Laminate and method for manufacturing the laminate

Abstract

One embodiment of the present invention pertains to a laminate or a method for manufacturing a laminate. This laminate has: a layer (A) which contains polyphenylene sulfide; and an adhesive layer (B) which contains an adhesive composition and at least a part of which is in contact with the layer (A), wherein the adhesive composition contains a graft-modified product, of at least one base polymer selected from among polyolefins, by means of a carbodiimide monomer having a carbodiimide group and a polymerizable double bond, 0.1-50 mmol of the carbodiimide group is contained per 100 g of the adhesive composition, and the density of the adhesive composition is 0.870-0.940 g / cm3.

Description

[Technical Field]

[0001] One embodiment of the present invention relates to a laminate or a method for manufacturing a laminate. [Background technology]

[0002] Polyphenylene sulfide (hereinafter referred to as "PPS") is characterized by high heat resistance and high chemical resistance, and is used in electronic components, machine components, medical components, hot water pipes, etc. However, because PPS is expensive, there are studies being conducted on combining it with different materials.

[0003] However, the terminal functional groups of PPS are known to have poor reactivity with functional groups present on the surface of other resins (e.g., conventionally known maleic anhydride-modified resins), resulting in poor adhesion to other resins. This has limited the use of PPS in lamination with other materials.

[0004] In order to solve these problems, Patent Document 1 discloses a laminate having a PPS-containing layer and a layer made of an adhesive composition containing a predetermined component, at least a portion of which is in contact with the PPS-containing layer, as a laminate having high adhesive strength with the PPS-containing layer. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2017 / 104731 Summary of the Invention

[0006] However, in response to recent increases in demand for physical properties, there is a demand for a laminate of a PPS-containing layer and an adhesive layer that has even higher adhesive strength than the laminate described in Patent Document 1. In particular, when forming a laminate by a method that does not allow for a long sealing time, such as co-injection molding, there is a strong demand for a PPS laminate that exhibits high adhesive strength even with a shorter sealing time.

[0007] One embodiment of the present invention provides a laminate that exhibits excellent adhesive strength between a PPS-containing layer and an adhesive layer even in a short sealing time, and a method for producing the same. [Means for solving the problem]

[0008] A configuration example of the present invention is as follows.

[0009] [1] A film having a layer (A) containing polyphenylene sulfide and an adhesive layer (B) containing an adhesive composition, At least a portion of the adhesive layer (B) is in contact with the layer (A), A laminate, wherein the adhesive composition satisfies the following requirements (i) to (iii): (i) At least one base polymer selected from polyolefins is graft-modified with a carbodiimide monomer having a carbodiimide group and a polymerizable double bond; (ii) the adhesive composition contains 0.1 to 50 mmol of carbodiimide groups per 100 g; (iii) Density is 0.870 to 0.940 g / cm 3 is.

[0010] [2] The laminate according to [1], wherein the carbodiimide monomer is at least one monomer selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (2):

[0011] [ka] [In formula (1), R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group or an aryl group which may have a substituent, In formula (2), R3 is a hydrogen atom or a methyl group, R4 is an alkyl group or an aryl group which may have a substituent, and m is an integer of 2 or greater.

[0012] [3] The laminate according to [1] or [2], wherein the layer (A) is made of polyphenylene sulfide.

[0013] [4] The laminate according to any one of [1] to [3], which is obtained by coextrusion molding, lamination molding, blow molding or coinjection molding.

[0014] [5] A method for producing a laminate, The laminate has a layer (A) containing polyphenylene sulfide and an adhesive layer (B) containing an adhesive composition, and at least a portion of the adhesive layer (B) is in contact with the layer (A), The production method includes a step 1 of co-extrusion molding, lamination molding, blow molding, or coinjection molding a resin composition containing polyphenylene sulfide and the adhesive composition, A method for producing a laminate, wherein the adhesive composition satisfies the following requirements (i) to (iii): (i) At least one base polymer selected from polyolefins is graft-modified with a carbodiimide monomer having a carbodiimide group and a polymerizable double bond; (ii) the adhesive composition contains 0.1 to 50 mmol of carbodiimide groups per 100 g; (iii) Density is 0.870 to 0.940 g / cm 3 is.

[0015] [6] The method for producing a laminate according to [5], wherein the carbodiimide monomer is at least one monomer selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (2):

[0016] [ka] [In formula (1), R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group or an aryl group which may have a substituent, In formula (2), R3 is a hydrogen atom or a methyl group, R4 is an alkyl group or an aryl group which may have a substituent, and m is an integer of 2 or greater.

[0017] [7] The method for producing a laminate according to [5] or [6], wherein the layer (A) is made of polyphenylene sulfide. [Effects of the Invention]

[0018] According to one embodiment of the present invention, it is possible to provide a laminate having excellent adhesive strength between a layer containing PPS, which is a resin having polar groups, and an adhesive layer even with a short sealing time (e.g., 5 seconds or less), and a method for producing the same. DETAILED DESCRIPTION OF THE INVENTION

[0019] <Laminate> A laminate according to one embodiment of the present invention comprises a layer (A) containing PPS and an adhesive layer (B) containing an adhesive composition, with at least a portion of layer (B) in contact with layer (A). Since the laminate has the layer (B), it has excellent interlayer adhesion, and even if the laminate is formed in a short sealing time of, for example, 5 seconds or less, or even if the laminate is heat-treated at a high temperature of, for example, 200 to 250°C, it is possible to obtain a laminate in which the interlayer adhesion strength is not easily reduced.

[0020] The laminate is not particularly limited as long as it contains the layer (A) and the layer (B), and may contain two or more layers of the layer (A), or may contain two or more layers of the layer (B). When two or more layers (A) are contained, these layers may be the same layer or different layers. Similarly, when two or more layers (B) are contained, these layers may be the same layer or different layers. The laminate is preferably a laminate including a layer (A) and a layer (B), particularly a laminate consisting of a layer (A) and a layer (B), or a laminate including a layer (A), a layer (B), and a layer (A) in this order, particularly a laminate in which a layer (A), a layer (B), and a layer (A) are laminated in this order.

[0021] The laminate containing the layer (A) and the layer (B) may be, for example, a laminate containing the layer (A), the layer (B), and the layer (C) in this order. The layer (C) is not particularly limited as long as it is a layer other than the layer (A) and the layer (B), and examples thereof include layers containing or consisting of metal; glass; wood; paper; cloth; thermoplastic resins such as polyester, polyamide, polyacetal, polycarbonate, poly(meth)acrylate, olefin polymer, polystyrene, rubber, modified fluororesin, biomass plastic, and other engineering plastics; and thermosetting resins.

[0022] The laminate is not limited to a laminate film (sheet) shape, and may be any of various known shapes such as a hollow container, a cup, a tray, and the like.

[0023] The laminate is preferably a laminate obtained by co-extrusion molding, lamination molding, blow molding or coinjection molding, since a laminate having excellent adhesive strength can be easily obtained.

[0024] <Layer (A) Containing Polyphenylene Sulfide> The layer (A) is not particularly limited as long as it contains polyphenylene sulfide (PPS), and is preferably a layer made of PPS (only).

[0025] The PPS may be a polymer made solely from biomass-derived raw materials, a polymer made solely from fossil fuel-derived raw materials, or a polymer made from both biomass-derived raw materials and fossil fuel-derived raw materials. It is preferable that the PPS is a polymer made from raw materials derived from biomass from the viewpoint of reducing the environmental load (mainly reducing greenhouse gas emissions).

[0026] Examples of the PPS include polymers formed by linking aromatic rings with sulfide bonds, such as branched or linear polyphenylene sulfide and copolymers thereof. Specific examples include poly(paraphenylene sulfide) and poly(metaphenylene sulfide). Furthermore, PPS may be a copolymer, such as a copolymer having, in addition to a unit consisting of an aromatic ring and a sulfide bond, an ether unit, a sulfone unit, a biphenyl unit, a naphthyl unit, a substituted phenyl sulfide unit, a trifunctional phenyl sulfide unit, or the like in the molecule. Specific examples include polythio-1,4-phenylene. Alternatively, commercially available PPS may be used as the PPS, such as Fortron FX4382T1 manufactured by Ticona and Torelina A900 manufactured by Toray Industries, Inc. As the PPS, one type may be used, or two or more types may be used.

[0027] The layer (A) may contain, as necessary, additives that are usually added to resins, such as phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, metal compounds, and metal salts of higher fatty acids, within the scope of the present invention. The additive may be an additive using only biomass-derived raw materials as its raw materials, an additive using only fossil fuel-derived raw materials, or an additive using both biomass-derived raw materials and fossil fuel-derived raw materials.

[0028] The thickness of the layer (A) is not particularly limited and may be appropriately selected depending on the application of the laminate, but is preferably 2 to 1000 μm.

[0029] <Adhesive layer (B)> The layer (B) is a layer containing an adhesive composition (hereinafter also referred to as "the present composition") and can be obtained using the present composition. The content of the present composition in layer (B) is preferably 80 to 100% by mass, more preferably 90 to 100% by mass.

[0030] The thickness of the layer (B) is not particularly limited and may be appropriately selected depending on the application of the laminate, but is preferably 2 to 1000 μm.

[0031] [Adhesive composition] The present composition satisfies the following requirements (i) to (iii). (i) The polymer includes a graft-modified product (hereinafter also referred to as "the modified product") of at least one base polymer selected from polyolefins with a carbodiimide monomer having a carbodiimide group and a polymerizable double bond. (ii) The composition contains 0.1 to 50 mmol of carbodiimide groups per 100 g. (iii) Density is 0.870 to 0.940 g / cm 3 is.

[0032] The amount of carbodiimide groups in the present composition is 0.1 to 50 mmol, preferably 0.2 to 20 mmol, and more preferably 0.5 to 5 mmol, per 100 g of the present composition. When the amount of carbodiimide groups is within the above range, it is possible to easily obtain the present composition that can firmly bond to an adherend, particularly a layer containing PPS, even when the composition is bonded at a low temperature at which the PPS does not thermally decompose. The amount of carbodiimide groups is specifically measured by the method described in the examples below.

[0033] The density of this composition, measured in accordance with JIS K 7210, is 0.870 to 0.940 g / cm 3 and preferably 0.880 to 0.925 g / cm 3 , more preferably 0.890 to 0.920 g / cm 3 is. When the density is within the above range, it is possible to easily obtain the composition that can firmly bond to an adherend, particularly a layer containing PPS, even when the composition is bonded at a low temperature at which the PPS does not thermally decompose.

[0034] The melt flow rate (MFR) of the composition, measured in accordance with JIS K 7210 at 190° C. under a load of 2.16 kg, is preferably 0.1 to 10 g / 10 min, more preferably 0.2 to 5 g / 10 min. When the MFR is within the above range, it is possible to easily form a desired laminate by a molding method such as coextrusion molding, lamination molding, blow molding, or coinjection molding, which is preferable.

[0035] The present composition is not particularly limited as long as it contains the present modified product, and may consist solely of the present modified product. Because the present composition contains the present modified product, it is possible to form a layer with high adhesive strength on an adherend, particularly on a layer containing PPS, even with a short sealing time. This modified product has higher reactivity with polar groups present in PPS and other materials than graft-modified products with glycidyl (meth)acrylate or acids or acid anhydrides, and therefore the composition containing this modified product has significantly superior adhesion to layers containing PPS. The present modified product is not a block copolymer or random copolymer of an olefinic monomer such as ethylene or propylene with the carbodiimide monomer, but a graft modified product, and by using the present modified product, the present composition exhibits the above-mentioned effects.

[0036] The present modified product used in the present composition may be one type or two or more types. The content of the present modified product in the present composition is not particularly limited, but from the viewpoints of moldability, controllability of adhesiveness, economic efficiency, etc., it is usually 0.5% by mass or more, preferably 1% by mass or more, and usually 60% by mass or less, preferably 50% by mass or less.

[0037] The present composition preferably contains the present modified product and one or more olefin polymers other than the present modified product. The olefin polymer that may be used in the present composition is not particularly limited as long as it is a polymer made from an olefin, and various known olefin polymers can be used. Specific examples include homopolymers or copolymers of α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene (e.g., high-pressure low-density polyethylene, linear low-density polyethylene (LLDPE), medium-density polyethylene, high-density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, low-crystalline or amorphous ethylene-propylene random copolymers, ethylene-1-butene random copolymers, and propylene-1-butene random copolymers), ethylene-vinyl acetate copolymers (EVA) or saponified products thereof, ethylene-(meth)acrylic acid copolymers or metal salts (ionomers) thereof, ethylene-cyclic olefin copolymers, and polymers obtained by graft-modifying these (co)polymers with polar compounds such as maleic acid or silane compounds. Among these, when the present composition contains a certain present modified product, the olefin polymer is preferably the same polymer as the base polymer used in the synthesis of the present modified product, in terms of excellent compatibility and ease of obtaining the present composition which better exhibits the desired effects.

[0038] The olefin-based polymer may be a polymer using only biomass-derived raw materials as its raw materials (e.g., olefin), a polymer using only fossil fuel-derived raw materials, or a polymer using both biomass-derived raw materials and fossil fuel-derived raw materials. It is preferable that the olefin polymer is a polymer made from a raw material derived from biomass from the viewpoint of reducing the environmental load (mainly reducing greenhouse gas emissions).

[0039] In this specification, biomass-derived raw materials refer to raw materials made from any (renewable) natural raw materials and their residues, such as those derived from plants or animals, including fungi, yeasts, algae, and bacteria, and include, for example, carbon. 14 C isotope 1×10 -12and has a biomass carbon concentration (unit: pMC) of about 100 pMC as measured in accordance with ASTM D6866. Biomass-derived raw materials can be obtained, for example, by conventionally known methods. For a certain polymer, if the production conditions of the polymer, such as the polymerization catalyst, polymerization process, and polymerization temperature, are the same, even if the polymer contains a biomass-derived raw material, 14 C isotope 1×10 -12 ~1×10 -14 The molecular structure of the polymers containing biomass-derived materials is the same as that of polymers made from fossil fuel-derived materials, except for the proportion of biomass-derived materials. Therefore, it is thought that the performance of polymers containing biomass-derived materials is the same as that of polymers made from fossil fuel-derived materials.

[0040] When the present composition contains the olefin-based polymer, the content of the olefin-based polymer in the present composition is not particularly limited, but from the viewpoints of moldability, controllability of adhesiveness, economic efficiency, etc., it is usually 40% by mass or more, preferably 50% by mass or more, and usually 99.5% by mass or less, preferably 99% by mass or less.

[0041] The present composition may contain various additives other than the present modified product and the olefin polymer, as needed, within the scope of not impairing the object of the present invention. Examples of the additives include softeners, stabilizers, fillers, antioxidants, crystal nucleating agents, waxes, thickeners, mechanical stability imparting agents, leveling agents, wetting agents, film-forming aids, crosslinking agents, preservatives, rust inhibitors, pigments, dispersants, antifreeze agents, antifoaming agents, tackifiers, other thermoplastic polymers, water, and organic solvents, and each of these may be used alone or in combination of two or more. The additive may be an additive using only biomass-derived raw materials as its raw materials, an additive using only fossil fuel-derived raw materials, or an additive using both biomass-derived raw materials and fossil fuel-derived raw materials.

[0042] The present composition can be used in various known adhesive forms, for example, as a water-dispersed adhesive, an organic solvent-based adhesive, or a hot-melt adhesive.

[0043] <This modified substance> The modified product is a graft-modified product of at least one base polymer selected from polyolefins with a carbodiimide monomer having a carbodiimide group and a polymerizable double bond, in other words, a graft-modified product in which at least one base polymer selected from polyolefins is graft-modified with a carbodiimide monomer having a carbodiimide group and a polymerizable double bond.The modified product can also be said to be a graft-modified product comprising at least one base polymer portion selected from polyolefins and a graft portion derived from a carbodiimide monomer having a carbodiimide group and a polymerizable double bond. The presence of the present modified product in layer (B) can be determined by infrared spectroscopic analysis.

[0044] The graft ratio in the present modified product is preferably 0.3 to 7% by mass, more preferably 0.5 to 5% by mass, from the viewpoints of ease of synthesis of the present modified product, ease of obtaining a graft modified product with superior adhesive properties, and preventing the obtained graft modified product from becoming too hard. the graft ratio is the mass of the structure derived from the carbodiimide monomer in the graft modified product, 1 It can be determined by H-NMR measurement, specifically by the method described in the examples below.

[0045] [Carbodiimide Monomer] The carbodiimide monomer used in graft-modifying the base polymer is not particularly limited as long as it is a compound having a carbodiimide group and a polymerizable double bond. However, in terms of better exerting the effects of the present invention, it is preferably a compound represented by the following formula (1) or (2): The carbodiimide monomer used when graft-modifying the base polymer may be of two or more types, but is usually of one type.

[0046] The carbodiimide monomer may be a biomass-derived monomer, a fossil fuel-derived monomer, or a biomass and fossil fuel-derived monomer. It is preferable that the carbodiimide monomer is a monomer derived from biomass or a monomer derived from biomass and fossil fuel from the viewpoint of reducing the environmental load (mainly reducing greenhouse gas emissions).

[0047] [ka]

[0048] In formula (1), R1 is a hydrogen atom or a methyl group, and a hydrogen atom is preferred from the viewpoint that the present modified product having a high grafting rate can be easily obtained.

[0049] In formula (1), R2 is an alkyl group or an aryl group which may have a substituent. The alkyl group which may have a substituent may be chain-like (may be linear or branched) or may contain an alicyclic ring. The number of carbon atoms in the alkyl group, which may have a substituent, is preferably 1 or more, more preferably 3 or more, and preferably 20 or less, more preferably 12 or less, and even more preferably 8 or less. The number of carbon atoms in the aryl group, which may have a substituent, is preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 12 or less, and even more preferably 8 or less.

[0050] Examples of the substituent that the alkyl group and aryl group may have include a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a carboxylic acid ester group having 1 to 8 carbon atoms, a sulfonic acid ester group having 1 to 8 carbon atoms, a carbonyl group having 1 to 8 carbon atoms, an amide group having 1 to 8 carbon atoms, an amino group having 1 to 8 carbon atoms, a sulfide group having 1 to 8 carbon atoms, a phosphate ester group having 1 to 8 carbon atoms, an alkylsilyl group having 1 to 8 carbon atoms, and an alkoxysilyl group having 1 to 8 carbon atoms.

[0051] Among these, R2 is preferably an aliphatic hydrocarbon group containing an alicyclic ring and having 4 to 20 carbon atoms, more preferably an alicyclic hydrocarbon group having 5 to 7 carbon atoms, from the viewpoints of the solubility of the carbodiimide monomer, ease of availability, ease of purification of the resulting graft-modified compound, and the like. Examples of the alicyclic ring include a cyclobutyl ring, a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and rings having a hydrocarbon group. The alicyclic ring may also be a polycyclic ring such as an adamantyl ring or a methyladamantyl ring.

[0052] [ka]

[0053] In formula (2), R3 is a hydrogen atom or a methyl group, and a methyl group is preferred from the viewpoint that the present composition having excellent adhesive strength to a layer containing PPS can be easily obtained.

[0054] In formula (2), R4 is an alkyl group or an aryl group which may have a substituent. The alkyl group which may have a substituent may be chain-like (may be linear or branched) or may contain an alicyclic ring. The number of carbon atoms in the alkyl group, which may have a substituent, is preferably 1 or more, more preferably 3 or more, and preferably 20 or less, more preferably 12 or less, and even more preferably 8 or less. The number of carbon atoms in the aryl group, which may have a substituent, is preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 12 or less, and even more preferably 8 or less. Examples of the alicyclic ring include a cyclobutyl ring, a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and rings having a hydrocarbon group. The alicyclic ring may also be a polycyclic ring such as an adamantyl ring or a methyladamantyl ring.

[0055] Examples of the substituent that the alkyl group and aryl group may have include a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a carboxylic acid ester group having 1 to 8 carbon atoms, a sulfonic acid ester group having 1 to 8 carbon atoms, a carbonyl group having 1 to 8 carbon atoms, an amide group having 1 to 8 carbon atoms, an amino group having 1 to 8 carbon atoms, a sulfide group having 1 to 8 carbon atoms, a phosphate ester group having 1 to 8 carbon atoms, an alkylsilyl group having 1 to 8 carbon atoms, and an alkoxysilyl group having 1 to 8 carbon atoms.

[0056] Among these, R4 is preferably an unbranched, unringed alkyl group, and more preferably an unbranched, unringed alkyl group having 3 to 7 carbon atoms, from the viewpoint that the present composition having excellent adhesive strength to a layer containing PPS can be easily obtained. Furthermore, R4 is preferably a branched, non-cyclic alkyl group, more preferably a branched, non-cyclic alkyl group having 3 to 7 carbon atoms, in view of improving the stability of the carbodiimide group in air and when heated, increasing the yield when synthesizing the present modified compound, and reducing the production cost. When R4 does not have a ring, the steric hindrance caused by the ring structure is suppressed, and the reactivity of the carbodiimide group becomes good.

[0057] Suitable examples of the alkyl group having no branch and no ring include an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and an n-nonyl group.

[0058] Preferred examples of the branched, non-ring alkyl group include an isopropyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a 1-methylbutyl group, a 1,2-dimethylpropyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylpropyl group, a 1,1-dimethylpropyl group, a 2,2-dimethylpropyl group, a 1-methylpentyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 1,2,2-trimethylpropyl group, a 2-methylpentyl group, a 2 ,2-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 3-methylpentyl group, 3,3-dimethylbutyl group, 4-methylpentyl group, 1-ethyl-2-methylpropyl group, 1-ethylbutyl group, 1,1-dimethylbutyl group, 1,1,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-methylhexyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4-dimethylpentyl group, 1,2,3-trimethylbutyl group, 1 ,2,2-trimethylbutyl group, 1,3,3-trimethylbutyl group, 2-methylhexyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 2,3,3-trimethylbutyl group, 1,1-dimethylpentyl group, 1,1,2-trimethylbutyl group, 1,1,3-trimethylbutyl group, 1,1,2,2-tetramethylpropyl group, 2,2-dimethylpentyl group, 2,2,3-trimethylbutyl group, 3-methylhexyl group, 3,4-dimethylpentyl group, 3,3-dimethyl Examples of such groups include a pentyl group, a 1-ethylpentyl group, a 1-ethyl-2-methylbutyl group, a 1-ethyl-3-methylbutyl group, a 1-ethyl-2,2-dimethylpropyl group, a 2-ethylpentyl group, a 2-ethyl-3-methylbutyl group, a 1-ethyl-1-methylbutyl group, a 1-ethyl-1,2-dimethylpropyl group, a 3-ethylpentyl group, a 1,1-diethylpropyl group, a 2,2-diethylpropyl group, a 1-propylbutyl group, a diisopropylmethyl group, and a 1-isopropylbutyl group.

[0059] In formula (2), m is an integer of 2 or more, and from the viewpoints of the solubility of the carbodiimide monomer, ease of availability, ease of purification of the resulting graft-modified product, etc., m is preferably an integer of 2 to 6, more preferably an integer of 2 to 4, and particularly preferably 2.

[0060] [Base polymer] The base polymer before being graft-modified with the carbodiimide monomer is at least one polymer selected from polyolefins. Specific examples of the olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and 4-methyl-1-pentene. The polyolefin may be a homopolymer of any of these olefins, a copolymer of two or more of these olefins, or a copolymer of one or more of these olefins with one or more of the following comonomers. Among these, the polyolefin is preferably at least one polymer selected from an ethylene-based polymer, a propylene-based polymer, and a butene-based polymer, and more preferably at least one polymer selected from an ethylene-based polymer and a propylene-based polymer from the viewpoints of excellent solubility in the solvent when a solvent is used during the graft reaction and excellent separability from impurities after the graft reaction. The base polymer of the present modified product may be of two or more types, but is usually of one type.

[0061] In order to more effectively achieve the effects of the present invention, the base polymer is preferably a polymer that does not have at least one active hydrogen-containing group selected from a carboxy group, an acid anhydride group, an amino group, a hydroxy group, and a thiol group. In addition, in order to further exert the effects of the present invention, it is also preferable that the base polymer is a polymer that does not have a carboxylic acid derivative group such as an acid halide, amide, imide, or ester, or a group that is easily converted by water or the like into a group having an active hydrogen, such as an epoxy group.

[0062] The weight average molecular weight (Mw) of the base polymer is not particularly limited, but from the viewpoint of ease of synthesis of the present modified product, it is preferably 100,000 or more, more preferably 150,000 or more, and preferably 1,000,000 or less, more preferably 700,000 or less. The number average molecular weight (Mn) of the base polymer is not particularly limited, but for the same reasons, it is preferably 40,000 or more, more preferably 50,000 or more, and preferably 500,000 or less, more preferably 300,000 or less. The molecular weight distribution (Mw / Mn) of the base polymer is not particularly limited, but is preferably 1.5 or more, more preferably 2.0 or more, and is preferably 6.0 or less, more preferably 5.0 or less.

[0063] The Mw and Mn values ​​were measured under the following conditions using a gel permeation chromatograph (GPC) model HLC-8321 GPC / HT manufactured by Tosoh Corporation. Separation columns: TSKgel GMH6-HT (2 columns) and TSKgel GMH6-HTL (2 columns) (both 7.5 mm I.D. x 30 cm, manufactured by Tosoh Corporation) Column temperature: 140℃ Mobile phase: o-dichlorobenzene (containing 0.025% dibutylhydroxytoluene (BHT)) Development speed: 1.0mL / min Sample concentration: 0.1% (w / v) Sample injection volume: 0.4 mL Detector: differential refractometer Calibration of the instrument: Calibration was carried out using monodisperse polystyrene (manufactured by Tosoh Corporation, #3std set).

[0064] The base polymer can be synthesized by a conventionally known method, or a commercially available product may be used. The conventionally known method is not particularly limited, and for example, a method using a coordination polymerization catalyst system containing a transition metal can be mentioned.Specifically, a synthesis method can be mentioned in which an olefin such as ethylene or propylene and, if necessary, a comonomer described below are (co)polymerized in the presence of a catalyst such as a magnesium chloride-supported titanium catalyst, a vanadium catalyst containing a soluble vanadium compound and an alkylaluminum halide compound, or a metallocene catalyst containing a metallocene compound and an organoaluminum oxy compound.

[0065] The base polymer may be made using only biomass-derived raw materials, only fossil fuel-derived raw materials, or both biomass-derived raw materials and fossil fuel-derived raw materials as its raw materials (e.g., monomers such as olefins and the comonomers described below). It is preferable that the base polymer is a polymer made from a raw material derived from biomass from the viewpoint of reducing the environmental load (mainly reducing greenhouse gas emissions).

[0066] [Ethylene polymer] The ethylene-based polymer is not particularly limited as long as the content of ethylene-derived structural units in the polymer is 50% by mass or more, and may be an ethylene homopolymer or a copolymer of ethylene and a comonomer. In the case of a copolymer, the structure thereof is not particularly limited.

[0067] The comonomer may be, for example, at least one monomer selected from propylene, α-olefins having 4 to 20 carbon atoms, and conjugated polyenes, and among these, propylene and α-olefins having 4 to 20 carbon atoms are preferred. The α-olefin having 4 to 20 carbon atoms may be linear or branched, and examples thereof include 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. The content of the comonomer-derived structural units in the ethylene polymer is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less, from the viewpoints of preventing blocking of pellets or powder, ease of handling, etc. In this specification, an ethylene polymer having a content of propylene-derived or butene-derived structural units of 50% by mass is referred to as an ethylene polymer.

[0068] [Propylene polymer] The propylene polymer is not particularly limited as long as the content of propylene-derived structural units in the polymer is 50% by mass or more, and may be a propylene homopolymer or a copolymer of propylene and a comonomer. The structure of these (co)polymers is not particularly limited.

[0069] The comonomer may be, for example, at least one monomer selected from ethylene, α-olefins having 4 to 20 carbon atoms, and conjugated polyenes, and among these, ethylene and α-olefins having 4 to 20 carbon atoms are preferred. Examples of the α-olefin having 4 to 20 carbon atoms include the same α-olefins having 4 to 20 carbon atoms as those listed in the section on ethylene polymers. The content of the comonomer-derived structural units in the propylene polymer is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less, from the viewpoints of preventing blocking of pellets or powder, ease of handling, etc. In this specification, a propylene polymer having a butene-derived structural unit content of 50% by mass is referred to as a propylene polymer.

[0070] [Butene polymer] The butene polymer is not particularly limited as long as the content of butene-derived structural units in the polymer is 50% by mass or more, and may be a homopolymer of butene, particularly 1-butene, or a copolymer of butene (particularly 1-butene) and a comonomer. The structure of these (co)polymers is not particularly limited.

[0071] The comonomer may be, for example, at least one monomer selected from ethylene, propylene, α-olefins having 5 to 20 carbon atoms, and conjugated polyenes, and among these, ethylene, propylene, and α-olefins having 5 to 20 carbon atoms are preferred. Examples of the α-olefin having 5 to 20 carbon atoms include the same α-olefins having 5 to 20 carbon atoms as those listed in the section on ethylene polymers. The content of the structural units derived from the comonomer in the butene polymer is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less, from the viewpoints of preventing blocking of pellets or powder and making handling easy, etc.

[0072] <Method for synthesizing the modified compound> The method for synthesizing the modified product is not particularly limited as long as a graft modified product can be obtained by graft-modifying the base polymer with the carbodiimide monomer, but from the viewpoint of ease of synthesis of the modified product, a method in which a radical initiator and the carbodiimide monomer are added to a solution in which the base polymer is dissolved or dispersed in a solvent, preferably a solution in which the base polymer is dissolved in an organic solvent, and then reacted (grafted) is preferred. Note that when a reaction apparatus having a stirring capacity capable of uniformly fluidizing the base polymer is used, a solvent may not be used. According to the above method, graft polymerization occurs, and thus a graft modified product is obtained.

[0073] The amount of the carbodiimide monomer used in the grafting reaction is preferably 10 to 1,000 mol, more preferably 10 to 800 mol, per mol of the base polymer, from the viewpoints that the present modified product having a graft rate within the above range can be easily obtained and that the production of a polymer of the carbodiimide monomer itself (hereinafter also referred to as "non-grafted polymer") can be suppressed.

[0074] Examples of the radical initiator include organic peroxides and azo compounds, and specific examples thereof include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxybenzoate)hexyne-3, 1,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(te Examples of suitable peroxides include organic peroxides such as tert-butylperoxyhexane, tert-butyl perbenzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate, tert-butyl perdiethyl acetate, and tert-butylperoxyisopropyl monocarbonate; and azo compounds such as azobisisobutyronitrile and dimethyl azoisobutyrate. Among these, preferred are organic peroxides such as dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,4-bis(tert-butylperoxyisopropyl)benzene, and tert-butylperoxyisopropyl monocarbonate. The radical initiators may be used alone or in combination of two or more.

[0075] The amount of the radical initiator used in the graft reaction is preferably 0.01 mol or more, more preferably 0.05 mol or more, and preferably 0.7 mol or less, more preferably 0.5 mol or less, per mol of carbodiimide monomer, from the viewpoints that the graft reaction occurs efficiently and the present modified product having a graft rate within the above range can be easily obtained.

[0076] The organic solvent is preferably an organic solvent that does not significantly inhibit the grafting reaction of the carbodiimide monomer and has affinity with the base polymer in the temperature range in which the grafting reaction is carried out. Specific examples of such organic solvents include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, and decane; alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and decahydronaphthalene; chlorinated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, and tetrachloroethylene; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and tert-butanol; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate; and ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran, and dioxyanisole. Furthermore, suspension polymerization and emulsion polymerization can also be carried out using water as a solvent. These solvents may be used alone or in combination of two or more. The use of these solvents preferably makes the reaction mixture a homogeneous phase, but it is acceptable for the reaction mixture to be a heterogeneous mixture of multiple phases.

[0077] Since the grafting reaction is carried out in a region where the liquid containing the base polymer can be stirred uniformly, the concentration of the base polymer in the liquid is usually set to 50 to 500 g / L, but to achieve a high grafting rate, it is preferably 200 to 500 g / L.

[0078] The radical initiator and the carbodiimide monomer may be added all at once to a liquid containing the base polymer (or the base polymer itself) to initiate the graft reaction. However, to achieve a high grafting rate, it is preferable to carry out the graft reaction by gradually adding them over a period of about 0.1 to 5 hours. When a radical initiator and a carbodiimide monomer are added to a base polymer or a liquid in which the base polymer is dissolved or dispersed in a solvent, the order of addition is not particularly limited. For example, when these are added sequentially as described above, the radical initiator and the carbodiimide monomer may be added sequentially, or the carbodiimide monomer may be added first and then the radical initiator may be added sequentially.

[0079] The grafting reaction is desirably carried out at a temperature of usually 60°C or higher, preferably 100°C or higher, usually 200°C or lower, preferably 160°C or lower, for usually 2 hours or longer, preferably 3 hours or longer, and usually 10 hours or shorter, preferably 8 hours or shorter.

[0080] The modified product obtained by the grafting reaction may be purified and isolated by known methods such as filtration, centrifugation, reprecipitation and / or washing to remove the solvent used, unreacted radical initiator and carbodiimide monomer, and by-produced non-grafted polymer. In this case, it is desirable to purify and isolate the present modified product so that the content of the non-grafted polymer contained in the present modified product is preferably 5% by mass or less, more preferably 2% by mass or less, in order to easily obtain the present composition having the above-mentioned superior adhesive properties.

[0081] <Method of manufacturing the present laminate> The method for producing the laminate varies depending on the shape, size, required physical properties, etc. of the final product and is not particularly limited, but from the viewpoint of easily producing the present laminate having the desired physical properties, such as excellent interlayer adhesion, it is preferable to produce it by a method including step 1 of co-extrusion molding, lamination molding, blow molding, or coinjection molding the present composition with a resin composition containing PPS, and more preferably by a method including a coinjection molding step. In particular, according to one embodiment of the present invention, a laminate having excellent adhesive strength can be produced even with a short sealing time, and therefore, the effects of the present invention can be more effectively exhibited. Therefore, it is preferable to produce the laminate by high-speed molding. As the co-extrusion molding, lamination molding, blow molding and coinjection molding, conventionally known methods may be used.

[0082] The temperature during production of the laminate is preferably 180 to 300°C, more preferably 200 to 250°C. Since the laminate contains the layer (B), a laminate having excellent adhesive strength can be easily obtained even if the time required for producing the laminate is short, specifically, 7 seconds or less, preferably 5 seconds or less.

[0083] Examples of the lamination molding include the following methods (1) and (2). (1) A method of heat-sealing preformed layers (A) and (B) using a calender roll molding machine, compression molding machine, or the like at a temperature equal to or higher than the melting point of at least one of the layers. (2) A method in which a preformed layer (A) or layer (B) is heat-sealed to another layer that is being extruded or calendared.

[0084] When a laminate is produced by pressing (heat sealing) preformed layers (A) and (B) using a compression molding machine in the method (1) above, for example, when heat sealing is performed at 230°C, a layer with high adhesive strength can be formed even if the heat sealing time is short, preferably 20 seconds or less, more preferably 10 seconds or less, and even more preferably 5 seconds or less.

[0085] An example of the co-extrusion molding is a method in which a resin composition containing PPS and the present composition are simultaneously extruded in a multi-layer extruder to form heat-sealed layers (A) and (B).

[0086] Examples of the co-injection molding include a method in which a molten PPS-containing resin composition and a molten present composition are injected into a mold simultaneously or at different injection times (e.g., two-layer injection molding, sandwich injection molding). [Example]

[0087] Hereinafter, one embodiment of the present invention will be described with reference to examples, but the present invention is not limited to these examples.

[0088] <Method for measuring graft ratio> The graft polymer obtained in the following synthesis example was measured using an AVANCE IIIcryo-500 nuclear magnetic resonance spectrometer (500 MHz) manufactured by Bruker Biospin under the following measurement conditions: measurement solvent: 1,1,2,2-tetrachloroethane-d2, measurement temperature: 120°C, spectrum width: 20 ppm, pulse repetition time: 7.0 seconds, pulse width: 5.00 μsec (45° pulse). 1 H-NMR spectrum was obtained. In the obtained spectrum, the graft ratio of the graft polymer obtained in the following synthesis example was calculated from the peak intensity ratio of the proton of the hydrocarbon group bonded to the carbodiimide group present at 3.0 ppm to 4.0 ppm to the peak intensity ratio of the protons bonded to all hydrocarbon groups originating from the base polymer present at 0.3 ppm to 2.5 ppm.

[0089] [Synthesis Example 1] A 1-L autoclave was charged with 25.0 g of LLDPE (base polymer, comonomer type: 1-hexene, comonomer amount: 1.6% by mass, Mw: 164,000, Mn: 63,000, Mw / Mn: 2.60) and 150 mL of toluene. The autoclave was then purged with nitrogen and sealed. The internal temperature of the autoclave was then raised to 140°C, and while maintaining this temperature, 28.1 mmol of vinylphenylcyclohexylcarbodiimide and 2.2 mmol of dicumyl peroxide (Percumyl D, NOF Corporation) were added over 2 hours while stirring at 400 rpm using a double anchor impeller. After stirring for another 2 hours, 250 mL of toluene was added over 15 minutes to dilute the reaction solution. The autoclave was then cooled to 50°C, the pressure was released, and the slurry-like reaction solution was removed. 400 mL of acetone was added to the resulting reaction solution, which was then stirred for 10 minutes. The stirred solution was then filtered to separate the solids and the filtrate. The process from adding acetone to the resulting solids to filtering was repeated two more times. These three filtrations removed unreacted vinylphenylcyclohexylcarbodiimide and vinylphenylcyclohexylcarbodiimide homopolymer. The solid content after the third filtration was dried in a vacuum dryer at 70° C. for 10 hours to obtain 25.71 g of graft polymer (P-1). The graft rate was 2.7% by mass.

[0090] [Synthesis Example 2] A 500 mL separable flask was charged with 25.0 g of polypropylene (base polymer, Mw: 313,000, Mn: 70,800, Mw / Mn: 4.42) and 110 mL of xylene, and the atmosphere inside the flask was replaced with nitrogen. The internal temperature was then raised to 120°C, and while maintaining that temperature, 28.1 mmol of vinylphenylcyclohexylcarbodiimide was added. Next, 2.2 mmol of tert-butylperoxyisopropyl monocarbonate (Perbutyl I, NOF Corporation) dissolved in 10 mL of xylene was added over 10 minutes while stirring at 400 rpm using a double anchor impeller. After stirring for an additional 3 hours, 200 mL of xylene was added to dilute the reaction solution. The internal temperature of the separable flask was then cooled to 50°C, and the slurry-like reaction liquid was removed. 400 mL of acetone was added to the resulting reaction liquid, which was then stirred for 10 minutes. The stirred liquid was then filtered to separate the solids and the filtrate. The process from adding acetone to the resulting solids to filtering was repeated three more times. These four filtrations removed unreacted vinylphenylcyclohexylcarbodiimide and vinylphenylcyclohexylcarbodiimide homopolymer. The solid content after the fourth filtration was dried in a vacuum dryer at 90° C. for 10 hours to obtain 25.13 g of graft polymer (P-2). The graft rate was 1.5% by mass.

[0091] [Synthesis Example 3] A 500 mL glass vessel was charged with 25.0 g of LLDPE (the same polymer as the base polymer used in Synthesis Example 1) and 110 mL of xylene, and the atmosphere inside the vessel was replaced with nitrogen. The internal temperature of the vessel was then raised to 120°C, and while maintaining that temperature, 35.0 mmol of ethyl methacrylate-tert-butylcarbodiimide was charged. Next, 2.2 mmol of tert-butylperoxyisopropyl monocarbonate (Perbutyl I, NOF Corporation) dissolved in 10 mL of xylene was added over 10 minutes while stirring at 400 rpm using a double anchor impeller. After stirring for an additional 3 hours, 200 mL of xylene was added to dilute the reaction solution. The internal temperature of the vessel was then cooled to 50°C, and the slurry-like reaction liquid was removed. 400 mL of acetone was added to the resulting reaction liquid, which was then stirred for 10 minutes. The stirred liquid was then filtered to separate the solids and the filtrate. The process from adding acetone to the resulting solids to filtering was repeated three more times. The solid content after the fourth filtration was dried in a vacuum dryer at 90° C. for 10 hours to obtain 25.49 g of graft polymer (P-3). The graft rate was 1.7% by mass.

[0092] [Synthesis Example 4] A 500 mL separable flask was charged with 15.0 g of polypropylene (the same polymer as the base polymer used in Synthesis Example 2) and 62 mL of xylene, and the atmosphere in the separable flask was replaced with nitrogen. The internal temperature was then raised to 120°C, and while maintaining that temperature, 22.1 mmol of ethyl methacrylate-tert-butylcarbodiimide was added. Next, 9.2 mmol of tert-butylperoxyisopropyl monocarbonate (Perbutyl I, manufactured by NOF Corporation) dissolved in 10 mL of xylene was added over 10 minutes while stirring at 400 rpm using a double anchor impeller. After stirring for an additional 3 hours, 150 mL of xylene was added to dilute the reaction solution. The internal temperature of the separable flask was then cooled to 50°C, and the slurry-like reaction liquid was removed. 400 mL of acetone was added to the resulting reaction liquid, which was then stirred for 10 minutes. The stirred liquid was then filtered to separate the solids and the filtrate. The process from adding acetone to the resulting solids to filtering was repeated three more times. These four filtrations removed unreacted ethyl methacrylate-tert-butylcarbodiimide and ethyl methacrylate-tert-butylcarbodiimide homopolymers. The solid content after the fourth filtration was dried in a vacuum dryer at 90° C. for 10 hours to obtain 15.37 g of graft polymer (P-4). The graft rate was 1.3 mass %.

[0093] [Synthesis Example 5] A 500 mL glass vessel was charged with 25.0 g of LLDPE (the same polymer as the base polymer used in Synthesis Example 1) and 110 mL of xylene, and the atmosphere inside the vessel was replaced with nitrogen. The internal temperature of the vessel was then raised to 120°C, and while maintaining that temperature, 4.69 g of glycidyl methacrylate was charged. Next, 0.39 g of tert-butylperoxyisopropyl monocarbonate (Perbutyl I, NOF Corporation) dissolved in 10 mL of xylene was added dropwise over 10 minutes using a double anchor impeller while stirring at a stirring speed of 400 rpm. Stirring was then continued for an additional 3 hours. Next, 250 mL of xylene was added, and the internal temperature of the vessel was gradually cooled to 50°C. The slurry-like reaction solution was then removed, and 400 mL of acetone was added to the resulting reaction solution and stirred for 10 minutes. The reaction solution was then filtered to separate the solids and the filtrate. The resulting solids were washed three times with 400 mL of acetone to remove unreacted glycidyl methacrylate and glycidyl methacrylate homopolymer. The obtained solid content was dried in a vacuum dryer at 90° C. for 10 hours to obtain 25.95 g of a graft polymer (CP-1), the graft rate of which was 2.4% by mass.

[0094] [Synthesis Example 6] A 500 mL glass vessel was charged with 25.0 g of LLDPE (the same polymer as the base polymer used in Synthesis Example 1) and 110 mL of xylene, and the atmosphere inside the vessel was replaced with nitrogen. The internal temperature of the vessel was then raised to 120°C, and while maintaining that temperature, 11 mmol of maleic anhydride was charged. Next, 0.8 mmol of tert-butylperoxyisopropyl monocarbonate (Perbutyl I, NOF Corporation) dissolved in 10 mL of xylene was added dropwise over 10 minutes while stirring at 400 rpm using a double anchor impeller. Stirring was then continued for an additional 3 hours. Next, 200 mL of xylene was added, and the internal temperature of the vessel was gradually cooled to 50°C. After that, the slurry-like reaction liquid was removed, and 400 mL of acetone was added to the resulting reaction liquid and stirred for 10 minutes. The reaction liquid was then filtered to separate the solids and the filtrate. The resulting solids were washed three times with 400 mL of acetone to remove unreacted maleic anhydride. The obtained solid content was dried in a vacuum dryer at 90° C. for 10 hours to obtain 25.17 g of a graft polymer (CP-2). The graft rate was 0.71% by mass.

[0095] [Synthesis Example 7] A 500 mL glass vessel was charged with 25.0 g of polypropylene (the same polymer as the base polymer used in Synthesis Example 2) and 110 mL of xylene, and the atmosphere inside the vessel was replaced with nitrogen. The internal temperature of the vessel was then raised to 120°C, and while maintaining that temperature, 33.4 mmol of maleic anhydride was charged. Next, 2.2 mmol of tert-butylperoxyisopropyl monocarbonate (Perbutyl I, NOF Corporation) dissolved in 10 mL of xylene was added dropwise over 10 minutes while stirring at a stirring speed of 400 rpm using a double anchor impeller. Stirring was then continued for an additional 3 hours. Next, 200 mL of xylene was added, and the internal temperature of the vessel was gradually cooled to 50°C. After that, the slurry-like reaction liquid was removed, and 400 mL of acetone was added to the resulting reaction liquid and stirred for 10 minutes. The reaction liquid was then filtered to separate the solids and the filtrate. The resulting solids were washed three times with 400 mL of acetone to remove unreacted maleic anhydride. The obtained solid content was dried in a vacuum dryer at 90° C. for 10 hours to obtain 25.01 g of a graft polymer (CP-3), the graft rate of which was 0.62% by mass.

[0096] <mfr> The MFR (g / 10 min) of the adhesive compositions obtained in the following Examples and Comparative Examples was measured in accordance with JIS K 7210 at 190° C. under a load of 2.16 kg.

[0097] <Carbodiimide group amount> The amount of carbodiimide groups (mmol) per 100 g of adhesive compositions obtained in the following Examples and Comparative Examples was calculated using the following formula (I). The results are shown in Tables 1 and 2 as the amount of carbodiimide groups (mmol / 100 g). (Graft rate [mass %] of graft modified compound used in adhesive composition / molecular weight of carbodiimide monomer used in synthesis of the graft modified compound) × 100 × amount of graft modified compound used in adhesive composition [mass %] / 10 (I)

[0098] <density> The densities (g / cm) of the adhesive compositions obtained in the following examples and comparative examples were 3 ) was measured in accordance with JIS K 7210. The results are shown in Tables 1 and 2.

[0099] [Example 1] Adhesive composition C-1 was obtained by kneading 11 parts by mass of the graft polymer (P-1) produced in Synthesis Example 1 and 89 parts by mass of LLDPE (the same polymer as the base polymer used in Synthesis Example 1) using a Labo Plastomill under conditions of a temperature of 190°C, a screw rotation speed of 60 rpm, and a kneading time of 10 minutes. The resulting adhesive composition C-1 had an MFR (190°C, 2.16 kg load) of 2.7 g / 10 min and a density of 0.903 g / cm 3 The amount of carbodiimide groups per 100 g of the composition was 1.3 mmol.

[0100] [Example 2] An adhesive composition C-2 was obtained in the same manner as in Example 1, except that 12 parts by mass of the graft polymer (P-2) produced in Synthesis Example 2 and 88 parts by mass of polypropylene (the same polymer as the base polymer used in Synthesis Example 2) were used. The resulting adhesive composition C-2 had an MFR (190°C, 2.16 kg load) of 0.6 g / 10 min and a density of 0.893 g / cm 3 The amount of carbodiimide groups per 100 g of the composition was 0.8 mmol.

[0101] [Example 3] An adhesive composition C-3 was obtained in the same manner as in Example 1, except that 16 parts by mass of the graft polymer (P-3) produced in Synthesis Example 3 and 84 parts by mass of LLDPE (the same polymer as the base polymer used in Synthesis Example 1) were used. The resulting adhesive composition C-3 had a density of 0.902 g / cm 3 The amount of carbodiimide groups per 100 g of the composition was 1.3 mmol.

[0102] [Example 4] An adhesive composition C-4 was obtained in the same manner as in Example 1, except that 13 parts by mass of the graft polymer (P-4) produced in Synthesis Example 4 and 87 parts by mass of polypropylene (the same polymer as the base polymer used in Synthesis Example 2) were used. The resulting adhesive composition C-4 had an MFR (190°C, 2.16 kg load) of 2.0 g / 10 min and a density of 0.892 g / cm 3 The amount of carbodiimide groups per 100 g of the composition was 0.8 mmol.

[0103] [Comparative Example 1] An adhesive composition CC-1 was obtained in the same manner as in Example 1, except that 8 parts by mass of the graft polymer (CP-1) produced in Synthesis Example 5 and 92 parts by mass of LLDPE (the same polymer as the base polymer used in Synthesis Example 1) were used. The resulting adhesive composition CC-1 had an MFR (190°C, 2.16 kg load) of 2.9 g / 10 min and a density of 0.904 g / cm 3 The amount of epoxy groups per 100 g of the composition was 1.3 mmol, and the composition did not contain any graft-modified product with a carbodiimide monomer.

[0104] Comparative Example 2 An adhesive composition CC-2 was obtained in the same manner as in Example 1, except that 18 parts by mass of the graft polymer (CP-2) produced in Synthesis Example 6 and 82 parts by mass of LLDPE (the same polymer as the base polymer used in Synthesis Example 1) were used. The resulting adhesive composition CC-2 had an MFR (190°C, 2.16 kg load) of 2.8 g / 10 min and a density of 0.902 g / cm 3 The amount of acid anhydride groups per 100 g of the composition was 1.3 mmol, and the composition did not contain any graft-modified product with a carbodiimide monomer.

[0105] Comparative Example 3 An adhesive composition CC-3 was obtained in the same manner as in Example 1, except that 13 parts by mass of the graft polymer (CP-3) produced in Synthesis Example 7 and 87 parts by mass of polypropylene (the same polymer as the base polymer used in Synthesis Example 2) were used. The resulting adhesive composition CC-3 had an MFR (190°C, 2.16 kg load) of 2.1 g / 10 min and a density of 0.892 g / cm 3 The amount of acid anhydride groups per 100 g of the composition was 0.8 mmol, and the composition did not contain any graft-modified product with a carbodiimide monomer.

[0106] <Adhesion evaluation> -Press sheet production Each of the adhesive compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 was press-molded under conditions of a temperature of 180°C, a pressure of 4 MPa, a preheating time of 5 minutes, and a pressing time of 3 minutes, and then rapidly cooled in a press molding machine set to 20°C to produce a pressed sheet having a thickness of 500 μm, a length of 80 mm, and a width of 80 mm.

[0107] -Laminate fabrication A polyphenylene sulfide (PPS) sheet (product name: Torelina, manufactured by Toray Industries, Inc.) having a thickness of 100 μm, a length of 80 mm, and a width of 80 mm was used. A PPS sheet, a press sheet and a PPS sheet were stacked in that order, and the stack was sandwiched between Teflon (registered trademark) sheets. Heat sealing was performed for 3 seconds using a heat sealer with the upper and lower press plate temperatures set to 230°C or 250°C to produce a three-layer laminate.

[0108] Peel test The upper PPS sheet (the PPS sheet on the (upper) side of the press plate) and the press sheet of the prepared laminate were T-peeled together at a peeling atmosphere temperature of 23°C, a peeling speed of 300 mm / min, and a peel width of 15 mm to measure the peel strength between the PPS sheet and the press sheet. The results are shown in Tables 1 and 2. Table 1 shows the results for ethylene-based adhesive compositions, and Table 2 shows the results for propylene-based adhesive compositions.

[0109] [Table 1]

[0110] [Table 2] < / mfr>

Claims

1. A laminated film having a layer (A) containing polyphenylene sulfide and an adhesive layer (B) containing an adhesive composition, At least a portion of the adhesive layer (B) is in contact with the layer (A), A laminate, wherein the adhesive composition satisfies the following requirements (i) to (iii): (i) A graft-modified product of at least one base polymer selected from polyolefins with a carbodiimide monomer having a carbodiimide group and a polymerizable double bond; (ii) the adhesive composition contains 0.1 to 50 mmol of carbodiimide groups per 100 g; (iii) Density is 0.870 to 0.940 g / cm 3 is.

2. 2. The laminate according to claim 1, wherein the carbodiimide monomer is at least one monomer selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (2): 【Chemistry 1】 [In formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 represents an alkyl group or an aryl group which may have a substituent, In formula (2), R 3 is a hydrogen atom or a methyl group, and R 4 represents an alkyl group or an aryl group which may have a substituent, and m is an integer of 2 or more.

3. 3. The laminate according to claim 1, wherein the layer (A) comprises polyphenylene sulfide.

4. The laminate according to claim 1 or 2, which is obtained by coextrusion molding, lamination molding, blow molding or coinjection molding.

5. A method for manufacturing a laminate, The laminate has a layer (A) containing polyphenylene sulfide and an adhesive layer (B) containing an adhesive composition, and at least a portion of the adhesive layer (B) is in contact with the layer (A), The production method includes a step 1 of co-extrusion molding, lamination molding, blow molding, or coinjection molding a resin composition containing polyphenylene sulfide and the adhesive composition, A method for producing a laminate, wherein the adhesive composition satisfies the following requirements (i) to (iii): (i) A graft-modified product of at least one base polymer selected from polyolefins with a carbodiimide monomer having a carbodiimide group and a polymerizable double bond; (ii) the adhesive composition contains 0.1 to 50 mmol of carbodiimide groups per 100 g; (iii) Density is 0.870 to 0.940 g / cm 3 is.

6. 6. The method for producing a laminate according to claim 5, wherein the carbodiimide monomer is at least one monomer selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (2): 【Chemistry 2】 [In formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 represents an alkyl group or an aryl group which may have a substituent, In formula (2), R 3 is a hydrogen atom or a methyl group, and R 4 represents an alkyl group or an aryl group which may have a substituent, and m is an integer of 2 or more.

7. The method for producing a laminate according to claim 5 or 6, wherein the layer (A) comprises polyphenylene sulfide.

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