WO2021172153A1

WO2021172153A1 - Graft modified product, adhesive, compatibilizer, and laminate

Info

Publication number: WO2021172153A1
Application number: PCT/JP2021/006047
Authority: WO
Inventors: 勝好原田; 市川　達也; 悠介溝渕; 千紘小松; 友哉後藤; 咲里田中
Original assignee: 三井化学株式会社
Priority date: 2020-02-27
Filing date: 2021-02-18
Publication date: 2021-09-02
Also published as: TW202138407A

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 products, adhesives, compatibilizers and laminates

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

Polyolefins such as polyethylene and polypropylene are excellent in mechanical strength, rigidity, heat resistance, chemical resistance, oil resistance, transparency, impact resistance at low temperatures, etc., and by utilizing these characteristics, films and sheets , Bottles and other packaging and coating materials, or wallpaper and other decorative materials.

However, since polyolefin does not contain a polar group in its molecule, it is compatible with polar resins such as polyester, polyphenylene sulfide, polyamide, polyacetal, polycarbonate, and polyacrylate, and metal, glass, paper, or the polar resin, etc. Adhesion with these materials was poor, and it was restricted that they could be used by blending with these materials or by laminating them.

In order to solve such a problem, a method of grafting a polar group-containing monomer on polyolefin to improve the compatibility and adhesiveness has been widely used. For example, a method of grafting glycidyl (meth) acrylate or the like on polyolefin is generally widely used (for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 6-145260

The modified polyolefin obtained by the method described in Patent Document 1 or the like can improve the compatibility and adhesiveness to some extent, but the compatibility and adhesiveness are not sufficient, and glycidyl (meth) acrylate is a glycidyl (meth) acrylate. There is a risk of mutagenicity, and care must be taken in handling, and there are problems such as the need to take measures for the working environment, especially for grafts in the molten state.

In one embodiment of the present invention, a highly safe monomer having a small load on the human body or the like can be used to form a layer having excellent adhesion to a base material having a polar group such as polyester or polyphenylene sulfide, and the polarity is described. Provided is a graft modified product having excellent compatibility with a resin.

As a result of the research conducted by the present inventor, it was found that the above problem can be solved according to the following configuration example. A configuration example of the present invention is as follows.

[1] A graft-modified product of at least one base polymer selected from an ethylene-based polymer and a propylene-based polymer with an epoxy monomer represented by the following 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 to 3. ]

[2] An adhesive containing the graft modified product according to [1].
[3] A compatibilizer containing the graft-modified product according to [1].

[4] A laminated body containing the layer (A) containing the graft modified product according to [1] and the base material layer (B).
[5] The laminate according to [4], wherein the base material layer (B) is a layer having a polar group.
[6] The laminate according to [5], wherein the polar group is a carboxy group or a hydroxy group.

According to one embodiment of the present invention, it is possible to form a layer having excellent adhesiveness to a base material having a polar group such as polyester or polyphenylene sulfide by using a highly safe monomer having a small load on the human body or the like. It is possible to provide a graft modified product having excellent compatibility with the polar resin.

FIG. 1 is a diagram showing the results of adhesion evaluation in the following examples.

≪Graft denatured body≫
The graft modified product according to the embodiment of the present invention (hereinafter, also referred to as “the present modified product”) is the following formula (1) of at least one base polymer selected from an ethylene polymer and a propylene polymer. It is a graft modified product with the represented epoxy monomer.
It can be said that this modified product is a graft-modified product in which at least one base polymer selected from an ethylene-based polymer and a propylene-based polymer is graft-modified with an epoxy monomer represented by the following formula (1). It can be said that it is a graft modified product containing at least one base polymer moiety selected from an ethylene polymer and a propylene polymer and a graft moiety derived from an epoxy monomer represented by the following formula (1).

According to this modified product, it is possible to form a layer having excellent adhesion to a base material having a polar group such as polyester or polyphenylene sulfide, while using a highly safe monomer that has a low load on the human body or the like. The modified product has excellent compatibility with polar resins such as polyester, polyphenylene sulfide, polyamide, polyacetal, polycarbonate, and polyacrylate.
Since glycidyl (meth) acrylate has an ester bond, it has a higher polarity than the epoxy monomer represented by the following formula (1), and the graft modified product with glycidyl (meth) acrylate has a polar group such as polyester or polyphenylene sulfide. It is considered that the modified product has excellent adhesion to the base material and compatibility with the polar resin, but this modified product has a polar group such as polyester or polyphenylene sulfide as compared with the graft modified product using glycidyl (meth) acrylate. It is remarkably excellent in adhesiveness to the material and compatibility with the polar resin.
Further, this modified product is excellent in storage stability as compared with, for example, a graft modified product using glycidyl (meth) acrylate.
Since this modified product is not a block copolymer or a random copolymer of a monomer such as ethylene or propylene and the epoxy monomer, but a graft modified product, the above effect is exhibited.

The graft ratio in the modified product is preferably 0.1 to 10% by mass from the viewpoints of ease of synthesis of the modified product and the ability to easily obtain a graft modified product having better compatibility and adhesiveness. , More preferably 0.1 to 5% by mass.
The graft ratio is the mass of the structure derived from the epoxy monomer in the graft modified product, and ^{can be determined by 1 1} H-NMR measurement, specifically, the method described in the following Examples.

<Epoxy monomer>
The epoxy monomer used for graft-modifying the base polymer is a compound represented by the following formula (1).
The epoxy monomer used for graft-modifying the base polymer may be two or more, but is usually one.

In the formula (1), R is a hydrogen atom or a methyl group, and a hydrogen atom is preferable from the viewpoint that the modified product having a high graft ratio can be easily obtained.
In the formula (1), X is —O— or a single bond, and a layer showing good compatibility at a low graft rate and good adhesiveness at a low graft rate can be easily formed. , Single bond is preferred.
In the formula (1), n is an integer of 0 to 3, and a layer showing good compatibility at a low graft ratio and good adhesiveness at a low graft ratio can be easily formed. An integer of 0 to 2 is preferable, and 0 or 1 is more preferable.

Specific examples of the epoxy monomer include vinylphenyloxylan (VPO), isopropenylphenyloxylan, vinylphenylglycidyl ether (VPGE), isopropenylphenylglycidyl ether (IPPGE), vinylphenylmethyloxylan, vinylphenylethyloxylan, and vinylphenylpropi. Luoxylane can be mentioned, and among these, VPO, VPGE, and IPPGE are preferable, VPO and IPPGE are more preferable, and VPO is particularly preferable, from the viewpoint of showing high reactivity and the like.

<Base polymer>
The base polymer before graft modification with the epoxy monomer is at least one polymer selected from an ethylene-based polymer and a propylene-based polymer.
The base polymer may be two or more kinds, but usually one kind.

The weight average molecular weight (Mw) of the base polymer is not particularly limited, but is preferably 100,000 or more, more preferably 150,000 or more, and preferably 500,000 from the viewpoint of ease of synthesis of the modified product. Below, it is more preferably 400,000 or less.
The number average molecular weight (Mn) of the base polymer is also not particularly limited, but for the same reason, it is preferably 40,000 or more, more preferably 50,000 or more, preferably 80,000 or less, more preferably 70, It is 000 or less.
The molecular weight distribution (Mw / Mn) of the base polymer is also not particularly limited, but is preferably 1.5 or more, more preferably 2.0 or more, preferably 5.0 or less, and more preferably 4.0 or less. ..

The Mw and Mn are values measured under the following conditions using an HLC-8321 GPC / HT type gel permeation chromatograph (GPC) manufactured by Tosoh Corporation.
Separation columns: TSKgel GMH6-HT (2 pcs) and GMH6-HTL (2 pcs) (both 7.5 mm ID x 30 cm, manufactured by Tosoh Corporation)
Column temperature: 140 ° C
Mobile phase: o-dichlorobenzene (containing 0.025% dibutylhydroxytoluene (BHT))
Development rate: 1.0 mL / min Sample concentration: 0.1% (w / v)
Sample injection volume: 0.4 mL
Detector: Differential refractometer Equipment calibration: Monodisperse polystyrene (manufactured by Tosoh Corporation, # 3std set) was used.

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 examples thereof include a method using a coordination polymerization catalyst system containing a transition metal. Specific examples thereof include a magnesium chloride-supported titanium catalyst, a soluble vanadium compound and an alkylaluminum halide compound. Synthesized by (co) polymerizing ethylene or propylene and, if necessary, a comonomer described below in the presence of a vanadium-based catalyst containing the above or a metallocene catalyst containing a metallocene compound and an organic aluminum oxy compound. The method can be mentioned.

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

Examples of the comonomer include at least one monomer selected from propylene, α-olefin having 4 to 20 carbon atoms and conjugated polyene, and among these, propylene and α-olefin having 4 to 20 carbon atoms are preferable. ..
The α-olefin having 4 to 20 carbon atoms may be linear or branched, and may be, for example, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, etc. Examples thereof include 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 unit in the ethylene polymer is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 30% by mass or less, from the viewpoint of easy handling without blocking of pellets and powders. It is 20% by mass or less. An ethylene-based polymer having a content of a constituent unit derived from propylene of 50% by mass is referred to as an ethylene-based polymer in the present specification.

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

Examples of the comonomer include at least one monomer selected from ethylene, an α-olefin having 4 to 20 carbon atoms and a conjugated polyene, and among these, ethylene and an α-olefin having 4 to 20 carbon atoms are preferable. ..
Examples of the α-olefin having 4 to 20 carbon atoms include α-olefins similar to the α-olefin having 4 to 20 carbon atoms mentioned in the column of ethylene-based polymers.
The content of the comonomer-derived structural unit in the propylene-based polymer is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 30% by mass or less, from the viewpoint of easy handling without blocking of pellets and powders. It is 20% by mass or less.

<Synthesis method of this denatured product>
The method for synthesizing the modified product is not particularly limited, and is not particularly limited as long as a graft-modified product obtained by graft-modifying the base polymer with the epoxy monomer is obtained. A method in which a radical initiator and the epoxy monomer are added to a solution in which a polymer is dissolved or dispersed in a solvent, preferably a solution in which the base polymer is dissolved in an organic solvent, is reacted (graft reaction) is preferable. When a reaction device having a stirring ability capable of uniformly flowing the base polymer is used, it is not necessary to use a solvent. According to the above method, graft polymerization occurs, so that a graft modified product can be obtained.

With respect to the amount of the epoxy monomer used in the graft reaction, the modified product having a graft ratio within the above range can be easily obtained, and a polymer of the epoxy monomer itself (hereinafter, also referred to as “non-grafted polymer”) is produced. It is preferably 10 to 1000 mol, more preferably 10 to 800 mol, with respect to 1 mol of the base polymer, from the viewpoint of being able to suppress the above.

Examples of the radical initiator include organic peroxides and azo compounds. Specifically, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexin-3, 1,4-bis (tert-). Butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperacetate, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexin-3,2,5-dimethyl-2,5-di (tert) -Butylperoxy) hexane, tert-butylperbenzoate, tert-butylperphenylacetate, tert-butylperisobutyrate, tert-butylper-sec-octate, tert-butylperpivalate, cumylperpivalate, tert- Organic peroxides such as butylperdiethyl acetate; azo compounds such as azobisisobutyronitrile and dimethylazoisobutyrate can be mentioned. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexin-3, 2,5-dimethyl-2,5-di (tert). Peroxides such as -butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.

The amount of the radical initiator used in the graft reaction is preferable with respect to 1 mol of the epoxy monomer from the viewpoint that the graft reaction occurs efficiently and the modified product having a graft ratio in the above range can be easily obtained. Is 0.01 mol or more, more preferably 0.05 mol or more, preferably 0.5 mol or less, and more preferably 0.3 mol or less.

As the organic solvent, an organic solvent that does not significantly inhibit the graft reaction of the epoxy monomer and has an affinity with the base polymer in the temperature range in which the graft reaction is performed is preferable. 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, cyclohexane and methylcyclohexane. Alicyclic hydrocarbon solvents such as decahydronaphthalene, chlorinated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene, methanol, ethanol, n-propanol, iso- Alcohol solvents such as propanol, n-butanol, sec-butanol, tert-butanol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and dimethyl phthalate, dimethyl ether, diethyl ether, di- Examples thereof include ether solvents such as n-amyl ether, tetrahydrofuran, and dioxyanisole. Further, 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. It is preferable that the reaction solution has a uniform phase by using these solvents, but a plurality of non-uniform phases may be used.

Since the graft reaction is carried out in a region where the liquid containing the base polymer can be uniformly stirred, the concentration of the base polymer in the liquid is usually set to 50 to 500 g / L, but a high graft ratio can be easily achieved. From the above, it is preferably 200 to 500 g / L.

The radical initiator and the epoxy monomer may be started by collectively adding the base polymer-containing liquid (or the base polymer itself) to initiate the graft reaction, but from the viewpoint that a high graft ratio can be easily achieved, it is 0. It is preferable to carry out the graft reaction by sequentially adding the mixture over a period of about 5 to 5 hours.

It is desirable that the graft reaction is usually carried out at a temperature of 60 to 200 ° C., preferably 100 to 160 ° C., for usually 2 to 10 hours, preferably 3 to 8 hours.

The modified product obtained by the graft reaction is obtained by filtering, centrifuging, reprecipitating and / or washing the solvent used, unreacted radical initiator or epoxy compound, by-produced non-grafted polymer, etc. It may be purified and isolated by using a known method such as combining if necessary.
In this case, the content of the non-grafted polymer contained in the modified product is preferably 5% by mass or less, from the viewpoint that the modified product having better compatibility and adhesiveness can be easily obtained. It is desirable to purify and isolate it so that it is more preferably 2% by mass or less.

<Use of this denatured product>
Since this modified product has excellent compatibility with polar resins such as polyester, polyphenylene sulfide, polyamide, polyacetal, polycarbonate, and polyacrylate, and olefin-based polymers, the phase of the composition containing these polar resins and olefin-based polymers. Since it has excellent adhesion to a container, metal, glass, paper, or the polar resin or olefin polymer, it has excellent dispersibility in an adhesive or olefin polymer to a substrate containing these. It can also be mixed with an olefin polymer and used as an olefin resin composition or the like. The olefin-based resin composition can be used as an adhesive (including a pressure-sensitive adhesive) and a compatibilizer, and can also be used, for example, in printing inks and paints.

The olefin-based polymer is not particularly limited as long as it is a polymer mainly composed of olefins, and various known olefin-based polymers can be used. Specifically, for example, a single or copolymer of α-olefin such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene (eg, 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, ethylene / α-olefin copolymer [eg, low crystalline or amorphous] Sexual ethylene / propylene random copolymer, ethylene / 1-butene random copolymer], propylene / α-olefin copolymer [eg, propylene / 1-butene random copolymer]), ethylene / vinyl acetate copolymer Combined (EVA), ethylene / (meth) acrylic acid copolymer or metal salt thereof, ethylene-cyclic olefin copolymer, these (co) copolymers were graft-modified with polar compounds such as maleic acid and silane compounds. Examples include copolymers.

The content of the modified product in the olefin resin composition is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more from the viewpoints of molding processability, controllability of adhesive ability, economy, and the like. It is usually 30% by mass or less, preferably 15% by mass or less.

When the modified product or the olefin-based resin composition is used for various purposes, various additions are made to the modified product or the olefin-based resin composition as necessary within a range that does not impair the effects of the present invention. The agent may be blended.
Examples of the additive include a softening agent, a stabilizer, a filler, an antioxidant, a crystal nucleating agent, a wax, a thickener, a mechanical stability imparting agent, a leveling agent, a wetting agent, a film-forming auxiliary, and a cross-linking agent. Agents, preservatives, rust inhibitors, pigments, fillers, dispersants, antifreezes, defoamers, tackifiers, other thermoplastic polymers, water, organic solvents, each of which is 1 The species may be used alone, or two or more species may be used.

≪Adhesive≫
Among the above-mentioned uses of the modified product, the modified product is a layer containing polyester or polyphenylene sulfide from the viewpoint that the effect of the present invention is more exhibited because it has excellent adhesiveness to polyester and polyphenylene sulfide. It is preferable to use it as an adhesive against.

The adhesive according to the embodiment of the present invention is not particularly limited as long as the modified product is included, and the modified product contained in the adhesive may be one type or two or more types.
The adhesive may be an adhesive consisting of only the modified product, or may contain one or more of the above-mentioned olefin-based polymer and additives, respectively.
The content of the modified product in the adhesive is not particularly limited, but is usually 5 to 100% by mass, preferably 10 to 100% by mass.

The adhesive can be used in various known forms, for example, an aqueous dispersion type adhesive, an organic solvent type adhesive, and a hot melt type adhesive.

Examples of the adhesive target of the adhesive include metal (film); glass; wood; paper; cloth; polyester, polyphenylene sulfide, polyamide, polyacetal, polycarbonate, polyacrylate, polyolefin, polystyrene, rubber, and other engineering plastics. A layer containing a thermoplastic resin or a thermosetting resin, or a layer composed of these;

≪Compatibility agent≫
Further, among the above-mentioned uses of the modified product, the modified product has compatibility with a polar resin due to an epoxy group (particularly reactivity with a polar resin having an active hydrogen group) and an ethylene-based polymer or a propylene-based weight. Since it has compatibility with olefin-based polymers due to the main chain skeleton containing coalescence, it is used as a compatibility agent between polar resins (particularly polar resins with active hydrogen groups) and olefin-based polymers. It is also preferable. A molded product obtained from a compatible composition containing a polar resin, an olefin-based polymer, and a present-modified product as a compatibilizer thereof can be obtained from the polar resin and the olefin-based polymer by the present-modified product. By improving the compatibility of the above, it is considered that the molded product has excellent mechanical properties such as impact resistance and has a smooth surface.

The modified product used in the compatible composition may be one kind or two or more kinds.
In addition, the compatible composition may contain one or more of the above-mentioned additives, respectively.
The content of the modified product in the compatible composition is not particularly limited, but 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, preferably 30% by mass or less. It is 25% by mass or less, more preferably 20% by mass or less.

The polar resin used in the compatible composition is not particularly limited, but engineering plastics having polarity are preferable, and more preferable examples are polyester (eg, PET, PBT, polylactic acid (PLA)), polyamide, and polyphenylene sulfide. (PPS), ethylene vinyl alcohol copolymer (EVOH) can be mentioned.
Examples of the active hydrogen group include a carboxy group, a hydroxy group, an amino group, a thiol group and the like.
The content of the olefin polymer in the compatible composition is not particularly limited, but 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, preferably 98% by mass or less. Is 90% by mass or less, more preferably 80% by mass or less.
The polar resin used in the compatible composition may be one kind or two or more kinds.

The olefin-based polymer used in the compatible composition may be one kind or two or more kinds. Specific examples thereof include polymers similar to the olefin-based polymers described in the column of uses of the modified product.
The content of the olefin polymer in the compatible composition is not particularly limited, but 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, preferably 80% by mass or less. Is 60% by mass or less, more preferably 50% by mass or less.

≪Laminated body≫
The laminate according to the embodiment of the present invention is not particularly limited as long as the layer (A) containing the modified product and the base material layer (B) are included, and includes two or more layers (A). It may be included, and may contain two or more layers of the base material layer (B). When two or more layers (A) are included, these layers may be the same layer or different layers. Similarly, when two or more base material layers (B) are included, these layers may be the same layer or different layers.
The laminated body includes a layer (A) and a base material layer (B), or a base material layer (B), a layer (A), and a base material layer (B) in this order. It is preferably a body.

The layer (A) can be obtained by using the modified product or the adhesive. It can be determined by infrared spectroscopic analysis that the modified product is contained in the layer (A).

The thickness of the layer (A) is not particularly limited and may be appropriately selected depending on the intended use of the laminated body, but is preferably 2 to 1000 μm.
Further, the thickness of the base material layer (B) is not particularly limited and may be appropriately selected depending on the intended use of the laminated body, but is preferably 2 to 1000 μm.

Examples of the base material layer (B) include metal (film); glass; wood; paper; cloth; polyester, polyphenylene sulfide, polyamide, polyacetal, polycarbonate, polyacrylate, polyolefin, polystyrene, rubber, and other engineering plastics. And the like; a layer made of a thermoplastic resin or a thermosetting resin;

Examples of the thermoplastic resin include various known thermoplastic resins such as polyolefins (eg polyethylene, polypropylene, poly4-methyl-1-pentene, polybutene), polyesters (eg polyethylene terephthalate (PET), polybutylene terephthalate (eg, polybutylene terephthalate). PBT), polyethylene terephthalate), polyphenylene sulfide, polyamide (eg nylon-6, nylon-66, polymethoxylen adipamide), polyvinyl chloride, polyvinylidene chloride, polymethylmethacrylate, vinylacetate, polyimide, ethylene -Vinyl acetate copolymer or its saponified product, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ethylene- (meth) acrylic acid copolymer or its metal salt (ionomer), thermoplastic polyurethane, biodegradable plastic (eg) : An aliphatic polyester such as polylactic acid) can be mentioned.

Examples of the thermosetting resin include various known thermosetting resins such as epoxy resin, unsaturated polyester resin, phenol resin, urea-melamine resin, polyurethane resin, silicone resin, and polyimide.

The base material layer (B) is preferably a layer having a polar group.
When such a base material layer (B) is used, the epoxy group in the modified product reacts with the polar group in the base material layer (B) to be in a bonded state, so that the layer (B) The adhesiveness between A) and the base material layer (B) is further improved. In this case, the layer (A) includes not only the modified product but also a state in which the epoxy group of the modified product reacts with the polar group of the base material layer (B).

Examples of the polar group include a carboxy group, a hydroxy group, an amino group, an ester group, and a carbonyl group. Among these, a carboxy group and a hydroxy group are preferable from the viewpoint of excellent reactivity with an epoxy group. The base material layer (B) may have two or more types of polar groups.
For example, polyester usually has a carboxy group and a hydroxy group at the end. Also, polyphenylene sulfide usually has a carboxy group at the end. Glass and metals also usually have a hydroxy group.

The thermoplastic resin and the thermosetting resin are usually added to the resin as needed, and are used as phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, metal compounds, and higher fatty acids. Additives such as metal salts may be contained within a range that does not impair the effects of the present invention.

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

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, and examples thereof include the following methods.
(1) A method of heat-sealing using a calendar roll molding machine, a compression molding machine, or the like at a temperature equal to or higher than the temperature at which at least one of the preformed layer (A) and the base material layer (B) is melted.
(2) A method of heat-sealing a preformed layer (A) or a base material layer (B) to another layer that is extrusion-molded or calendar-molded.
(3) When a layer containing a thermoplastic resin is used as the base material layer (B), the layer (A) and the base material layer (B) are extruded at the same time with a multi-layer extrusion molding machine and heat-sealed (co-fused). (Extrusion molding) method.
(4) When a layer containing a thermoplastic resin is used as the base material layer (B), the injection timing of the molten layer (A) forming material and the melted base material layer (B) forming material is shifted. A method of injecting into a mold (eg, two-layer injection molding, sandwich injection molding).

Since the laminate has the layer (A) containing the modified product, it has excellent interlayer adhesiveness, and even if the laminate is heat-treated at a high temperature of, for example, 230 to 250 ° C., the interlayer adhesive strength is lowered. A difficult laminate can be obtained.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

<Measurement method of graft rate>
The graft ratio was measured using an AVANCE III cryo-500 type nuclear magnetic resonance apparatus (500 MHz) manufactured by Bruker Biospin Co., Ltd., measurement solvent: 1,1,2,2-tetrachloroethane-d2, measurement temperature: 120 ° C., spectrum. Under the measurement conditions of width: 20 ppm, pulse repetition time: 7.0 seconds, pulse width: 5.00 μsec (45 ° pulse), ¹ H-NMR spectrum was measured and the grafted epoxy monomer or maleic anhydride The graft ratio was calculated by measuring the amount.

[Example 1]
25. LLDPE (base polymer, comonomer species: 1-hexene, comonomer amount: 1.6% by mass, Mw: 164,000, Mn: 63,000, Mw / Mn: 2.60) in a 1 L glass container. 150 mL of 0 g and toluene were charged, and the container was replaced with nitrogen and then sealed. Then, the internal temperature of the container was raised to 140 ° C., and while maintaining that temperature, 50 mL of a toluene solution in which 4.11 g of vinylphenyloxylane (VPO) was dissolved and 0.6 g of dicumyl peroxide (DCP) were dissolved. 50 mL of the toluene solution was fed over 2 hours while stirring at a stirring speed of 400 rpm using a double anchor blade. Then, after stirring for another 2 hours, 250 mL of toluene was fed to dilute the reaction solution.
The internal temperature of the vessel was cooled to 50 ° C., and after depressurization, the reaction solution was taken out, 400 mL of tetrahydrofuran was added to the reaction solution, and the mixture was stirred for 10 minutes. Then, the reaction solution was filtered and separated into a solid content and a filtrate. The obtained solid content was washed twice with 400 mL of tetrahydrofuran and once with 400 mL of acetone, and dried in a vacuum dryer at 70 ° C. for 10 hours to obtain a graft polymer (P-1). The yield of the graft polymer (P-1) was 25.34 g (mass increase: 0.34 g). The graft ratio was 1.7% by mass.

[Example 2]
A graft polymer (P-2) was synthesized in the same manner as in Example 1 except that 4.08 g of vinyl phenylglycidyl ether (VPGE) was used instead of VPO. The yield of the graft polymer (P-2) was 25.30 g (mass increase: 0.30 g). The graft ratio was 1.5% by mass.

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

[Comparative Example 1]
A 500 mL glass container was charged with 25.0 g of LLDPE (base polymer) similar to the LLDPE used in Example 1 and 110 mL of xylene, and the container was replaced with nitrogen. Then, the internal temperature of the container was raised to 120 ° C., 4.69 g of glycidyl methacrylate (GMA) was charged into the container, and then tert-butylperoxyisopropyl monocarbonate (perbutyl I,) dissolved in 10 mL of xylene was charged. 0.39 g (manufactured by Nichiyu Co., Ltd.) was added dropwise over 10 minutes, and the mixture was stirred at a stirring speed of 400 rpm for 3 hours using a double anchor blade. Then, 250 mL of xylene was added, the temperature was raised to 120 ° C. again, and then 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 solution was filtered and separated into a solid content and a filtrate. The obtained solid content was washed twice with 400 mL of acetone and dried in 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). The graft ratio was 2.4% by mass.

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

<Adhesion evaluation>
-Preparation of press sheet Each of the graft polymers obtained in Example 1 and Comparative Example 1 was press-molded under the conditions of temperature 180 ° C., pressure 4 MPa, residual heat time 5 minutes, and pressurization time 3 minutes, and then set to 20 ° C. A press sheet having a thickness of 500 μm, a length of 80 mm, and a width of 80 mm was produced by quenching with a press molding machine. Here, in order to measure the peeling strength by the following T-shaped peeling, a thick press sheet is intentionally formed.

-Preparation of laminated body A polyethylene terephthalate (PET) sheet (product name: Lumirror T60, manufactured by Toray Industries, Inc.) having a thickness of 50 μm, a length of 80 mm, and a width of 80 mm was used as a base material layer.
The PET sheet, the press sheet and the PET sheet were stacked in this order, and the stacked sheets were sandwiched between Teflon sheets, and the press plate (bottom) temperature was set to 230 ° C. and the press plate (top) temperature was set to 230 ° C. to 250 ° C. Heat sealing was performed for 5 seconds with a heat sealer to prepare a laminated body consisting of three layers.

-Peeling test With respect to the laminate obtained above, the upper PET sheet (PET sheet in contact with the press plate (upper)) and the press sheet are separated under the conditions of a peeling atmosphere temperature of 23 ° C., a peeling speed of 300 mm / min, and a peel width of 15 mm. The peeling strength between the PET sheet and the press sheet was measured by T-shaped peeling, and the average value (n = 5) was calculated. The results are shown in Table 2 and FIG.

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

・ Melting and kneading conditions Kneading machine: Labplast mill manufactured by Toyo Seiki Co., Ltd. (2-axis batch type melting and kneading device)
Kneading temperature: 260 ° C
Screw rotation speed: 100 rpm
Kneading time: 5 minutes Resin amount: 30 g

When the obtained PET / LLDPE resin composition was observed with a transmission electron microscope (TEM, manufactured by Hitachi High-Tech Co., Ltd., transmission electron microscope H-7650), the island phase of LLDPE was dispersed in PET, which is the sea phase. Was there.
The area of each island phase in the TEM observation image was measured, the diameter of each island phase when converted to a perfect circle was obtained, and the average value thereof was taken as the particle size of the island phase. The results are shown in Table 3.

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

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

When the graft polymer (P-1) was used, the particle size of the island phase of LLDPE was smaller than when the graft polymer (P-5) was used or when the graft polymer was not used. It is considered that this is because the graft polymer (P-1) improved the compatibility between PET and LLDPE.

Claims

A graft-modified product of at least one base polymer selected from an ethylene-based polymer and a propylene-based polymer with an epoxy monomer represented by the following 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 to 3. ]
An adhesive containing the graft modified product according to claim 1.
A compatibility agent containing the graft modified product according to claim 1.
A laminated body containing the layer (A) containing the graft modified product according to claim 1 and the base material layer (B).
The laminate according to claim 4, wherein the base material layer (B) is a layer having a polar group.
The laminate according to claim 5, wherein the polar group is a carboxy group or a hydroxy group.