JPH10101871A - Resin composition and laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminate, excellent in extrusion or injection meltability and useful as an adhesive between a polyolefin-based resin layer and a fluorine- based resin layer or an acrylic resin layer. SOLUTION: This resin composition is obtained by compounding (A) 100 pts.wt. acrylic graft copolymer obtained according to the following method for production with (B) 1-200 pts.wt. acrylic resin and (C) 1-200 pts.wt. fluorine- based resin (with the proviso that the sum total of the components B and C is <=300 pts.wt.): The acrylic graft copolymer A is obtained by reacting (a) an olefinic resin having at least one functional group in one molecule with (b) a radically polymerizable monomer having a functional group reactive with the functional group, providing (c) a radically polymerizable olefinic resin and radically copolymerizing 100 pts.wt. resin (c) with (d) an alkyl acrylate or an alkyl methacrylate (the number of carbon atoms in the alkyl group is 1-8) in an amount of 10-500 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive resin composition comprising an acrylic graft copolymer and an olefin resin, and an olefin resin and a fluorine resin obtained by using the resin composition as an adhesive. The present invention relates to a laminate or a laminate of an olefin resin and an acrylic resin.

[0002]

2. Description of the Related Art Nonpolar olefin resins such as polyethylene and polypropylene are widely used in the fields of household electric appliances, automobile parts, packaging materials and the like because of their advantages such as low cost, light weight, and good moldability. . However, olefin resins do not have sufficient antifouling properties, weather resistance, and chemical resistance to nonpolar solvents.

On the other hand, fluororesins are excellent in antifouling properties, weather resistance, chemical resistance, solvent resistance, and abrasion resistance.
It has been studied to apply a fluorine-based resin to the surface of an olefin-based resin.However, the fluorine-based resin has poor adhesion to various base materials, and the coating formed even when the fluorine-based resin is applied to the surface of various base materials. There is a disadvantage that the film is easily peeled. In addition, acrylic resins are widely used as various molded articles and acrylic paints because of their excellent weather resistance, design properties, and transparency, and various studies have been made on composites of olefin resins and acrylic resins.

However, it is hard to say that the adhesion between an olefin resin represented by polyethylene or polypropylene having no polar group and a fluorine resin or an acrylic resin is not sufficient, and various methods have been used to improve this. Are being considered. For example, as a method for improving the adhesion between an olefin resin and a fluorine resin, a polymerization product obtained by copolymerizing an acrylic monomer and / or a fluorine unsaturated monomer with a radically polymerizable olefin resin is used as a primer. (JP-A-4-20538) and a method of utilizing a composition comprising polyolefin, polyvinylidene fluoride and acryl-grafted polyolefin as an adhesive layer (JP-A-5-295182). However, these adhesive compositions have insufficient spreadability at the time of melting, and it has been difficult to mold thermoplastic resins by extrusion or injection molding methods generally used.

As a method for improving the adhesiveness with an acrylic resin, a method of using a resin composition comprising an acrylic resin, a polyolefin and an acrylic graft polyolefin as an adhesive between a polyolefin layer and an acrylic resin layer (Japanese Patent Laid-Open Publication No. No. 5-295183), but this composition also has a drawback that the spreadability at the time of melting is not sufficient and the moldability is poor.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition having excellent adhesion between an olefin resin layer and a fluorine resin layer or an acrylic resin layer, and excellent melt spreadability during molding. To provide.

[0007]

According to the present invention, 100 parts by weight of an acrylic graft copolymer (A) obtained by the following method are mixed with 1 to 200 parts by weight of an acrylic resin (B) and a fluororesin (C). ) 1 to 200 parts by weight [However, the sum of the components (B) and (C) is 3 parts per 100 parts by weight of the component (A).
Not more than 00 parts by weight. ] Is provided.

Acrylic graft copolymer (A): Radical polymerizable monomer having a functional group reactive with the olefin resin (a) having at least one functional group per molecule (A) b) is reacted to obtain a radically polymerizable olefin-based resin (c), and 100 parts by weight of the resin (c) is further added to an alkyl acrylate or an alkyl methacrylate (provided that the alkyl group has 1 to 1 carbon atoms). 8) A copolymer obtained by subjecting (d) to radical copolymerization at a ratio of 10 to 500 parts by weight.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Acrylic graft copolymer (A) Olefin resin having at least one functional group in one molecule (a) Olefin resin (a) having at least one functional group in one molecule is It can be obtained by reacting an existing polyolefin with an unsaturated compound having a desired functional group, or copolymerizing various olefins with a desired functional group and an unsaturated compound having an ethylenically unsaturated bond.

In a method of reacting an unsaturated compound having a desired functional group with an existing polyolefin, the precursor polyolefin may be, for example, polyethylene,
Polyα-olefins such as polypropylene, polybutene-1, ethylene-propylene copolymer, ethylene-butene copolymer or copolymers thereof, α-olefins such as ethylene-propylene-diene copolymer, isobutene-isoprene copolymer -Copolymer of olefin and conjugated diene, polybutadiene, polyconjugated diene such as polyisoprene, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer or hydrogenated product thereof, styrene-isoprene copolymer, styrene A copolymer of an aromatic vinyl compound such as an isoprene-styrene block copolymer, a styrene-butadiene-isoprene-styrene block copolymer, or a hydrogenated product thereof and a conjugated diene, and chlorinated products of these polyolefins.

Among these polyolefins, styrene elastomers such as polyethylene, polypropylene, chlorinated polyethylene, chlorinated polypropylene, styrene-butadiene-styrene block copolymer and hydrogenated products thereof are preferable. Examples of the functional group introduced into the polyolefin of these precursors include a carboxylic acid or an anhydride thereof, an epoxy group, a hydroxyl group, an isocyanate group, an oxazoline group, and a carbodiimide group. When a carboxylic acid (including an acid anhydride thereof) group is introduced into a polyolefin, preferred unsaturated compounds having such a functional group include (meth) acrylic acid, fumaric acid, maleic acid and its anhydride, and itacone. Unsaturated carboxylic acids such as acids and anhydrides thereof, crotonic acid and anhydrides thereof, citraconic acid and anhydrides thereof, and anhydrides thereof.

When an epoxy group is introduced into the polyolefin, preferred unsaturated compounds include glycidyl (meth) acrylate, 3,4-epoxycyclohexenylmethyl (meth) acrylate, mono- and diglycidyl esters of maleic acid, and itacone. Unsaturated carboxylic acid glycidyl esters such as mono- and diglycidyl esters of acids, mono- and diglycidyl esters of allylsuccinic acid, glycidyl esters of p-styrenecarboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl Glycidyl ether such as ether, p-glycidylstyrene, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-
Epoxy olefins such as 1-butene, vinylcyclohexene monoxide and the like can be mentioned.

Suitable compounds for introducing a hydroxyl group into the polyolefin include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate; N-methylol (meth) acrylamide, 2-hydroxyethyl acrylate-6-hexanolide addition polymer, alkenyl alcohol such as 2-propen-1-ol, alkynyl alcohol such as 2-propyn-1-ol, hydroxyvinyl ether, and the like. Can be

When an isocyanate group is introduced into the polyolefin, preferred unsaturated compounds include 2-isocyanatoethyl (meth) acrylate, methacryloyl isocyanate, vinyl isocyanate and isopropenyl isocyanate.

When an oxazoline group is introduced into the polyolefin, a preferred unsaturated compound is 2-vinyl-
2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-5,6-dihydro-4H-1, 3-oxazine, 4,4,6-trimethyl-2-vinyl-5,6-dihydro-4H-1,3-
Oxazine, 2-isopropenyl-2-oxazoline,
4,4-dimethyl-2-isopropenyl-2-oxazoline and the like.

When a carbodiimide group is introduced into a polyolefin, preferred unsaturated compounds include methylvinylcarbodiimide, isopropenylmethylcarbodiimide and the like. The reaction between the polyolefin and the unsaturated compound having a functional group is carried out by a conventional method using a radical initiator.

Copolymers obtained by copolymerization of various olefins with an unsaturated compound having a desired functional group include ethylene- (meth) acrylic acid copolymer and ethylene-2-hydroxyethyl (meth) Acrylate copolymer, ethylene-glycidyl (meth) acrylate copolymer, ethylene-polyethylene glycol mono (meth) acrylate copolymer, ethylene-vinyl acetate-
(Meth) acrylic acid copolymer, ethylene-ethyl (meth) acrylate- (anhydride) maleic acid copolymer, ethylene-vinyl acetate- (anhydride) maleic acid copolymer, ethylene-vinyl acetate-2-hydroxyethyl ( (Meth) acrylate copolymer, ethylene-vinyl acetate-glycidyl (meth) acrylate copolymer, ethylene-vinyl acetate-polyethylene glycol mono (meth) acrylate copolymer, partially saponified ethylene-vinyl acetate copolymer, and the like. No.

The copolymerization reaction between various olefins and an unsaturated compound having a desired functional group is carried out by a conventional method using a radical initiator. Among these copolymers, ethylene- (meth) acrylic acid copolymer, ethylene-glycidyl (meth) acrylate copolymer, ethylene-ethyl (meth) acrylate- (anhydride) maleic acid copolymer,
Most preferred is an ethylene-vinyl acetate-glycidyl (meth) acrylate copolymer.

Radical polymerizable monomer (b) Examples of the radical polymerizable monomer having a functional group reactive with the olefin resin (a) having at least one functional group in one molecule include a hydroxyl group, A radical polymerizable monomer having an epoxy group, an isocyanate group, an oxazoline group, and a carbodiimide group is exemplified.

Examples of the radical polymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
Examples include hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate, N-methylolacrylamide, N-methylolmethacrylamide, and hydroxyvinyl ether.

Examples of the radical polymerizable monomer having an epoxy group include glycidyl ethers such as glycidyl (meth) acrylate, allyl glycidyl ether and 2-methylallyl glycidyl ether; 3,4-epoxy-1-butene; Epoxy olefins such as -epoxy-3-methyl-1-butene; mono- and diglycidyl esters of maleic acid; mono- and diglycidyl esters of itaconic acid;

Examples of the radical polymerizable monomer having an isocyanate group include 2-isocyanatoethyl (meth) acrylate, methacryloyl isocyanate, vinyl isocyanate, and isopropenyl isocyanate. Radical polymerizable monomers having an oxazoline group include 2-vinyl-2-oxazoline and 5-methyl-2.
-Vinyl-2-oxazoline, 4,4-dimethyl-2-
Vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-5,6-dihydro-4H-1,3-oxazine,
4,4,6-trimethyl-2-vinyl-5,6-dihydro-4H-1,3-oxazine, 2-isopropenyl-
2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline and the like.

Examples of the radically polymerizable monomer having a carbodiimide group include methylvinylcarbodiimide, isopropenylmethylcarbodiimide and the like. Among the above monomers, 2-hydroxyethyl (meth) acrylate is a radical polymerizable monomer having a hydroxyl group,
Glycidyl methacrylate is most preferred as the radical polymerizable monomer having an epoxy group, and 2-isocyanatoethyl methacrylate is most preferred as the radical polymerizable monomer having an isocyanate group.

Radical polymerizable olefin resin (c) Radical polymerizable monomer (b) is added to olefin resin (a) having at least one functional group in one molecule,
The functional group in the radical polymerizable monomer (b) is 0.001 to 10 equivalents, preferably 0.01 to 10 equivalents to 1 equivalent of the functional group.
Addition of 5 equivalents, especially 0.05 to 1 equivalent, gives a radically polymerizable olefin resin (c) having an ethylenically unsaturated bond. When the amount of the functional group of the radical polymer (b) is less than 0.001 equivalent to the amount of the functional group of (a), the radical polymerizable olefin resin and an acrylic acid alkyl ester or a methacrylic acid alkyl ester (d) described later are used. When copolymerizing (1) and (2), the amount of the homopolymer of the alkyl acrylate or the alkyl methacrylate (d) increases, which is not preferable.

Alkyl acrylate or alkyl methacrylate (d) Examples of the alkyl acrylate or alkyl methacrylate include ester reactants of acrylic acid or methacrylic acid with an aliphatic alcohol having 1 to 8 carbon atoms. . Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and among them, methyl methacrylate is most preferred. Further, among the above-mentioned alkyl acrylate or alkyl methacrylate (d), 40
Less than weight percent can be replaced by other unsaturated monomers.

Examples of such other copolymerizable monomers include hydroxy (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. Alkyl (meth) acrylate, diethylaminomethyl (meth) acrylate, dialkylamino (meth) acrylate such as diethylaminoethyl (meth) acrylate, glycidyl methacrylate, (meth) acrylamide, (meth) acrylonitrile, trifluoroethyl (meth) acrylate, Tetrafluoropropyl (meth) acrylate, hexafluorobutyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorononyl (meth) acrylate, heptadecuff Orodeshiru (meth) acrylate fluoroalkyl (meth) acrylates such as, tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, monochloro-trifluoroethylene, 1-chloro-2,2-difluoroethylene, 1,1
-Dichloro-2,2-difluoroethylene, vinylidene chlorofluoride, hexafluoropropene, 3,
3,3,2-tetrafluoropropene, trifluoromethylethylene, 2-fluoropropene, 2-chloro-
1,1,3,3,3-pentafluoropropene, 1,
1,2-trichloro-3-trifluoropropene, perfluoro-1-butene, perfluoro-1-heptene,
Perfluoro-1-nonene, 8-H-perfluoro-1
-Octene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene,
Fluorine-containing unsaturated monomers such as perfluorododecyl ethylene, vinyl acetate, vinyl chloride, ethyl vinyl ether,
Vinyl ethers such as butyl vinyl ether and hexyl vinyl ether; aromatic compounds having a vinyl group such as vinyl ketone, styrene and α-methylstyrene; and olefins such as ethylene, propylene, butene and isoprene.

The acrylic graft copolymer (A) used in the present invention is based on the above-mentioned alkyl acrylate or alkyl methacrylate (d) based on 100 parts by weight of the radically polymerizable olefin resin (c).
From 10 to 500 parts by weight, preferably from 20 to 300 parts by weight, most preferably from 50 to 300 parts by weight.

When the amount of the alkyl acrylate or the alkyl methacrylate (d) is less than 10 parts by weight, the adhesive strength with the fluorine resin layer or the acrylic resin layer is insufficient. Poor adhesion to the layer. This copolymerization reaction uses an organic solvent such as toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, and cellosolve acetate as a reaction solvent, and uses benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide or the like as a polymerization catalyst. Of an azobis compound such as azobisisobutyronitrile, etc. with respect to an alkyl acrylate or an alkyl methacrylate (d) in an amount of 0.1 to 1
0% by weight, preferably 1-5% by weight, 50-200%
The reaction can be carried out by heating at 1 ° C. for 1 to 20 hours. In this case, the total amount of the radically polymerizable olefin resin (c) and the alkyl acrylate or alkyl methacrylate (d) is adjusted so that the total amount of the reaction catalyst is 5 to 50% by weight in the reaction product. It is preferable to adjust the temperature and to carry out the reaction in an atmosphere of an inert gas such as a nitrogen gas or in a gas stream. In order to reduce the residual monomer, an azobis compound and a peroxide may be used in combination as a polymerization initiator. After polymerization, the powder is separated, washed and dried to obtain a powdery acrylic graft copolymer (A).

Acrylic Resin (B) The acrylic resin (B) in the resin composition of the present invention includes (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, -Ethylhexyl (meth) acrylate,
Homopolymers or copolymers such as cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, and N-methylol (meth) acrylamide are exemplified. Among these, polymethyl methacrylate is preferred. As these acrylic resins, those containing a filler, a coloring agent, various stabilizers, a conductive agent, and the like can be used as necessary.

Fluorine Resin (C) As the fluorine resin (C) in the resin composition of the present invention, vinyl fluoride, vinylidene fluoride, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoroalkyl Examples include homopolymers or copolymers of vinyl ether or the like, and copolymers of these fluorine-based monomers and α-olefins such as ethylene and propylene. Among these, polyvinylidene fluoride is most preferable in terms of adhesiveness and moldability. As these fluororesins, those containing a filler, a coloring agent, various stabilizers, a conductive agent, and the like can be used as necessary.

Resin Composition The resin composition of the present invention is obtained by adding one part of the acrylic resin (B) to 100 parts by weight of the acrylic graft copolymer (A).
1 to 200 parts by weight, preferably 10 to 150 parts by weight, and 1 to 200 parts by weight, preferably 5 to 1 part by weight of the fluororesin (C).
00 parts by weight. However, the sum of the components (B) and (C) is 3 with respect to 100 parts by weight of the component (A).
The amount is not more than 00 parts by weight, preferably 15 to 150 parts by weight, particularly preferably 10 to 50 parts by weight.

If the amount of the acrylic resin (B) exceeds 200 parts by weight, the adhesive strength with the olefin resin layer is reduced. If the amount of the fluorine-based resin (C) is too large, the adhesive strength to the acrylic resin layer or the olefin-based resin layer is reduced. Furthermore, acrylic resin (B) and fluorine resin (C)
Is too large, the adhesion to the olefin resin layer is not sufficient. The weight ratio of the acrylic resin (B) to the fluorine resin (C) is preferably 5/99 to 95 /.
5, particularly preferably 10/90 to 90/10.

The resin composition of the present invention is preliminarily mixed and blended with an acrylic graft copolymer, an acrylic resin and a fluororesin from the viewpoint of dispersibility during melt-kneading using an extruder or an injection molding machine. This is preferably extruded into a strand and pelletized for use. The method of mixing and blending is not particularly limited, and a predetermined amount of two kinds of resins is mixed using a mixing device such as a V blender, a ribbon blender, and a super mixer. Next, the obtained mixture is
Kneader used for ordinary thermoplastic resin, for example,
The resin composition is prepared by melt-kneading using a single-screw or multi-screw kneading extruder, a roll, and a Banbury mixer, extruding into a strand, and cutting, or cooling and pulverizing the melt.

The temperature at the time of melt-kneading is 120 to 280 ° C., preferably 140 to 260 ° C., and it is preferable to granulate at a screw rotation speed of usually about 60 to 350 rpm. The resin composition of the present invention may contain a filler, a coloring agent, various stabilizers, a conductive agent, and the like, if necessary.

Laminate The laminate of the present invention is obtained by melt-bonding an olefin resin layer and a fluorine resin layer or an olefin resin layer and an acrylic resin layer via the above resin composition. The molding method is not particularly limited, and molding methods generally used for thermoplastic resins, that is, injection molding, hollow molding, extrusion molding, sheet molding, thermoforming,
Molding methods such as rotational molding, lamination molding, and press molding can be applied.

Specifically, the following method can be used. The olefin resin, resin composition, and fluorine resin or acrylic resin are individually melt-kneaded using separate extruders, and then supplied to one multi-layer molding die and merged in the die. Multi-hold co-extrusion molding method in which the olefin resin, the resin composition, and the fluororesin or acrylic resin are individually melt-kneaded, and they are combined by a flow distribution device. Feed block type co-extrusion molding method in which the olefin resin and the resin composition are fed to a co-extrusion die and co-extruded into a sheet from the die; Extrusion laminating method; Laminating by extrusion; extruding olefin resin into co-extruded film of fluororesin or acrylic resin and resin composition Extrusion lamination method of laminating in the molten state of the forming process; Extrusion lamination method of laminating an olefin resin film on the surface of the resin composition on the laminated film in the molten state of the co-extrusion molding process of the fluororesin or acrylic resin and the resin composition An extrusion lamination method in which a fluororesin film or an acrylic resin film is laminated on the surface of the resin composition on a laminated film in a molten state in the process of co-extrusion of an olefin resin and a resin composition; extrusion molding of a fluororesin or an acrylic resin Extrusion lamination method of laminating a co-extruded laminated film of olefin resin and resin composition on the molten film in the process; Extrusion of fluoro resin or acrylic resin and resin composition on the molten film of the olefin resin in the extrusion process Extrusion lamination method for laminating extruded laminated films The film molten film of the resin composition leads between the olefin resin layer and the fluororesin layer or acrylic resin layer, there is a sandwich laminating method of melt-bonding lamination.

The molding temperature at that time is 150 to 260 ° C., preferably 170 to 230 ° C. At the time of molding, an antioxidant, a light stabilizer,
Resin additives such as ultraviolet absorbers, lubricants, and flame retardants can be blended. The thickness of each layer of the laminate obtained by such a method is not particularly limited, and can be determined according to the use. For example, the olefin resin layer is 0.0
05 to 5 mm, preferably 0.1 to 3 mm, the acrylic resin layer and the fluorine resin layer are 0.01 to 5 mm, preferably 0.05 to 2 mm, and the resin composition layer is 1 to 500 μm, preferably about 10 to 100 μm. It is.

As the olefin resin for the laminated molded article, polyethylene, polypropylene, polybutene-1,
Ethylene-propylene copolymers, poly-α-olefins such as ethylene-butene copolymers or copolymers thereof,
Ethylene-propylene-diene copolymer, isobutene-
Copolymers of α-olefins such as isoprene copolymers and conjugated dienes, or vinyl esters such as these α-olefins and acetates, (meth) acrylic acid, maleic anhydride, methyl (meth) acrylate, (meth) ) Unsaturated carboxylic acids such as ethyl acrylate and its esters, aromatic vinyl monomers such as styrene, and other unsaturated monomers such as vinyltrimethoxysilane and vinylsilane such as γ (meth) acryloyloxypropylmethoxysilane. Random, block or graft copolymers. Of these, polyethylene and polypropylene are most preferred. These olefinic resins may be used as fillers,
Those containing a colorant, various stabilizers, a conductive agent, and the like can be used. For the acrylic resin layer, it can be selected from the acrylic resins (B) described above. Among these, polymethyl methacrylate is preferred. The fluororesin can be selected from the above-mentioned fluororesins (C), and polytetrafluoroethylene is preferable.

[0039]

Next, the present invention will be described with reference to examples, but the present invention is not limited to the examples unless it exceeds the gist.

Synthesis of Acrylic Graft Copolymer (A) (Synthesis Example 1) 160 kg of toluene was placed in a reactor equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, and ethylene-anhydrous maleic was used as the olefin resin (a). Acid
40 kg of an ethyl acrylate copolymer (trade name: Bondyne LX-4110, manufactured by Sumitomo Chemical Co., Ltd.) and 104 g of hydroquinone monomethyl ether were charged, and the system was heated to 110 ° C. in an air stream and dissolved. To this, 1.423 kg of 2-hydroxyethyl acrylate and 1.044 kg of dimethylbenzylamine were added and reacted at the same temperature for 8 hours.

An infrared absorption spectrum analysis of the obtained radical copolymerizable olefin resin showed that 32% of the carboxyl groups of the ethylene-maleic anhydride-ethyl acrylate copolymer were esterified with 2-hydroxyethyl acrylate. I was Then, after purging the system with nitrogen,
The temperature was lowered to 80 ° C., 240 kg of toluene, 60 kg of methyl acrylate and 360 g of azobisisobutyronitrile were added, and the reaction was carried out at the same temperature for 2 hours. The operation of further adding 360 g of azobisisobutyronitrile and reacting for 2 hours was repeated four times. This reaction solution was added to 1500 kg of methyl alcohol to precipitate a polymerization product, which was then separated and dried to obtain an acrylic graft copolymer (I-1).

(Synthesis Example 2) Toluene 16 was introduced into a reactor equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer.
0 kg, ethylene-glycidyl methacrylate copolymer (trade name, manufactured by Sumitomo Chemical Co., Ltd.) as the olefin resin (a):
40 kg of Bondfast 2c) and 104 g of hydroquinone monomethyl ether were charged, and the inside of the system was heated to 110 ° C. under an air stream and dissolved. Add acrylic acid to this.
61 kg, tetramethylammonium bromide 1.04
4 kg was added, and the reaction was carried out at the same temperature for 8 hours.

As a result of oxidation measurement of the obtained radical copolymerizable olefin resin solution, 42% of the epoxy groups of the ethylene-glycidyl methacrylate copolymer were esterified with acrylic acid. Subsequently, after the inside of the system was replaced with nitrogen, the temperature was lowered to 80 ° C., and 240 kg of toluene, 60 kg of methyl acrylate, and azobisisobutyronitrile 360
g was added and reacted at the same temperature for 2 hours. The operation of further adding 360 g of azobisisobutyronitrile and reacting for 2 hours was repeated four times. This reaction solution was added to 1500 kg of methyl alcohol to precipitate a polymerization product, which was then separated and dried to obtain an acrylic graft copolymer (I-2).

Example 1 10 kg of the acrylic graft copolymer (I-1) obtained in Synthesis Example 1 was used as an acrylic resin with polymethyl methacrylate (trade name, manufactured by Kuraray Co., Ltd.).
1 kg of Parapet GF1000) and polyvinylidene fluoride as a fluororesin (trade name: KF, manufactured by Kureha Chemical Co., Ltd.)
1000) was mixed for 2 minutes in a blender (Kawata: Supermixer).

The mixture was melt-kneaded in a twin-screw extruder [trade name: PCM30φ, manufactured by Ikegai Iron Works Co., Ltd.] under kneading conditions of a resin temperature of 240 ° C. and a screw rotation speed of 250 rpm.
Pelletized. Using the pellets of the obtained resin composition, the adhesive strength and the melt spreadability were evaluated by the methods described below. Table 2 shows the results.

<Melting Spreadability> The above pellets were tested at a test temperature of 190 using Capillograph 1-B (manufactured by Toyo Seiki Seisaku-sho, Ltd.)
The resin sheet is extruded at a temperature of 10 ° C. and an extrusion speed of 10 mm / min, and the extruded resin sheet is wound into a roll. The take-up speed of the take-up roll was increased, and the take-up speed at which the sheet was broken was measured.

<Adhesive Strength> The resin composition pellets were prepared by using high-density polyethylene (Mitsubishi Chemical Corporation: Mitsubishi Polyethylene HB330) as an olefin resin and polyvinylidene fluoride (Kureha Chemical Company: KF1) as a fluorine resin.
000), and polymethyl methacrylate (trade name: GF, manufactured by Kuraray Co., Ltd.) as an olefin resin and an acrylic resin.
1000), and the adhesive strength was measured by the following method.

The olefin resin (a) and the fluorine resin or the acrylic resin (c) are extruded by a 50 mmφ extruder.
The pellets (b) of the resin composition were each melt-kneaded at 210 ° C. by a 40 mmφ extruder, and the three kinds of resins were combined and laminated by a flow rate distribution device and formed into a three-layer sheet by a so-called feed block method, which was supplied to a die. Die is 300mm
A coat hanger die of width was used. The obtained three-layer sheet [thickness (a) / (b) / (c) = 0.1 mm / 0.05
mm / 0.1 mm] was measured for peel strength using an Instron tensile tester.

Examples 2 to 8 Evaluations were made in the same manner as in Example 1 except that the amounts of the acrylic resin and the fluorine resin were changed as shown in Table 1.

Example 9 10 kg of the acrylic graft copolymer (I-2) obtained in Synthesis Example 2, 3 kg of polymethyl methacrylate (Parapet GF1000) and 1 kg of polyvinylidene fluoride (KF1000) were blended with a blender (Kawata Corporation). (Super mixer).

This mixture was melt-kneaded with a twin-screw extruder [trade name: PCM30φ, manufactured by Ikegai Iron Works Co., Ltd.] under the kneading conditions of a resin temperature of 240 ° C. and a screw rotation speed of 250 rpm to obtain a composition, and then pelletized. Evaluation was performed in the same manner as in Example 1 using the pellets of the obtained resin composition.

(Comparative Example 1) Evaluation was made in the same manner as in Example 1 except that the acrylic resin and the fluorine resin were not added.

Comparative Example 2 Evaluation was performed in the same manner as in Example 1 except that the composition of the adhesive resin composition was changed as shown in Table 1.

Comparative Example 3 1 kg of the acrylic graft copolymer (I-1) obtained in Synthesis Example 1 and 4 kg of low-density polyethylene (trade name: Mitsubishi Polyethylene LF480M, manufactured by Mitsubishi Chemical Corporation) as an olefin resin Further, 6 kg of polyvinylidene fluoride (trade name: KF1000, manufactured by Kureha Chemical Co., Ltd.) as a fluorine resin is blended with a blender (manufactured by Kawata:
Super Mixer) for 2 minutes.

The mixture was melt-kneaded with a twin-screw extruder [trade name: PCM30φ, manufactured by Ikegai Iron Works Co., Ltd.] under kneading conditions of a resin temperature of 240 ° C. and a screw rotation speed of 250 rpm to obtain a composition, and then pelletized. Evaluation was performed in the same manner as in Example 1 using the pellets of the obtained resin composition.

Comparative Example 4 Evaluation was made in the same manner as in Comparative Example 3 except that the amounts of the olefin resin and the fluorine resin were changed as shown in Table 1.

Comparative Example 5 1 kg of the acrylic graft copolymer (I-1) obtained in Synthesis Example 1 and low-density polyethylene (trade name: Mitsubishi Polyethylene LF48 manufactured by Mitsubishi Chemical Corporation)
0M) and 6 kg of polymethyl methacrylate (trade name: GF1000, manufactured by Kuraray Co., Ltd.) were mixed for 2 minutes using a blender (Kawata, super mixer).

A resin temperature of 140 ° C. to 260 ° C. was applied to this mixture using a twin screw extruder [trade name: PCM30φ manufactured by Ikegai Ironworks Co., Ltd.].
The composition was melt-kneaded under a kneading condition of 250 ° C. and a screw rotation speed of 250 rpm to obtain a composition, which was then pelletized. Evaluation was performed in the same manner as in Example 1 using the pellets of the obtained resin composition.

Comparative Examples 6 to 8 Evaluations were made in the same manner as in Comparative Example 5 except that the amounts of the olefin resin and the acrylic resin were changed as shown in Table 1. Table 2 shows the results.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

The resin composition obtained by the present invention has excellent melt moldability and is useful as a melt adhesive for laminating an olefin resin layer and a fluorine resin layer or an olefin resin layer and an acrylic resin layer. It is.

Claims (5)

[Claims] 1. 100 parts by weight of an acrylic graft copolymer (A) obtained by the following method, 1 to 200 parts by weight of an acrylic resin (B) and 1 to 200 parts by weight of a fluororesin (C) [ , The sum of the components (B) and (C) is 100 parts by weight of the component (A),
It is 300 parts by weight or less. ] The resin composition which mix | blends. Acrylic graft copolymer (A): A radical polymerizable monomer (b) having a functional group reactive with the olefin resin (a) having at least one functional group in one molecule. The reaction is carried out to obtain a radically polymerizable olefin resin (c), and alkyl acrylate or alkyl methacrylate (the alkyl group having 1 to 8 carbon atoms) is added to 100 parts by weight of the resin (c).
An acrylic graft copolymer obtained by subjecting (d) to radical copolymerization at a ratio of 10 to 500 parts by weight. 2. The functional group of the olefin resin (a) having at least one functional group in one molecule is selected from a carboxyl group, an epoxy group, a hydroxyl group, an isocyanate group, an oxazoline group and a carbodiimide group. The resin composition according to claim 1. 3. A radically polymerizable olefin resin (c).
Is obtained by reacting 2-hydroxyalkyl acrylate (b) with ethylene-maleic anhydride-ethyl acrylate copolymer (a). 4. A radically polymerizable olefin resin (c)
Is obtained by reacting an acrylic acid (b) with an ethylene-glycidyl methacrylate copolymer (a). 5. A laminate in which an olefin resin layer and a fluororesin layer or an acrylic resin layer are bonded via the resin composition according to claim 1.