TW202138407A - Graft modified product, adhesive, compatibilizer, and laminate - Google Patents

Abstract

One embodiment according to the present invention pertains to a graft modified product, an adhesive, a compatibilizer, or a laminate, wherein the graft modified product is formed from at least one base polymer selected from an ethylene-based polymer and a propylene-based polymer using an epoxy monomer represented by formula (1). [In formula (1), R is a hydrogen atom or a methyl group, X is -O- or a single bond, and n is an integer of 0-3.].

Description

Graft modified body, adhesive, compatibilizer and laminate

One embodiment of the present invention relates to a graft-modified body, an adhesive, a compatibilizer, or a laminate.

Polyolefins such as polyethylene and polypropylene have excellent mechanical strength, rigidity, heat resistance, chemical resistance, oil resistance, transparency, and impact resistance at low temperatures. Therefore, they are widely used as films and sheets by taking advantage of these properties. Packaging materials and coating materials such as bottles, cans, etc., or used as decorative materials such as wallpaper.

However, because polyolefin molecules do not contain polar groups, they lack compatibility with polar resins such as polyester, polyphenylene sulfide, polyamide, polyacetal, polycarbonate, and polyacrylate; and For example, the adhesion between metal, glass, paper, or the above-mentioned polar resins, etc., is therefore limited to mixing with these materials or layering.

In order to solve this problem, conventional methods have been widely adopted to graft monomers containing polar groups on polyolefins to improve the above-mentioned compatibility and adhesion. For example, a method of grafting polyolefin with glycidyl (meth)acrylate or the like is generally widely adopted (for example, Patent Document 1). [Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 6-145260

(The problem to be solved by the invention)

The modified polyolefin obtained by the method described in the above-mentioned Patent Document 1, although the above-mentioned compatibility and adhesiveness can be improved to a certain extent, the compatibility and adhesiveness are still insufficient, and (meth)acrylic acid Glycidyl ester has the possibility of mutagenicity, so special attention must be paid to handling, especially when grafting in the molten state, there are problems such as the need for countermeasures in the operating environment.

An embodiment of the present invention is to provide: using a monomer with a low load on the human body and the like and with high safety, it is possible to form a layer with excellent adhesion to a substrate having a polar group such as polyester and polyphenylene sulfide, and is compatible with the above A grafted modified body with excellent compatibility between polar resins. (Technical means to solve the problem)

The inventors of the present invention conducted intensive studies and found that the above-mentioned problems can be solved by following the following configuration examples. The configuration example of the present invention is as follows.

[1] A graft-modified product, which is obtained by selecting at least one matrix polymer from ethylene-based polymer and propylene-based polymer, and graft-modifying the epoxy monomer represented by the following formula (1) .

[式(1)中，R係氫原子或甲基；X係-O-或單鍵；n係0~3之整數。][化1]

[In formula (1), R is a hydrogen atom or a methyl group; X is -O- or a single bond; n is an integer of 0-3. ]

[2] An adhesive containing the graft-modified body described in [1]. [3] A compatibilizer containing the graft-modified body described in [1].

[4] A layered product comprising: a layer (A) containing the graft-modified body described in [1], and a base layer (B). [5] The layered product according to [4], wherein the base material layer (B) is a layer having a polar group. [6] The layered product according to [5], wherein the polar group is a carboxyl group or a hydroxyl group. (Compared to the effect of the previous technology)

According to an embodiment of the present invention, it is possible to provide a layer with a low load on the human body and the like and high safety to form a layer with excellent adhesion to substrates with polar groups such as polyester and polyphenylene sulfide, and A graft-modified body with excellent compatibility with the above-mentioned polar resins.

"Grafting Modified Body" The grafted modified body of one embodiment of the present invention (hereinafter also referred to as "this modified body") is at least one matrix polymer selected from ethylene-based polymers and propylene-based polymers, using the following formula (1 ) A grafted modification of the epoxy monomer shown in. This modified body can be said to be a graft modification in which at least one matrix polymer selected from an ethylene-based polymer and a propylene-based polymer is graft-modified by the epoxy monomer represented by the following formula (1) It can also be said that it contains at least one matrix polymer part selected from ethylene-based polymer and propylene-based polymer, and a grafted part derived from the epoxy monomer represented by the following formula (1) Modified body.

According to this modified body, even if a monomer with low load on the human body is used and high safety, a layer with excellent adhesion to substrates with polar groups such as polyester and polyphenylene sulfide can be formed. This modified body It has excellent compatibility with polar resins such as polyester, polyphenylene sulfide, polyamide, polyacetal, polycarbonate, and polyacrylate. Because the glycidyl (meth)acrylate has an ester bond, it has higher polarity than the epoxy monomer represented by the following formula (1). The grafted modified body using glycidyl (meth)acrylate can It is considered that the adhesion to polar base substrates such as polyester and polyphenylene sulfide and the compatibility with the above-mentioned polar resins are excellent, but this modified body is better than using glycidyl (meth)acrylate The grafted modified body has significantly better adhesion to substrates with polar groups such as polyester and polyphenylene sulfide, and compatibility with the above-mentioned polar resins. Furthermore, the present modified body has better storage stability than a grafted modified body using, for example, glycidyl (meth)acrylate. In addition, because the modified body is not a block copolymer or random copolymer of monomers such as ethylene and propylene and the above-mentioned epoxy monomer, but is a grafted modified body, the above effects can be achieved.

The grafting rate of the present modified body, from the viewpoints of the ease of synthesis of the present modified body, and the ease of obtaining a grafted modified body with more excellent compatibility and adhesion, is preferably 0.1-10% by mass, More preferably, it is 0.1 to 5% by mass. The above-mentioned grafting rate refers to the quality of the structure derived from the epoxy monomer in the grafted modified product, and ^{can be obtained by 1} H-NMR measurement (specifically, using the method described in the following examples).

＜Epoxy monomer＞ The epoxy monomer system used for graft modification of the above-mentioned matrix polymer is a compound represented by the following formula (1). The epoxy monomer system used for graft modification of the above-mentioned matrix polymer may be two or more types, but usually only one type.

[化2]

In the formula (1), R is a hydrogen atom or a methyl group. From the viewpoint of easily obtaining the present modified body with a high grafting rate, it is preferably a hydrogen atom. In formula (1), X is -O- or a single bond. From the viewpoints of low grafting rate, good compatibility, and easy formation of a layer with low grafting rate and good adhesion, the single bond is preferred . In formula (1), n is an integer of 0~3. From the viewpoint of low grafting rate, good compatibility, and easy formation of a layer with low grafting rate and good adhesion, it is preferably 0~2 The integer of is more preferably 0 or 1.

Specific examples of the above-mentioned epoxy monomers include, for example, vinyl phenyl oxirane (VPO), isopropenyl phenyl oxirane, vinyl phenyl oxirane (VPGE), isopropenyl Phenyl propylene oxide (IPPGE), vinyl phenyl methyl oxirane, vinyl phenyl ethyl oxirane, vinyl phenyl propyl oxirane, among these, from In terms of high reactivity, VPO, VPGE, and IPPGE are preferred, VPO and IPPGE are more preferred, and VPO is particularly preferred.

＜Matrix polymer＞ The matrix polymer before graft modification with the above-mentioned epoxy monomer is a polymer of at least one selected from an ethylene-based polymer and a propylene-based polymer. The above-mentioned matrix polymer system may be two or more types, but usually only one type.

The weight average molecular weight (Mw) of the matrix polymer is not particularly limited. From the viewpoint of ease of synthesis of the present modified body, etc., it is preferably 100,000 or more, more preferably 150,000 or more, and more preferably 500,000 or less, More preferably, it is below 400,000. The number average molecular weight (Mn) of the matrix polymer is also not particularly limited. For the same reason, it is preferably 40,000 or more, more preferably 50,000 or more, and more preferably 80,000 or less, and more preferably 70,000 or less. The molecular weight distribution (Mw/Mn) of the aforementioned matrix polymer is also not particularly limited, and is preferably 1.5 or more, more preferably 2.0 or more, and preferably 5.0 or less, more preferably 4.0 or less.

The above-mentioned Mw and Mn are values measured using Tosoh Corporation's HLC-8321 GPC/HT Gel Permeation Chromatography Analyzer (GPC) under the following conditions. Separation column: TSKgel GMH6-HT (2) and GMH6-HTL (2) (both are 7.5mmI.D.×30cm, manufactured by Tosoh Corporation) Column temperature: 140℃ Mobile phase: o-dichlorobenzene (containing 0.025% dibutylhydroxytoluene (BHT)) Expansion speed: 1.0mL/min Sample concentration: 0.1%(w/v) Sample injection volume: 0.4mL Detector: Differential refractometer Device calibration: Monodisperse polystyrene (manufactured by Tosoh Co., Ltd., #3std set) is used

The above-mentioned matrix polymer system can be synthesized by a conventionally known method, and a commercially available product can also be used. The above-mentioned conventional and well-known methods are not particularly limited. For example, a method using a coordination polymerization catalyst system containing a transition metal can be used. Specific examples include: a magnesium chloride-supported titanium catalyst, containing a soluble vanadium compound and alkane In the presence of a vanadium-based catalyst based on aluminum halide compounds, or a metallocene catalyst containing a metallocene compound and an organoaluminum oxy compound, (co)polymerizes ethylene or propylene, and optionally a comonomer described later The method of synthesis.

[Ethylene polymer] The above-mentioned ethylene-based polymerization system is mentioned before it belongs to a polymer with a content of more than 50% by mass of structural units derived from ethylene. The rest is not particularly limited, and it may be a monomer of ethylene or ethylene. Copolymer with comonomer. In the case of copolymers, there is no particular limitation in terms of structure.

The above-mentioned copolymerization monomer system may include, for example, selecting at least one monomer from propylene, α-olefin with 4 to 20 carbons, and conjugated polyene. Among them, propylene and α with 4 to 20 carbons are preferred. -Olefins. The above-mentioned α-olefins with 4 to 20 carbon atoms may be linear or branched, for example: 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene Ene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene , 1-hexadecene, 1-octadecene, 1-eicosene. The content of the structural unit derived from the comonomer in the ethylene-based polymer is preferably 50% by mass or less, and more preferably 30% by mass, from the viewpoints of preventing agglomeration of particles and powders and easy handling. Less than 20% by mass, especially good. In addition, an ethylene-based polymer having a content of 50% by mass of structural units derived from propylene is referred to as an "ethylene-based polymer" in this specification.

[Propylene-based polymer] The above-mentioned propylene-based polymerization system is mentioned before it belongs to the polymer with a content of more than 50% by mass of structural units derived from propylene. The rest is not particularly limited, and it may be a monomer of propylene or propylene. Copolymer with comonomer. The structure of these (co)polymers is not particularly limited.

The above-mentioned copolymerization monomer system can select at least one monomer from ethylene, α-olefin with 4 to 20 carbons, and conjugated polyene, among which ethylene and α-olefin with 4 to 20 carbons are preferred. Olefins. The above-mentioned α-olefin having 4 to 20 carbon atoms may be the same α-olefin as the α-olefin having 4 to 20 carbon atoms exemplified for the ethylene-based polymer. The content of the structural unit derived from the comonomer in the propylene-based polymer is preferably 50% by mass or less, and more preferably 30% by mass, from the viewpoints of preventing agglomeration of particles and powders and easy handling. Less than 20% by mass, especially good.

＜The synthesis method of this modified body＞ The synthesis method of the present modified body is not particularly limited. It is mentioned before the grafted modified body that is grafted and modified by the above-mentioned matrix polymer and the above-mentioned epoxy monomer can be obtained, and the rest is not particularly limited. From the viewpoint of easy synthesis of the modified body, etc., it is preferable to add free radicals to a solution in which the matrix polymer has been dissolved or dispersed in a solvent, and more preferably, a solution in which the matrix polymer is dissolved in an organic solvent. A method of reacting the initiator and the above-mentioned epoxy monomer (grafting reaction). In addition, when it has a reaction device capable of stirring the matrix polymer homogeneously, the solvent may not be used. According to the above method, since graft polymerization is initiated, a graft-modified body can be obtained.

The amount of epoxy monomer used in the above-mentioned grafting reaction can be easily obtained from the present modified body with the grafting rate within the above-mentioned range, and the polymer capable of inhibiting the self-organization of the epoxy monomer (hereinafter also referred to as From the viewpoint of formation of "non-grafted polymer"), relative to 1 mol of the matrix polymer, it is preferably 10 to 1000 mol, more preferably 10 to 800 mol.

The above-mentioned radical initiator system may be, for example, organic peroxides and azo compounds. Specific systems can include, for example: benzyl peroxide, dichlorobenzyl peroxide, dicumyl peroxide, di-tertiary butyl peroxide, 2,5-dimethyl-2,5-bis(over Oxidized benzoate) hexyne-3, 1,4-bis(tert-butyl isopropyl peroxide) benzene, laurel peroxide, tert-butyl peroxyacetate, 2,5-dimethyl- 2,5-Di-(tertiary butyl peroxide) hexyne-3, 2,5-dimethyl-2,5-bis(tertiary butyl peroxide) hexane, tertiary butyl peroxide Ester, tertiary butyl phenyl peroxyacetate, tertiary butyl peroxy isobutyrate, tertiary butyl peroxy second caprylate, tertiary butyl peroxy trimethylacetate, trimethyl peroxyacetate iso Organic peroxides such as Cumyl perpivalate and tert-butyl diethyl acetate; Azo compounds such as azobisisobutyronitrile and dimethyl azoisobutyrate. Among these, dicumyl peroxide, di-tertiary butyl peroxide, 2,5-dimethyl-2,5-bis(tertiary butyl peroxide) hexyne-3, 2 are preferred. Peroxides such as ,5-dimethyl-2,5-bis(tertiary butyl peroxide) hexane and 1,4-bis(tertiary butyl isopropyl peroxide) benzene.

The amount of the radical initiator used in the above grafting reaction is based on the viewpoints that the grafting reaction can be initiated efficiently and the present modified body with the grafting rate within the above range can be easily obtained. The monomer is 1 mol, preferably 0.01 mol or more, more preferably 0.05 mol or more, more preferably 0.5 mol or less, more preferably 0.3 mol or less.

The organic solvent is preferably an organic solvent that does not significantly inhibit the graft reaction of the epoxy monomer and has an affinity for the matrix polymer in the temperature range where the graft reaction proceeds. Specific examples of such organic solvents include, for example, 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 hexane, methylcyclohexane, and decalin; chlorinated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, and tetrachloroethylene Solvents; alcoholic solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, and tertiary butanol; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethyl acetate, Ester solvents such as dimethyl phthalate; ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran, and dioxyanisole. In addition, water may be used as a solvent, and suspension polymerization or emulsion polymerization may be performed. These solvent systems may be used individually by 1 type, and may use 2 or more types. By using these solvents, the reaction liquid can be made into a homogeneous phase, which is preferable, but it can also be a heterogeneous plural phase.

Because the solution containing the matrix polymer undergoes the grafting reaction in a homogeneously stirred area, the concentration of the matrix polymer in the solution is usually set to 50~500g/L. From the viewpoint of easily achieving a high grafting rate, it is more The best series is 200~500g/L.

The free radical initiator and epoxy monosystem are collectively added to the matrix-containing polymer solution (or the matrix polymer itself) to start the grafting reaction, but it is easy to achieve high grafting rate, etc. From a viewpoint, it is preferable to add the grafting reaction gradually over a period of about 0.5 to 5 hours.

The above-mentioned grafting reaction is preferably carried out at a temperature of usually 60 to 200°C, preferably 100 to 160°C, for usually 2 to 10 hours, preferably 3 to 8 hours.

The modified body obtained by the above-mentioned grafting reaction can also be used in combination with solvents, unreacted radical initiators, epoxy compounds, by-product non-grafted polymers, etc., as required, for example: filtration , Centrifugal separation, re-precipitation operations and/or washing, etc., are refined/isolated using well-known methods. In this case, from the viewpoint of easily obtaining the present modified body with more excellent compatibility and adhesion, etc., it is preferable that the content of the non-grafted polymer contained in the present modified body is preferably 5% by mass. Below, preferably 2% by mass or less, refining/segregating is performed.

＜Use of this modified body＞ Because this modified body has excellent compatibility with polar resins such as polyester, polyphenylene sulfide, polyamide, polyacetal, polycarbonate, polyacrylate, and olefin polymers, it can also be used Effectively used as a compatibilizer for compositions containing such polar resins and olefin polymers; and because of its excellent adhesion with metals, glass, paper, or the above polar resins, olefin polymers, etc., it is effective It is used as an adhesive to substrates containing these; and because it has excellent dispersibility to olefin-based polymers, it can also be mixed with olefin-based polymers and used as olefin-based resin compositions. The olefin-based resin composition can be used in adhesives (including pressure-sensitive adhesives) and compatibilizers, and can also be used in, for example, printing inks and coatings.

The above-mentioned olefin-based polymerization system is based on an olefin-based polymer, and the rest is not particularly limited, and various well-known olefin-based polymers can be used. Specific examples include: ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and other α-olefins alone or copolymers [for example: high pressure method low density Polyethylene, linear low density polyethylene (LLDPE), medium density polyethylene, high density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene-α-olefin copolymer Combinations (e.g., low crystalline or amorphous ethylene-propylene random copolymers, ethylene-1-butene random copolymers), propylene and α-olefin copolymers (e.g., propylene and 1-butene random copolymers) Combination)], ethylene-vinyl acetate copolymer (EVA), ethylene-(meth)acrylic acid copolymer or its metal salt, ethylene-cyclic olefin copolymer, and these (co)polymers after the use of butene A polymer in which polar compounds such as diacids and silane compounds are graft-modified.

The content of the modified body in the above-mentioned olefin resin composition is not particularly limited. From the viewpoints of molding processability, controllability of bonding ability, economic efficiency, etc., it is usually 1% by mass or more, preferably 5% by mass or more. In addition, it is usually 30% by mass or less, preferably 15% by mass or less.

When the modified body and the above-mentioned olefin-based resin composition are used in various applications, they may be blended with the modified body and the above-mentioned olefin-based resin composition as necessary within a range that does not impair the effects of the present invention. Various additives. The additives may include, for example, softeners, stabilizers, fillers, antioxidants, crystal nucleating agents, waxes, tackifiers, mechanical stability imparting agents, leveling agents, wetting agents, film forming aids, and crosslinking Agents, preservatives, rust inhibitors, pigments, fillers, dispersants, antifreezes, defoamers, tackifiers, other thermoplastic polymers, water, and organic solvents, each of which can be used alone or one Two or more types can be used.

"Adhesive" Among the above-mentioned uses of the present modified body, since it has excellent adhesion to polyester and polyphenylene sulfide, from the viewpoint of further exerting the effects of the present invention, the present modified body is preferably used as p-polyester and polyphenylene sulfide. Adhesive for thioether (containing these layers).

The adhesive of one embodiment of the present invention is provided before containing the above-mentioned modified body, and the rest is not particularly limited. The modified system contained in the adhesive may be one type or two or more types. . The above-mentioned adhesive system may consist of only the adhesive of the present modified body, or may contain one or more of the above-mentioned olefin polymer and additives, respectively. The content of the modified body in the adhesive is not particularly limited, and is usually 5-100% by mass, preferably 10-100% by mass.

The above-mentioned adhesive system can be used in various forms, such as a water-dispersed adhesive, an organic solvent-based adhesive, and a hot-melt adhesive.

Examples of the bonding object of the above-mentioned adhesive include: metal (film); glass; wood; paper; cloth; polyester, polyphenylene sulfide, polyamide, polyacetal, polycarbonate, polyacrylate, and polyolefin , Polystyrene, rubber, engineering plastics other than these, such as layers containing thermoplastic resins, thermosetting resins, or layers composed of these.

"Compatibilizer" Furthermore, in the above-mentioned use of the modified body, because the modified system has compatibility with polar resins composed of epoxy groups (especially reactivity with polar resins with active hydrogen groups), and with Compatibility between olefin-based polymers composed of the main chain skeleton of ethylene-based polymers or propylene-based polymers, so it is also preferable to use polar resins (especially polar resins with active hydrogen groups) and olefins Department of polymer compatibilizer. A molded body obtained from a compatible composition of this modified body containing a polar resin, an olefin-based polymer, and these compatibilizing agents. The modified body can improve the relationship between the polar resin and the olefin-based polymer. Based on the compatibility, it can be judged that it can be a molded body with excellent mechanical properties such as impact resistance and a smooth surface.

The present modification system used in the above-mentioned compatible composition may be only one type or two or more types. In addition, the above-mentioned compatible composition may each contain one or two or more of the above-mentioned additives. The content of the modified body in the above-mentioned compatible composition is not particularly limited, and is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and usually 30% by mass or less, It is preferably 25% by mass or less, and more preferably 20% by mass or less.

The polar resin used in the above-mentioned compatible composition is not particularly limited. It is preferably an engineering plastic with polarity, and more preferable examples include polyester (e.g., PET, PBT, polylactic acid (PLA)), poly Amide, polyphenylene sulfide (PPS), ethylene-vinyl alcohol copolymer (EVOH). Examples of the above-mentioned active hydrogen group include a carboxyl group, a hydroxyl group, an amino group, and a thiol group. The content of the olefin polymer in the above-mentioned compatible composition is not particularly limited, and is usually 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, and usually 98% by mass or less, It is preferably 90% by mass or less, and more preferably 80% by mass or less. The polar resin system used in the above-mentioned compatible composition may be only one type or two or more types.

The olefin-based polymerization system used in the above-mentioned compatible composition may be only one type or two or more types. The specific example may be, for example, the same polymer as the olefin polymer described in the use of the modified product. The content of the olefin polymer in the above-mentioned compatible composition is not particularly limited, and is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and usually 80% by mass or less, It is preferably 60% by mass or less, and more preferably 50% by mass or less.

"Layered Body" The layered system of one embodiment of the present invention is provided with: the layer (A) containing the above-mentioned modified body, and the base material layer (B). The rest is not particularly limited, and the layer (A) may also contain Two or more layers, and this base material layer (B) may contain two or more layers. When two or more layers (A) are contained, these layer systems may be the same layer or different layers. In addition, when two or more base material layers (B) are contained, these layers may be the same layer or different layers in the same manner. The above-mentioned laminate is preferably a laminate including a layer (A) and a base layer (B), or a laminate including a base layer (B), a layer (A), and a base layer (B) in this order.

The above-mentioned layer (A) can be obtained by using the above-mentioned modified body or the above-mentioned adhesive. This layer (A) contains the modified substance, which can be judged by infrared spectroscopy analysis.

The thickness of the above-mentioned layer (A) is not particularly limited, and can be appropriately selected according to the use of the laminate, and is preferably 2 to 1000 μm. Furthermore, the thickness of the above-mentioned base material layer (B) is not particularly limited, and can be appropriately selected according to the use of the laminate, and is preferably 2 to 1000 μm.

The above-mentioned base material layer (B) may be, for example, metal (film); glass; wood; paper; cloth; polyester, polyphenylene sulfide, polyamide, polyacetal, polycarbonate, polyacrylate, poly A layer made of thermoplastic resin or thermosetting resin, such as olefin, polystyrene, rubber, and engineering plastics other than these.

The above-mentioned thermoplastic resins are various well-known thermoplastic resins, such as polyolefins (e.g., polyethylene, polypropylene, poly-4-methyl-1-pentene, polybutene), polyesters (e.g., poly-p-phenylene) Ethylene dicarboxylate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate), polyphenylene sulfide, polyamide (for example: nylon-6, nylon-66, poly M-xylene hexadiamide), polyvinyl chloride, polyvinylidene chloride, polymethyl methacrylate, polyvinyl acetate, polyimide, ethylene-vinyl acetate copolymer or its saponified product, polyethylene Alcohol, polyacrylonitrile, polycarbonate, polystyrene, ethylene-(meth)acrylic acid copolymer or its metal salt (ionic polymer), thermoplastic polyurethane, biodegradable plastic (e.g., polylactic acid) And other aliphatic polyesters).

The above-mentioned thermosetting resins are various well-known thermosetting resins, such as epoxy resins, unsaturated polyester resins, phenol resins, urea/melamine resins, polyurethane resins, silicone resins, and polyimides.

The above-mentioned base material layer (B) is preferably a layer having a polar group. If such a base material layer (B) is used, since the epoxy groups in the above-mentioned modified body react with the polar groups in the base material layer (B) to form a bonded state, the above-mentioned layer (A) ) Adhesion to the above-mentioned base material layer (B). In this case, the above-mentioned layer (A) contains not only the present modified body, but also a state in which the epoxy group of the present modified body reacts with the polar group of the base layer (B).

Examples of the polar group system include a carboxyl group, a hydroxyl group, an amino group, an ester group, and a carbonyl group. Among these, from the viewpoint of excellent reactivity with an epoxy group, etc., a carboxyl group and a hydroxyl group are preferred. The said base material layer (B) may contain 2 or more types of polar groups. For example, polyester usually has a carboxyl group and a hydroxyl group at the terminal. Moreover, polyphenylene sulfide usually has a carboxyl group at the terminal. Glass and metals also usually have hydroxyl groups.

The above-mentioned thermoplastic resins and thermosetting resins, within the range that does not impair the effects of the present invention, may be added to resins as needed, such as: phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and metals Compounds, metal salts of higher fatty acids and other additives.

The above-mentioned laminate is not limited to a laminate film (sheet) shape, and may have various well-known shapes such as a hollow container, a cup, and a plate.

The manufacturing method of the above-mentioned laminated body varies according to the shape, size, and required physical properties of the final product, and there is no special limitation. For example, the following method: (1) At least one of the pre-formed layer (A) and the base layer (B) is thermally welded at a temperature higher than the melting temperature using a roll forming machine, a compression forming machine, or the like. (2) A method of thermally fusing the pre-formed layer (A) or the substrate layer (B) to other layers formed by extrusion and rolling. (3) When the base layer (B) is a layer containing a thermoplastic resin, the molding layer (A) and the base layer (B) are simultaneously extruded using a multi-layer extrusion molding machine, and thermally fused (co-extrusion molding) )Methods. (4) When the base layer (B) is a layer containing a thermoplastic resin, the molten layer (A) forming material and the molten base layer (B) forming material are shot out of the mold at staggered injection timings Internal (for example: 2-layer injection molding, sandwich injection molding) method.

Since the above-mentioned laminate is provided with the layer (A) containing the above-mentioned modified body, the layer adhesion is excellent, and even if the laminate is subjected to heat treatment at a high temperature of, for example, 230 to 250°C, it is possible to obtain a laminate whose layer adhesion is not easily reduced body. [Example]

Hereinafter, the present invention will be described using embodiments, but the present invention is not limited to these embodiments.

<Method for measuring the grafting rate> The grafting rate was measured using the AVANCEIIIcryo-500 nuclear magnetic resonance device (500MHz) manufactured by Bruker BioSpin Co., Ltd., and the measuring solvent: 1,1,2,2-tetrachloroethane-d2, Measuring temperature: 120℃, spectral bandwidth: 20ppm, pulse repetition time: 7.0 seconds, pulse width: 5.00μsec (45° pulse), measure ¹ H-NMR mass spectrum, by measuring the grafted epoxy monomer The amount of body or maleic anhydride is calculated, and the grafting rate is calculated.

[Example 1] Put in a 1L glass container: LLDPE (matrix polymer, comonomer species: 1-hexene, comonomer amount: 1.6% by mass, Mw: 164,000, Mn: 63,000, Mw/Mn: 2.60) 25.0 g, And 150 mL of toluene, and the container is sealed after nitrogen replacement. Then, the internal temperature of the container was increased to 140°C, and while maintaining the temperature, 50 mL of a toluene solution in which 4.11 g of vinyl phenyl oxirane (VPO) had been dissolved, and the dissolved dicumyl peroxide ( DCP) 0.6g of toluene solution 50mL, using double-anchor blades, while stirring at a stirring speed of 400rpm, while feeding for 2 hours. After further stirring for 2 hours, 250 mL of toluene was fed to dilute the reaction liquid. The internal temperature of the vessel was cooled to 50°C, the reaction solution was taken out after depressurization, 400 mL of tetrahydrofuran was added to the reaction solution, and the mixture was stirred for 10 minutes. Then, the reaction liquid was filtered and separated into a solid part and a filtrate. The obtained solid content was washed twice with 400 mL of tetrahydrofuran, and washed once with 400 mL of acetone, and then dried with a 70°C vacuum dryer for 10 hours to obtain a graft polymer (P-1). The yield of the graft polymer (P-1) was 25.34 g (mass increase amount: 0.34 g). In addition, the grafting rate was 1.7% by mass.

[Example 2] The graft polymer (P-2) was synthesized in the same manner as in Example 1, except that 4.08 g of vinyl phenyl glycidyl ether (VPGE) was used instead of VPO. The yield of the graft polymer (P-2) was 25.30 g (mass increase amount: 0.30 g). In addition, the grafting rate was 1.5% by mass.

[Example 3] The graft polymer (P-3) was synthesized in the same manner as in Example 1, except that 3.25 g of isopropenyl phenyl glycidyl ether (IPPGE) was used instead of VPO. The graft rate of the graft polymer (P-3) was 0.4% by mass.

[Comparative Example 1] In a 500 mL glass container, 25.0 g of LLDPE (matrix polymer), which is the same as the LLDPE used in Example 1, and 110 mL of xylene were charged, and the container was sealed with nitrogen after replacement. Then, the internal temperature of the container was raised to 120°C, 4.69 g of glycidyl methacrylate (GMA) was placed in the container, and then the tertiary butyl peroxymonocarbonate dissolved in 10 mL of xylene was dropped over 10 minutes 0.39 g of isopropyl ester (PERBUTYL I, manufactured by NOF Corporation) was stirred for 3 hours at a stirring speed of 400 rpm using a double-anchor blade. Then, 250 mL of xylene was added, and after raising the temperature to 120°C again, the internal temperature of the container was gradually cooled to 50°C. Then, the reaction solution was taken out, 400 mL of acetone was added to the obtained reaction solution, and the mixture was stirred for 10 minutes. Then, the reaction liquid was filtered and separated into a solid part and a filtrate. The obtained solid content was washed twice with 400 mL of acetone, and then dried with a vacuum dryer at 70° C. for 10 hours to obtain a graft polymer (P-4). The yield of the graft polymer (P-4) was 25.95 g (mass increase: 0.95 g). In addition, the grafting rate was 2.4% by mass.

[Comparative Example 2] In Comparative Example 1, except that 4.69 g of glycidyl methacrylate (GMA) was substituted and 3.4 g of maleic anhydride (MAH) was used instead, the graft polymerization was obtained in the same manner as in Comparative Example 1.物(P-5). The yield of the graft polymer (P-5) was 25.56 g (mass increase: 0.56 g). In addition, the grafting rate was 1.8% by mass.

[Table 1] Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Graft polymer P-1 P-2 P-3 P-4 P-5 Epoxy monomer VPO VPGE IPPGE GMA MAH Matrix polymer LLDPE LLDPE LLDPE LLDPE LLDPE Mass increase (g) 0.34 0.30 - 0.95 0.56 Grafting rate (mass%) 1.7 1.5 0.4 2.4 1.8

＜Continue to evaluate＞ ・Making of stamping sheet The graft polymers obtained in Example 1 and Comparative Example 1 were subjected to press forming under the conditions of temperature 180°C, pressure 4MPa, residual heat time of 5 minutes, and press time of 3 minutes, and then used a press forming machine set at 20°C Rapid cooling was performed to produce a stamped sheet with a thickness of 500 μm, a length of 80 mm, and a width of 80 mm. In addition, here, the peel strength was measured by the following T-type peeling to form a thick stamped sheet that was as thick as possible.

・Production of laminated body The base material layer used a polyethylene terephthalate (PET) sheet (product name: LUMIRROR T60, manufactured by Toray Co., Ltd.) with a thickness of 50 μm, a length of 80 mm, and a width of 80 mm. Stack the PET flakes, stamped flakes and PET flakes in sequence, and then sandwich the overlapped ones with Teflon sheets, set the temperature of the stamping plate (bottom) to 230℃, and the temperature of stamping plate (top) to 230℃~250 A heat sealer at ℃ performs heat sealing for 5 seconds to produce a laminated body composed of three layers.

・Peel test For the laminate obtained as described above, the upper PET sheet (the PET sheet adjacent to the punching plate (upper)) and the punched sheet were subjected to T-type peeling under the conditions of peeling environment temperature of 23°C, peeling speed of 300mm/min, and peeling width of 15mm. Measure the peel strength of the PET sheet and the punched sheet, and calculate the average value (n=5). The results are shown in Table 2 and Figure 1.

[Table 2] Graft polymer Epoxy monomer Temperature of stamping plate (upper) (℃) 230 240 250 Average peel strength (N) Example 1 P-1 VPO 4.44 6.99 8.57 Comparative example 1 P-4 GMA 0.77 2.49 4.08

[Example 4] Polyethylene terephthalate (PET, manufactured by Mitsui Chemicals Co., Ltd., J005) 75 parts by mass, LLDPE (comonomer species: 1-hexene, comonomer amount: 1.6% by mass, Mw: 164,000, Mn: 63,000, Mw/Mn: 2.60) 20 parts by mass, and 5 parts by mass of the graft polymer (P-1) obtained in Example 1 were melt-kneaded under the following conditions to produce a PET/LLDPE resin composition.

・Melt kneading conditions Kneading machine: Experimental plastic impact grinder manufactured by Toyo Seiki Co., Ltd. (two-shaft batch type melting and kneading device) Mixing temperature: 260℃ Screw revolution: 100rpm Mixing time: 5 minutes Resin amount: 30g

The obtained PET/LLDPE resin composition was observed with a transmission electron microscope (TEM, Hitachi High-Tech Co., Ltd., transmission electron microscope H-7650), and it was found that there are islands scattered in the PET belonging to the marine phase. Relative to LLDPE. The area of each island phase in the TEM observation image is measured, the diameter of each island phase when each island phase is converted to a perfect circle is calculated, and the average value of these is defined as the island phase particle size. The results are shown in Table 3.

[Comparative Example 3] In Example 4, except that the graft polymer (P-1) was substituted and the graft polymer (P-5) obtained in Comparative Example 2 was used instead, PET was produced in the same manner as in Example 4. /LLDPE resin composition, the island phase particle size is measured. The results are shown in Table 3.

[Comparative Example 4] In Example 4, except that the graft polymer (P-1) was not used, the PET/LLDPE resin composition was produced in the same manner as in Example 4, and the island phase particle size was measured. The results are shown in Table 3.

[table 3] Example 4 Comparative example 3 Comparative example 4 composition PET 75 75 75 LLDPE 20 20 25 P-1 5 P-5 5 Island particle size (μm) 0.46 0.66 2.79

When the graft polymer (P-1) is used, the island phase particle size of LLDPE is smaller than when the graft polymer (P-5) is used, and the case where the graft polymer is not used. This phenomenon can be thought to be caused by the use of grafted polymer (P-1) to improve the compatibility of PET and LLDPE.

Fig. 1 is a graph of subsequent evaluation results of the following examples.

Claims (6)

[A graft-modified body is obtained by graft-modifying at least one matrix polymer selected from ethylene-based polymers and propylene-based polymers using an epoxy monomer represented by the following formula (1); [化1]

[In formula (1), R is a hydrogen atom or a methyl group; X is -O- or a single bond; n is an integer from 0 to 3]. An adhesive containing the graft-modified body of claim 1. A compatibilizer containing the graft-modified body of claim 1. A laminated body comprising: a layer (A) containing the grafted modified body of claim 1 and a substrate layer (B). The laminate according to claim 4, wherein the substrate layer (B) is a layer having a polar group. The laminate of claim 5, wherein the polar group is a carboxyl group or a hydroxyl group.

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