Examples 1-14 and Comparative Examples 1-8, the amount of resin residue in the kneading apparatus after mixing was visually evaluated, and the apparatus contamination was assessed according to the following criteria. The results are shown in Tables 1 and 2. ◎: There is almost no resin residue left in the mixing device after mixing. ○: There is little resin residue left in the mixing device after mixing. △: There is a slightly large amount of resin residue in the mixing device after mixing. ×: There is an extremely large amount of resin residue in the mixing device after mixing.

[0170] [Table 1]

[0171] [Table 2]

[0172] The amounts in Tables 1 and 2 are given in parts by mass. The abbreviations in Tables 1 and 2 are as follows: (Abbreviations and details of compounds) PE: Polyethylene, product name "LLDPE RLL1BF", manufactured by Rhombic Co., Ltd. PP: Polypropylene, product name "Novatec PP MA3", manufactured by Nippon Polypropylene Co., Ltd. TAPIOPLAST: Thermoplastic starch, product name "TAPIOPLAST TPS", SMS Company

Claims

1. Polyolefin resin (A), thermoplastic starch (B), and It comprises at least one resin (C) selected from the group consisting of rosin resins, petroleum resins, and terpene resins, The resin (C) is a rosin-based resin, The rosin-based resin is at least one selected from the group consisting of hydrogenated rosin, disproportionated rosin, polymerized rosin, α,β-unsaturated carboxylic acid-modified rosin, rosin esters, and rosinphenol. The content ratio ((A) / (B)) of the polyolefin resin (A) to the thermoplastic starch (B) is 60 / 40 to 90 / 10. The content of the resin (C) in the resin composition is 0.5 to 2 parts by mass with respect to 100 parts by mass of the total of the polyolefin resin (A) and the thermoplastic starch (B). A resin composition that is a molten and kneaded product.

2. The resin composition according to claim 1, wherein component (A) is at least one selected from the group consisting of polyethylene and polypropylene.

3. A molded article obtained from the resin composition according to claim 1 or 2.

4. It comprises at least one resin (C) selected from the group consisting of rosin resins, petroleum resins, and terpene resins, The resin (C) is a rosin-based resin, The rosin-based resin is at least one selected from the group consisting of hydrogenated rosin, disproportionated rosin, polymerized rosin, α,β-unsaturated carboxylic acid-modified rosin, rosin esters, and rosin phenol. This is a modifier for polyolefin resin / starch composite compositions, which are molten and kneaded products. The ratio of polyolefin resin to starch-based material in the polyolefin resin / starch composite composition is 60 / 40 to 90 / 10. The amount of the modifier used is 0.5 to 2 parts by mass per 100 parts by mass of the total of the polyolefin resin and starch-based material. Modifier for polyolefin resin / starch composite compositions.

5. The modifier for polyolefin resin / starch composite composition according to claim 4, wherein the polyolefin resin is at least one selected from the group consisting of polyethylene and polypropylene.

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