Resin composition and laminate having layers formed from the resin composition

Abstract

The object of the present invention is to obtain a resin composition that further improves the adhesion to a substrate layer when used as an adhesive layer in a laminate, and a laminate containing layers formed from the resin composition that exhibits superior interlayer adhesive strength. The present invention relates to a resin composition and a laminate containing layers of the resin composition, the resin composition being characterized by containing: 5 to 70 wt% of an propylene polymer (A); 30 to 95 wt% of a soft propylene polymer (B); 0.1 to 20 wt% of an propylene polymer obtained by grafting modification with an olefinic unsaturated monomer (C); 0 to 20 wt% of polyethylene (D); and 1 to 30 wt% of an ethylene-α-olefin random copolymer (E), wherein the total amount of (A), (B), (C), (D), and (E) is set to 100 wt%.

Description

Technical Field

[0001] The present invention relates to a resin composition that further improves adhesion to a substrate layer when used as an adhesive layer in a laminate, and to a laminate containing layers formed from the resin composition that exhibit superior interlayer adhesive strength. Background Technology

[0002] Packaging films, designed to impart gas barrier, water vapor barrier, and oil resistance, utilize multilayer films formed from resins such as ethylene-vinyl acetate copolymer (EVOH), polyamide (PA), polyester, polyethylene terephthalate (PET), and polypropylene (PP). As a method for forming multilayer films, co-extrusion molding is commonly used because all layers are composed of thermoplastic resins, resulting in easy molding and excellent interlayer adhesion.

[0003] On the other hand, in applications where packaging films have higher rigidity, biaxially stretched films or uniaxially stretched films are used as the substrate layer (substrate film). In applications requiring light-shielding and high barrier properties, aluminum (Al) foil, aluminum vapor-deposited films, or transparent vapor-deposited films formed of aluminum oxide or silicon oxide are used as layers of multilayer films.

[0004] One method for obtaining such a biaxially stretched film or uniaxially stretched film, or a multilayer film having an Al foil, an Al vapor-deposited film, or a transparent vapor-deposited film, involves applying an adhesive to the bonding surface of a pre-formed layer of the stretched film, Al foil, Al vapor-deposited film, etc., and a layer of a heat-fusible film, etc., and then bonding the film by dry lamination (dry lamination).

[0005] However, dry lamination has problems such as the toxicity of residual solvents contained in the adhesive and the complexity of the process. Therefore, extrusion lamination without adhesive is also used to achieve multi-layering.

[0006] On the other hand, in order to improve the bonding strength between layers, extrusion lamination uses a method of extruding and laminating molten adhesive resin onto the surface of pre-formed stretch film, Al foil, Al vapor-deposited film, etc. However, there are problems such as the adhesion between the two layers not necessarily increasing, and the resulting multilayer film peeling at the interface between the substrate layer and the adhesive resin layer.

[0007] As compositions with excellent adhesive strength, a modified polyolefin composition for bonding containing an propylene polymer, a tackifier, a graft-modified propylene polymer, polyethylene, and an ethylene-α-olefin random copolymer has been proposed (Patent Document 1), or a resin composition containing an propylene resin, an propylene copolymer, an ethylene-α-olefin copolymer, and a polyethylene resin, which are modified polypropylene obtained by modifying unsaturated carboxylic acids or their derivatives (Patent Document 2).

[0008] However, because the modified polyolefin composition for bonding proposed in Patent Document 1 contains a tackifier, there is a risk of smoke during extrusion molding, or when a multilayer film containing a layer formed by the modified polyolefin composition for bonding is used as a packaging material for oily foods and beverages, there is a risk of the tackifier leaking into the food and beverages. The resin composition proposed in Patent Document 2 does not contain a tackifier, but the bonding strength is still insufficient. Depending on the application, a resin composition for bonding with superior bonding strength is required.

[0009] Existing technical documents

[0010] Patent documents

[0011] Patent Document 1: Japanese Patent Application Publication No. 2004-269688

[0012] Patent Document 2: Japanese Patent Application Publication No. 2012-188662 Summary of the Invention

[0013] The technical problem that the invention aims to solve

[0014] The object of the present invention is to obtain a resin composition that, when used as an adhesive layer in a laminate, has further improved adhesion to a substrate layer, and a laminate containing layers formed from the resin composition with superior interlayer adhesive strength.

[0015] Technical solutions for solving technical problems

[0016] This invention relates to a resin composition comprising:

[0017] The following propylene polymers (A) range from 5% to 70% by weight;

[0018] The following soft propylene polymers (B) range from 95% to 30% by weight;

[0019] The following propylene polymers (C) obtained by grafting with olefinic unsaturated monomers in the range of 0.1 to 20% by weight;

[0020] The following polyethylene (D) in the range of 0 to 20% by weight; and

[0021] The following ethylene-α-olefin random copolymers (E) range from 1 to 30% by weight.

[0022] Among them, the total weight of (A), (B), (C), (D) and (E) is set to 100% by weight.

[0023] Propylene polymers (A):

[0024] A propylene-based polymer having a content of 80 to 100 mol% of structural units derived from propylene and a content of less than 20 mol% of structural units derived from ethylene and / or α-olefins other than propylene, wherein the total content of structural units derived from propylene and the total content of structural units derived from ethylene and / or α-olefins other than propylene is set at 100 mol%.

[0025] The density, measured according to ASTM D1505, is 0.89 g / cm³. 3 above.

[0026] Soft propylene polymers (B):

[0027] A soft propylene polymer having a content of 50 to 95 mol% of structural units derived from propylene and a content of 5 to 50 mol% of structural units derived from ethylene and / or α-olefins other than propylene, wherein the total content of structural units derived from propylene and the total content of structural units derived from ethylene and / or α-olefins other than propylene is set at 100 mol%.

[0028] The density, measured according to ASTM D1505, is less than 0.89 g / cm³. 3 .

[0029] Propylene polymers (C) obtained by grafting and modifying with olefinic unsaturated monomers:

[0030] A modified propylene polymer is obtained by grafting an propylene polymer (c) containing 50 to 100 mol% of propylene-derived structural units and less than 50 mol% of ethylene and / or α-olefins other than propylene with olefin unsaturated monomers. In the propylene polymer (c), the total content of propylene-derived structural units and ethylene and / or α-olefins other than propylene is set to 100 mol.

[0031] Polyethylene (D):

[0032] The content of structural units derived from ethylene is 90–100 mol%.

[0033] The density, measured according to ASTM D1505, is between 0.90 and 0.94 g / cm³. 3 The range.

[0034] Ethylene-α-olefin random copolymer (E):

[0035] The content of structural units derived from ethylene ranges from 50 to 88 mol%, and the content of structural units derived from α-olefins ranges from 12 to 50 mol%. The total content of structural units derived from ethylene and structural units derived from α-olefins is set at 100 mol.

[0036] The density, measured according to ASTM D1505, is less than 0.90 g / cm³. 3 .

[0037] Invention Effects

[0038] The resin composition of the present invention has good extrudability and excellent adhesion strength to the substrate, thus providing a resin composition that can maintain good adhesion to the substrate layer and a laminate comprising layers formed from the resin composition. Detailed Implementation

[0039] <Propylene Polymer (A)>

[0040] The propylene polymer (A), one of the components contained in the resin composition of the present invention, is a propylene polymer in which the content of structural units derived from propylene is in the range of 80 to 100 mol%, preferably 81 to 99 mol%, more preferably 82 to 98 mol%, and the content of structural units derived from ethylene and / or α-olefins other than propylene is in the range of 0 to 20 mol%, preferably 1 to 19 mol%, more preferably 2 to 18 mol%, wherein the total content of structural units derived from propylene and the content of structural units derived from ethylene and / or α-olefins other than propylene is set as 100 mol%, and the density measured by ASTM D1505 is 0.89 g / cm³. 3 The preferred concentration is 0.89–0.92 g / cm³. 3 More preferably 0.89~0.91g / cm 3 The resin composition of the present invention containing propylene copolymer (A) with a density within the above-mentioned range has an excellent balance between softness and mechanical strength, and also has high adhesion to other layers.

[0041] The propylene polymer (A) of the present invention can specifically be a propylene homopolymer or a copolymer of propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms.

[0042] Examples of α-olefins having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene are particularly preferred as at least one olefin selected from ethylene and α-olefins. One or more of ethylene and α-olefins may be used; for example, ethylene and 1-butene may be used.

[0043] The copolymers of propylene and these α-olefins can be random copolymers or block copolymers. The content of structural units derived from these α-olefins in the copolymer of α-olefins and propylene can be 0 to 20 mol%, preferably 1 to 19 mol%.

[0044] The propylene polymer (A) of the present invention preferably satisfies the following requirement (a).

[0045] (a) The melting point (Tm) measured using a differential scanning calorimeter (DSC) is in the range of 120°C or higher, more preferably 120 to 170°C, and even more preferably 130 to 165°C.

[0046] The melt flow rate (MFR) of the propylene polymer (A) of the present invention, measured according to ASTM D 1238 at 230°C and a load of 2.16 kg, is typically in the range of 0.01 to 1000 g / 10 min, preferably 0.05 to 100 g / 10 min.

[0047] Examples of the propylene-based polymer (A) of the present invention include propylene homopolymers with excellent heat resistance, block copolymers with excellent balance between heat resistance and flexibility, such as block copolymers (block PP) that typically have 3 to 30% by mass of n-decane-soluble rubber components, and random copolymers (random PP) with excellent balance between flexibility and transparency, such as random copolymers (random PP) with a melting point (Tm) of 120°C or higher, preferably 130 to 150°C, as measured by differential scanning calorimetry (DSC). In order to obtain the target physical properties, appropriate selection can be made from these, or two or more propylene-based polymers (A) with different melting points and rigidities can be used together.

[0048] The propylene polymer (A) of the present invention can be manufactured, for example, by polymerizing propylene using a Ziegler catalyst system comprising a solid catalyst component containing magnesium, titanium, halogen and electron donor as essential components, an organoaluminum compound and an electron donor, or a metallocene catalyst system using a metallocene compound as one of the catalyst components, or by copolymerizing propylene with other α-olefins.

[0049] <Soft Acrylic Polymer (B)>

[0050] The soft propylene polymer (B), one of the components contained in the resin composition of the present invention, is a soft propylene polymer in which the content of structural units derived from propylene is in the range of 50-95 mol%, preferably 60-94 mol%, more preferably 70-93 mol%, and the content of structural units derived from ethylene and / or α-olefins other than propylene, preferably α-olefins with 4-20 carbon atoms, is in the range of 5-50 mol%, preferably 6-40 mol%, more preferably 7-30 mol%. The total content of structural units derived from propylene and structural units derived from ethylene and / or α-olefins other than propylene is set at 100 mol%, and the density measured by ASTM D1505 is less than 0.89 g / cm³. 3 The preferred concentration is 0.85–0.89 g / cm³. 3 More preferably 0.86~0.88g / cm³ 3 The resin composition of the present invention, containing a soft acrylic polymer (B) with a density within the above-mentioned range, exhibits an excellent balance between softness and mechanical strength, and also has high adhesion to other layers.

[0051] Examples of α-olefins with 4 to 20 carbon atoms include 3-methyl-1-butene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

[0052] The olefin selected from ethylene and α-olefins is particularly preferred, with ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene being particularly preferred. One or more of the ethylene and α-olefins may be used, for example, ethylene and 1-butene may be used.

[0053] The soft propylene polymer (B) of the present invention preferably satisfies the following requirement (b).

[0054] (b) The melting point (Tm) measured using a differential scanning calorimeter (DSC) is below 110°C, preferably 40 to 110°C, more preferably 45 to 108°C, or the melting point is not observable.

[0055] "Unobservable melting point" means that no melting peak with a melting heat of 1 J / g or higher was observed in the differential scanning calorimetry (DSC) range of -150 to 200 °C. When the melting point (Tm) meets the above conditions, the above melting point (Tm) is preferred from the perspective of compatibility with propylene-based polymers and transparency.

[0056] The details of the melting point determination conditions are described in the examples described later.

[0057] The MFR of the soft propylene polymer (B) of the present invention, measured according to ASTM D 1238 at 230°C and 2.16 kg load, is typically 0.01 to 100 g / 10 min, preferably 0.01 to 30 g / 10 min.

[0058] The soft propylene polymer (B) of the present invention preferably has a single glass transition temperature, and the glass transition temperature (Tg) measured using a differential scanning calorimeter (DSC) is typically in the range of -50 to 10°C, preferably -45 to 0°C, and more preferably -40 to 0°C.

[0059] When the glass transition temperature (Tg) of the soft propylene polymer (B) is within the above range, the packaging material with the obtained resin composition exhibits excellent cold resistance, low-temperature characteristics, and stress absorption performance, and is therefore preferred.

[0060] <Propylene polymers (C) obtained by grafting and modifying with olefinic unsaturated monomers>

[0061] It is a propylene polymer (C) obtained by grafting and modifying an olefinic unsaturated monomer as one of the components contained in the resin composition of the present invention (hereinafter sometimes simply referred to as "modified propylene polymer (C)").

[0062] The modified propylene polymer (C) of the present invention is a modified propylene polymer obtained by grafting an propylene polymer (c) in which the content of structural units derived from propylene is 50 to 100 mol% and the content of structural units derived from ethylene and / or α-olefins other than propylene is 50 mol% or less, using an olefin unsaturated monomer. The total content of structural units derived from propylene and structural units derived from ethylene and / or α-olefins other than propylene is set to 100 mol.

[0063] The propylene-based polymer (c) of the present invention is a homopolymer of propylene and / or a propylene-α-olefin copolymer. The α-olefin is not limited, but ethylene and α-olefins having 4 to 20 carbon atoms are preferred examples. These α-olefins can be a single type or two or more types. Preferred α-olefins are ethylene and α-olefins having 4 to 10 carbon atoms, with ethylene and α-olefins having 4 to 8 carbon atoms being particularly preferred. The content of propylene-derived structural units in the propylene-α-olefin copolymer is in the range of 50 to 100 mol%, preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and the content of structural units derived from ethylene and / or α-olefins other than propylene is in the range of 0 to 50 mol%, preferably 0 to 40 mol%, more preferably 0 to 30 mol%, wherein the total content of propylene-derived structural units and the content of ethylene and / or α-olefins other than propylene is set to 100 mol%.

[0064] The method for manufacturing the propylene polymer (c) of the present invention is not particularly limited, and known methods using known catalysts such as Ziegler-Natta catalysts and metallocene catalysts can be cited.

[0065] Examples of olefinic unsaturated monomers, preferably unsaturated carboxylic acids and / or their derivatives, that can be grafted onto the propylene polymer (c) of the present invention include unsaturated compounds having one or more carboxylic acid groups, esters of compounds having carboxylic acid groups and alkyl alcohols, and unsaturated compounds having one or more carboxylic anhydride groups.

[0066] Examples of unsaturated groups in unsaturated compounds include vinyl groups, vinylidenes, and unsaturated cyclic hydrocarbon groups. Unsaturated carboxylic acids and / or their derivatives can be used alone or in combination of two or more. Among these olefinically unsaturated monomers, unsaturated dicarboxylic acids or their anhydrides are suitable, with maleic acid, nadic acid, or their anhydrides being particularly preferred.

[0067] The method for grafting the propylene polymer (c) of the present invention with an olefin unsaturated monomer is not particularly limited, and existing known graft polymerization methods such as solution polymerization and melt mixing can be used. For example, there are methods such as melting the propylene polymer (c) and adding an olefin unsaturated monomer to carry out a grafting reaction; or dissolving the propylene polymer (c) in a solvent to form a solution, and then adding an olefin unsaturated monomer to it to carry out a grafting reaction, etc.

[0068] In the modified propylene polymer (C) of the present invention, the amount of structural units from the olefinic unsaturated monomer, converted according to the structural units from maleic anhydride, is preferably 0.01 to 5% by mass or 0.01 to 5.0% by mass, more preferably 0.05 to 3.5% by mass.

[0069] Resin compositions containing modified propylene polymers (C) in amounts of structural units derived from olefinic unsaturated monomers within the above-mentioned range can yield resin compositions with an excellent balance between moldability and adhesion.

[0070] <Polyethylene (D)>

[0071] Regarding polyethylene (D), which is one of the components contained in the resin composition of the present invention, the content of structural units derived from ethylene is 90 to 100 mol%, and the density measured by ASTM D1505 is 0.90 to 0.94 g / cm³. 3 The preferred concentration is 0.91–0.93 g / cm³. 3 The range.

[0072] The polyethylene (D) of the present invention is a homopolymer of ethylene manufactured and sold as high-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE), or a copolymer of ethylene and at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms, and is an ethylene-based polymer with ethylene as the main component.

[0073] Examples of α-olefins with 3 to 20 carbon atoms include propylene, 3-methyl-1-butene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. One or more of these α-olefins may be used.

[0074] The polyethylene (D) of the present invention, measured according to ASTM D1238 at 190°C and a load of 2.16 kg, typically has a molecular weight filtration rate (MFR) of 0.1 to 10 g / 10 min, preferably 0.5 to 8 g / 10 min, and more preferably 1 to 6 g / 10 min. Resin compositions of the present invention containing polyethylene (D) with an MFR within the above range exhibit an excellent balance between flexibility and mechanical strength, as well as high adhesion to other layers.

[0075] The method for manufacturing polyethylene (D) of the present invention is not particularly limited, and can be manufactured using known methods such as high-pressure methods or methods using known catalysts such as Ziegler-Natta catalysts or metallocene catalysts. Furthermore, as long as the material satisfies the requirements of moldability and has the strength to withstand use when molded, there are no particular limitations on stereoregularity, molecular weight, etc. Commercially available resins can also be used directly.

[0076] <Ethylene-α-olefin random copolymer (E)>

[0077] In the ethylene-α-olefin random copolymer (E), one of the components contained in the resin composition of the present invention, the content of structural units derived from ethylene ranges from 50 to 88 mol%, and the content of structural units derived from α-olefin ranges from 12 to 50 mol%. The total content of structural units derived from ethylene and structural units derived from α-olefin is set as 100 mol%. The density of the ethylene-α-olefin random copolymer (E), as measured by ASTM D1505, is less than 0.90 g / cm³. 3 .

[0078] The preferred α-olefins for copolymerization with ethylene are those with 3 to 20 carbon atoms, such as propylene, 3-methyl-1-butene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. One or more of these α-olefins may be used.

[0079] In the ethylene-α-olefin random copolymer (E) of the present invention, the content of structural units derived from ethylene is preferably in the range of 50 to 88 mol%, more preferably 60 to 86 mol%, and even more preferably 60 to 85 mol%, and the content of structural units derived from α-olefin is preferably in the range of 12 to 50 mol%, more preferably 14 to 40 mol%, and even more preferably 15 to 40 mol%.

[0080] The ethylene-α-olefin random copolymer (E) of the present invention preferably has a density of 0.85 to 0.90 g / cm³. 3 More preferably 0.86~0.90g / cm³ 3 The range.

[0081] The MFR of the ethylene-α-olefin random copolymer (E) of the present invention, measured according to ASTM D 1238 at 190°C and a load of 2.16 kg, is typically 0.1 to 100 g / 10 min, preferably in the range of 0.5 to 50 g / 10 min. The resin compositions of the present invention containing the ethylene-α-olefin random copolymer (E) with an MFR within the above range exhibit an excellent balance between flexibility and mechanical strength, as well as high adhesion to other layers.

[0082] The ethylene-α-olefin random copolymer (E) of the present invention preferably satisfies the following requirement (e).

[0083] (e) The melting point (Tm) measured using a differential scanning calorimeter (DSC) is below 110°C, preferably 40 to 85°C, more preferably 40 to 60°C, or the melting point cannot be observed.

[0084] "Unobservable melting point" means that no crystallization melting peak with a melting heat of more than 1 J / g was observed in the range of -150 to 200 °C during differential scanning calorimetry. Regarding the above melting point (Tm), the resin composition of the present invention containing an ethylene-α-olefin random copolymer (E) that meets the above conditions has an excellent balance between softness and mechanical strength, and also has high adhesion to other layers.

[0085] The details of the melting point determination conditions are described in the examples described later.

[0086] The method for producing the ethylene-α-olefin random copolymer (E) of the present invention is not particularly limited, and known methods using known catalysts such as Ziegler-Natta catalysts and metallocene catalysts can be cited as examples.

[0087] Resin Compositions

[0088] The resin composition of the present invention contains:

[0089] The above-mentioned propylene polymer (A) is in the range of 5 to 70% by weight, preferably 5 to 50% by weight, and more preferably 5 to 30% by weight;

[0090] The above-mentioned soft propylene polymer (B) is in the range of 30-95% by weight, preferably 35-95% by weight, and more preferably 40-95% by weight;

[0091] The propylene polymer (C) obtained by grafting and modifying with olefinic unsaturated monomers is in the range of 0.1 to 20% by weight, preferably 0.5 to 15% by weight, and more preferably 1 to 10% by weight.

[0092] The aforementioned polyethylene (D) ranges from 0 to 20% by weight, preferably 1 to 20% by weight, more preferably 1 to 19% by weight, further preferably 2 to 18% by weight, and particularly preferably 10 to 18% by weight; and

[0093] The above-mentioned ethylene-α-olefin random copolymer (E) is in the range of 1 to 30% by weight, preferably 2 to 29% by weight, and more preferably 3 to 28% by weight.

[0094] Among them, the total weight of (A), (B), (C), (D) and (E) is set to 100% by weight.

[0095] The resin composition of the present invention, by containing the above-mentioned components (A), (B), (C) and (E) within the above-mentioned range, can obtain a resin composition with excellent balance between moldability and adhesion.

[0096] The resin composition of the present invention, by containing the above-mentioned components (A), (B), (C), (D), and (E) within the above-mentioned range, can obtain a resin composition with excellent balance between moldability and adhesion.

[0097] The resin composition of the present invention has excellent adhesion to other materials, and therefore can also be used as a resin composition for adhesives, such as a resin composition for hot melt adhesives.

[0098] The resin compositions of the present invention typically exhibit a medium flow rate (MFR) of 1–50 g / 10 min, preferably 5–30 g / 10 min, as measured according to ASTM D 1238 at 230°C and a load of 2.16 kg. Resin compositions with an MFR within this range demonstrate an excellent balance between moldability and adhesion.

[0099] Without prejudice to the purpose of the present invention, the resin composition of the present invention may also contain other thermoplastic resins such as polyolefin resins, resin additives (e.g., heat stabilizers, weather stabilizers and other stabilizers, crosslinking agents, crosslinking aids, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, fillers, mineral oil softeners, petroleum resins, waxes, etc.).

[0100] In this invention, the content of the tackifier in the resin composition is preferably 0% by weight or more and less than 1% by weight, more preferably 0% by weight. Here, 0% by weight means no tackifier is present.

[0101] Examples of such thickeners include aliphatic hydrocarbon resins made primarily from C4 fractions, C5 fractions, mixtures thereof, or any fractions thereof obtained by cracking petroleum, naphtha, etc., such as isoprene and 1,3-pentadiene in the C5 fraction; aromatic hydrocarbon resins made primarily from styrene derivatives and indene in the C9 fraction obtained by cracking petroleum, naphtha, etc.; aliphatic / aromatic copolymerized hydrocarbon resins obtained by copolymerizing any fraction from the C4 / C5 fraction with the C9 fraction; alicyclic hydrocarbon resins obtained by hydrogenating aromatic hydrocarbon resins; synthetic terpene hydrocarbon resins having structures containing aliphatic, alicyclic, and aromatic compounds; terpene hydrocarbon resins made from α,β-pinene in turpentine; coumarone-indene hydrocarbon resins made from indene and styrene in coal tar naphtha; low molecular weight styrene resins; and rosin hydrocarbon resins.

[0102] Methods for manufacturing resin compositions

[0103] The olefin polymer composition of the present invention can be manufactured by various known methods, for example by melt-blending and dry-blending the above-mentioned propylene polymer (A), the above-mentioned soft propylene polymer (B), the above-mentioned propylene polymer (C) obtained by grafting modification with olefin unsaturated monomers, the above-mentioned polyethylene (D), and the above-mentioned ethylene-α-olefin random copolymer (E) in amounts within the above range.

[0104] Layered structures

[0105] The laminate of the present invention is a laminate comprising a layer formed of the resin composition of the present invention described above, for example, a laminate having a layer formed of the resin composition of the present invention laminated on at least one side of a substrate layer.

[0106] The laminate of the present invention does not have any particular limitation on the shape of the substrate layer, such as it can be a membrane, container, tube or the like.

[0107] As the substrate used in this invention, any polymer with film-forming ability, or paper, aluminum foil, cellophane, etc., can be used. Examples of such polymers include high-density polyethylene, medium-density polyethylene, low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, ionomers, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and other olefin copolymers; vinyl copolymers such as polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylate, and polyacrylonitrile; polyamides such as nylon 6, nylon 66, nylon 7, nylon 10, nylon 1, nylon 12, nylon 610, and poly(m-phenylene adipamide); polyesters such as polyethylene terephthalate, polyethylene terephthalate / isophthalate, and polybutylene terephthalate; polyvinyl alcohol; ethylene-vinyl alcohol copolymer; and polycarbonate.

[0108] When the substrate of the present invention has an inorganic compound vapor-deposited layer or a metal layer on at least one side of the substrate, the resulting laminate has better aesthetics and gas barrier properties, and is therefore preferred.

[0109] When a substrate having an inorganic vapor-deposited layer or a metal layer on at least one side is used, the layer of the resin composition of the present invention can be in contact with the inorganic vapor-deposited layer or the metal layer of the substrate (i.e., the side of the substrate layer having the above-mentioned resin composition can have an inorganic vapor-deposited layer or a metal layer), or it can be in contact with the opposite side. When the inorganic vapor-deposited layer is disposed on the outside, one or more protective layers can also be stacked.

[0110] As this protective layer, polymers or paper, aluminum foil, cellophane, etc., that can be used for the aforementioned substrate layer can be used, such as polyethylene terephthalate.

[0111] The substrate of this invention can be appropriately selected according to the purpose. For example, when the packaged item is a perishable food, resins with excellent transparency, rigidity, and gas permeability resistance, such as polyamide, polyvinylidene chloride, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, and polyester, can be selected. For pastries, fiber packaging, etc., polypropylene, which has good transparency, rigidity, and water permeability resistance, can be selected as the outer layer. In addition, if the substrate is a polymer, it can be uniaxially stretched or biaxially stretched. Furthermore, the substrate may also include a printing surface and a primer.

[0112] Inorganic compounds used for inorganic compound vapor deposition include metals such as aluminum, gold, and silver; oxides such as aluminum oxide, silicon oxide, magnesium oxide, and zinc indium oxide; but considering price and gas barrier properties, aluminum, aluminum oxide, and silicon oxide are more suitable.

[0113] There are no particular limitations on the thickness of the vapor-deposited layer, but it is preferred to be within a certain range. The scope, more preferably in The range.

[0114] As a method for obtaining a laminate using the resin composition of the present invention, examples include melting the resin composition of the present invention and one or more other resins constituting the laminate separately using separate extruders on a pre-formed substrate, and then feeding the melted mixture into a die with a structure of two or more layers, co-extruding and laminating the mixture onto the substrate such that the resin composition of the present invention is located on the substrate side; or, melting and extruding the composition between two layers of the pre-formed substrate, i.e., a so-called sandwich lamination method, etc. The die used here can be a so-called flat die, and can be any form using a single manifold or a multi-manifold with a black box.

[0115] It should be noted that there is no particular limitation on the thickness of the layer using the resin composition of the present invention, but it is preferably in the range of 0.1 to 1000 μm.

[0116] The resin composition of the present invention exhibits excellent adhesion to both the metal layer and the resin. Therefore, the laminate of the present invention is suitable for food packaging such as snacks and dry foods.

[0117] Example

[0118] The present invention will be described in more detail below with reference to embodiments, but the present invention is not limited to these embodiments.

[0119] The polymers used in the examples and comparative examples are shown below.

[0120] [Propylene polymer (A)]

[0121] As a propylene-based polymer (A), a random copolymer of propylene-ethylene-1-butene (PP) was used.

[0122] Propylene content = 87 mol%, ethylene content = 7 mol%, 1-butene content = 6 mol%, MFR (230℃, 2.16 kg load) = 7 g / 10 min, density = 0.90 g / cm³ 3 Melting point (Tm) = 141℃.

[0123] [Soft Acrylic Polymer (B)]

[0124] As a soft propylene polymer (B), a propylene-ethylene random copolymer (PER) was used.

[0125] Propylene content = 79 mol%, ethylene content = 21 mol%, MFR (230℃, 2.16 kg load) = 20 g / 10 min, density = 0.86 g / cm³ 3 Melting point (Tm) = 109℃, glass transition temperature (Tg) = -33℃.

[0126] [Propylene polymers (C) obtained by grafting and modifying with olefinic unsaturated monomers]

[0127] Maleic anhydride-modified propylene homopolymer (modified PP) was used as the modified propylene polymer (C).

[0128] MFR (230℃, 2.16kg load) = 100g / 10min, density = 0.90g / cm³ 3 Maleic anhydride graft modification amount = 3.0% by mass.

[0129] [Polyethylene (D)]

[0130] As polyethylene (D), the following high-pressure low-density polyethylene was used.

[0131] Low-density polyethylene (LDPE-1) produced by high-pressure process

[0132] MFR (190℃, 2.16kg load) = 4g / 10min, density = 0.92g / cm³ 3 .

[0133] Low-density polyethylene (LDPE-2) produced by high-pressure process

[0134] MFR (190℃, 2.16kg load) = 7g / 10min, density = 0.92g / cm³ 3 .

[0135] [Ethylene-α-olefin random copolymer (E)]

[0136] As an ethylene-α-olefin random copolymer (E), the following ethylene-1-butene copolymers were used.

[0137] Ethylene-1-butene copolymer (EBR-1)

[0138] MFR (230℃, 2.16kg load) = 7g / 10min, density = 0.87g / cm³ 3 Ethylene content = 85 mol%, 1-butene content = 15 mol%.

[0139] Ethylene-1-butene copolymer (EBR-2)

[0140] MFR (230℃, 2.16kg load) = 70g / 10min, density = 0.87g / cm³ 3 Ethylene content = 85 mol%, 1-butene content = 15 mol%.

[0141] Ethylene-1-butene copolymer (EBR-3)

[0142] MFR (230℃, 2.16kg load) = 7g / 10min, density = 0.89g / cm³ 3 Ethylene content = 90 mol% (82 wt%), 1-butene content = 10 mol% (18 wt%).

[0143] Ethylene-propylene copolymer (EPR)

[0144] MFR (230℃, 2.16kg load) = 8g / 10min, density = 0.87g / cm³ 3 Ethylene content = 80 mol%, propylene content = 20 mol%.

[0145] The physical properties of the polymer and resin compositions used in the examples and comparative examples were determined using the following methods.

[0146] [Methods for determining physical properties]

[0147] Melt Flow Rate (MFR)

[0148] MFR was determined according to ASTM D1238. The MFR of propylene polymers (A), flexible propylene polymers (B), propylene polymers modified by grafting with olefinic unsaturated monomers (C), ethylene-α-olefin copolymers (E), and resin compositions was determined at 230°C and a 2.16 kg load. The MFR of polyethylene (D) was determined at 190°C and a 2.16 kg load.

[0149] <Density>

[0150] The density was determined according to ASTM D1505 (density gradient tube method).

[0151] <Polymer Composition>

[0152] pass 13 C-NMR was used to determine the content of ethylene-derived structural units and α-olefin-derived structural units in the copolymer using the following apparatus and conditions.

[0153] The quantification of ethylene and α-olefin contents was performed using a JECX400P nuclear magnetic resonance (NMR) system manufactured by NEC Corporation. A mixed solvent of deuterated o-dichlorobenzene / deuterated benzene (80 / 20 volume %) was used as the solvent. The sample concentration was 60 mg / 0.6 mL, the measurement temperature was 120 °C, and the observed nuclei were... 13 C(100MHz), the sequence was a single-pulse proton decoupled sequence with a pulse width of 4.62μs (45° pulse), a repetition time of 5.5 seconds, a cumulative number of times of 8000, and the measurement was performed with 29.73ppm as the chemical shift reference value.

[0154] <Amount of structural units from olefinic unsaturated monomers (grafting modification amount)>

[0155] Regarding the amount of structural units from the olefinic unsaturated monomer (grafting modification amount), the peak from the above structural units was determined using an infrared absorption analyzer (1790 cm⁻¹ when using maleic anhydride). ﹣1 The intensity of the ) was quantified using a pre-made standard curve.

[0156] Melting point (Tm), glass transition temperature (Tg)

[0157] The Tm and Tg of the raw materials for the following adhesives were determined by differential scanning calorimetry (DSC) using the following method.

[0158] A sample of approximately 5 mg was sealed in an aluminum dish. Using a Seiko Instruments Inc. DSCRDC220, the temperature was increased from room temperature to 200 °C at a rate of 10 °C / min. After holding at 200 °C for 5 minutes, the temperature was decreased from 200 °C to -100 °C at a rate of 10 °C / min. The temperature was then held at -100 °C for 5 minutes, and then increased to 200 °C at a rate of 10 °C / min. The melting point (Tm) and glass transition temperature (Tg) were determined from the endothermic curve at this point.

[0159] When multiple peaks are detected during measurement, the temperature of the peak detected at the highest temperature side is defined as the melting point (Tm).

[0160] [Example 1]

[0161] <Preparation of Resin Compositions>

[0162] A resin composition was obtained by melt-blending propylene polymer (A) PP: 26 wt%, soft propylene polymer (B) PER: 45 wt%, propylene polymer (C) modified PP obtained by grafting with olefinic unsaturated monomers: 4 wt%, and ethylene-α-olefin random copolymer (E) EBR-1: 25 wt% using a single-screw extruder at 230°C. The resulting resin composition had an MFR of 14 g / 10 min and a density of 0.88 g / cm³. 3 .

[0163] <Fabrication of Laminated Structures>

[0164] Commercially available polypropylene (F329RA manufactured by Priman Polymer Co., Ltd., MFR (230°C): 27 g / 10 min) and the above-mentioned resin composition were co-extruded at 230°C into a T-die with a die temperature of 310°C using a co-extrusion film forming machine with a screw having a diameter of 50 mm and an effective length L / D = 28. Extruded polypropylene and resin composition are laminated in the feed block of a T-die, with polypropylene as the outer layer and resin composition as the inner layer. The film-like laminate, with both the outer and inner layers being 20 μm thick and approximately 40 μm thick, is in contact with the aluminum side of an aluminum PET film (aluminum layer: 20 μm / polyethylene terephthalate layer: 12 μm) in a molten state (extrusion lamination). It is cooled using a cooling roller with pinch rollers and wound at a speed of 25 m / min to obtain a multilayer film for evaluating adhesive strength (polypropylene layer: 20 μm / resin composition layer: 20 μm / aluminum layer: 20 μm / polyethylene terephthalate layer: 12 μm).

[0165] [Moldability]

[0166] When forming a laminate using the co-extrusion coating molding method described above, evaluate whether there is edge oscillation at the end of the molten film.

[0167] [Interlayer adhesion of multilayer films]

[0168] After storing the resulting multilayer film laminate at room temperature for one week, the laminate was cut into 15 mm wide pieces, and the interlayer adhesion between the aluminum layer and the resin composition layer was evaluated using the T-peel method. The evaluation was conducted using a tensile testing machine at 23°C. The crosshead speed was set to 300 mm / min.

[0169] The properties of the obtained resin compositions and laminates are shown in Table 1.

[0170] [Examples 2-9]

[0171] Except for the formulation shown in Table 1, the adhesive was prepared in the same manner as in Example 1, and the laminate was manufactured using the same method as in Example 1.

[0172] The physical properties of the resulting adhesive and laminate are shown in Table 1.

[0173] [Comparative Examples 1-6]

[0174] Except for the formulation shown in Table 1, the adhesive was prepared in the same manner as in Example 1, and the laminate was manufactured using the same method as in Example 1.

[0175] The properties of the obtained resin compositions and laminates are shown in Table 2.

[0176] [Table 1]

[0177]

[0178] [Table 2]

[0179]

[0180] [Example 10]

[0181] Aluminum vapor-deposited PET film (12 μm) was used instead of aluminum PET film as the substrate, and the formulation was changed to that shown in Table 2. Otherwise, the resin composition was prepared in the same manner as in Example 1, and the laminate was manufactured using the same method as in Example 1.

[0182] The properties of the obtained resin compositions and laminates are shown in Table 3.

[0183] [Table 3]

[0184]

Claims

1. A resin composition, characterized in that, contain: The following propylene polymers (A) range from 5% to 50% by weight; The following soft propylene polymers (B) range from 30% to 95% by weight. The following propylene polymers (C) obtained by grafting and modifying with olefinic unsaturated monomers in the range of 0.5 to 15% by weight. The following polyethylene (D) ranges from 1 to 20% by weight; and The following ethylene-α-olefin random copolymers (E) range from 1% to 30% by weight. The total amount of (A), (B), (C), (D), and (E) is set to 100% by weight. Acrylic polymer (A) is an propylene polymer in which the content of structural units derived from propylene is in the range of 80 to 100 mol%, and the content of structural units derived from ethylene and / or α-olefins other than propylene is in the range of 20 mol%. The total content of structural units derived from propylene and structural units derived from ethylene and / or α-olefins other than propylene is defined as 100 mol%. The density of propylene polymer (A) as measured by ASTM D1505 is 0.89 g / cm³. 3 above, Soft propylene polymer (B) is a soft propylene polymer in which the content of structural units derived from propylene ranges from 50 to 95 mol% and the content of structural units derived from ethylene and / or α-olefins other than propylene ranges from 5 to 50 mol%. The total content of structural units derived from propylene and structural units derived from ethylene and / or α-olefins other than propylene is defined as 100 mol%. The density of soft propylene polymer (B), as measured by ASTM D1505, is less than 0.89 g / cm³. 3 , The propylene polymer (C) obtained by grafting modification with an olefinically unsaturated monomer is a modified propylene polymer obtained by grafting an olefinically unsaturated monomer onto a propylene polymer (c) in which the content of structural units derived from propylene is 50-100 mol% and the content of structural units derived from ethylene and / or α-olefins other than propylene is less than 50 mol%. In the propylene polymer (C), the total content of structural units derived from propylene and structural units derived from ethylene and / or α-olefins other than propylene is set as 100 mol%. In the propylene polymer (C) obtained by grafting modification with an olefinically unsaturated monomer, the amount of structural units from the olefinically unsaturated monomer is 0.01-5.0% by mass. The olefinically unsaturated monomer is an unsaturated dicarboxylic acid or its anhydride. The content of ethylene-derived structural units in polyethylene (D) is 90–100 mol%, and the density of polyethylene (D) as measured by ASTM D1505 is 0.90–0.94 g / cm³. 3 Scope The content of ethylene-α-olefin random copolymer (E) derived from ethylene ranges from 60 to 85 mol%, and the content of α-olefin-derived structural units ranges from 15 to 40 mol%. The total content of ethylene-derived and α-olefin-derived structural units is defined as 100 mol%. The density of the ethylene-α-olefin random copolymer (E), as measured by ASTM D1505, is less than 0.90 g / cm³. 3 , In the ethylene-α-olefin random copolymer (E), the α-olefin constituting the ethylene-α-olefin random copolymer (E) is an α-olefin with 3 to 8 carbon atoms.

2. The resin composition according to claim 1, characterized in that: The soft propylene polymer (B) is a propylene-ethylene copolymer.

3. The resin composition according to claim 1 or 2, characterized in that: The propylene polymer (C) obtained by grafting modification with olefinic unsaturated monomers is a propylene polymer (C) obtained by grafting modification with maleic anhydride.

4. The resin composition according to claim 1 or 2, characterized in that: The resin composition is a resin composition without tackifier.

5. The resin composition according to claim 1 or 2, characterized in that: The resin composition is an adhesive resin composition.

6. A laminated body, characterized in that: It comprises a layer formed from the resin composition of any one of claims 1 to 4.

7. The laminate as described in claim 6, characterized in that: A layer formed of the resin composition is laminated on at least one side of the substrate layer.

8. The laminate as described in claim 7, characterized in that: The substrate layer has an inorganic compound vapor-deposited layer on the surface of the resin composition in the stack of the substrate layers.

9. The laminate as described in claim 8, characterized in that: The inorganic compound vapor deposition layer is an aluminum vapor deposition layer.

10. The laminate as described in claim 7, characterized in that: The substrate layer has a metal layer on the side of the resin composition in the stack of the substrate layers.

11. The laminate as described in claim 10, characterized in that: The metal layer is an aluminum layer.

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