WO2017141326A1

WO2017141326A1 - Resin compound and resin composition

Info

Publication number: WO2017141326A1
Application number: PCT/JP2016/054324
Authority: WO
Inventors: 裕之細川
Original assignee: ナトコ株式会社
Priority date: 2016-02-15
Filing date: 2016-02-15
Publication date: 2017-08-24
Also published as: JPWO2017141326A1; JP6643581B2

Abstract

This resin compound has: a main chain comprising an acid-modified polyolefin; and a graft chain comprising a vinyl polymer linked to a carbon atom forming the polyolefin backbone of the main chain, wherein the graft chain contains a first vinyl monomer having a hydroxy group as one of the structural units thereof, and the hydroxy group is linked to a carbon atom.

Description

Resin compound and resin composition

The present invention relates to a resin compound used as a paint, an adhesive, or a primer paint, and a resin composition containing the resin compound.

In some cases, the surface of a molded product is painted for the purpose of imparting wear resistance or scratch resistance to a molded product made of a resin material or a metal material, or improving its design. At that time, depending on the material of the molded product, there is a problem that sufficient adhesion cannot be ensured between the surface of the molded product and the top coating, and the top coating is easily peeled off. One reason for this is that the polarities differ greatly depending on the various materials forming the molded article, and there is a difference in surface free energy from the top coat. Conventionally, in order to avoid such a situation, by applying a primer paint on the surface of the molded product in advance, the effect of the surface free energy existing between the molded product surface and the top coat is eliminated, and the molded product surface Ensuring the adhesion of the top coat to the surface is being carried out.

As such a primer coating, a resin having a polyolefin polymer as a main skeleton is widely known. For example, Patent Document 1 discloses the use of a resin compound containing an acid-modified polyolefin as a primer coating. Patent Document 1 discloses that a resin compound obtained by graft-polymerizing a vinyl monomer containing a vinyl monomer having a phosphate group to an acid-modified polyolefin resin is used as a primer paint.

International Publication No. 2014/148330

However, since the adhesiveness of the resin compound used in the primer paint disclosed in Patent Document 1 varies greatly depending on the material of the molded product to be applied, the types of applicable molded products are limited. It was. For example, adhesion to synthetic resins such as nylon resin and polybutylene terephthalate resin, metals such as tinplate and aluminum, engineering plastics, etc. was not sufficient.

The present invention has been made in view of these conventional techniques, and an object of the present invention is to provide a resin compound having a wide range of application that exhibits suitable adhesion to various molded articles of different materials and the resin compound. It is providing the resin composition containing.

In order to achieve the above object, the resin compound of one embodiment of the present invention comprises a main chain composed of an acid-modified polyolefin and a vinyl polymer bonded to carbon atoms that constitute the polyolefin skeleton of the main chain. A resin compound having a graft chain, wherein the graft chain is a graft chain having one hydroxyl group-containing first vinyl monomer as a constituent unit, and the hydroxyl group is bonded to a carbon atom. It is a hydroxyl group.

In the above resin compound, the first vinyl monomer having a hydroxyl group is preferably a (meth) acrylic acid monomer.
In the above resin compound, the (meth) acrylic acid monomer is preferably a polyalkylene glycol ester of (meth) acrylic acid.

In the above resin compound, the graft chain is preferably a graft chain having a second vinyl monomer having an alkyl group having 8 to 14 carbon atoms as one of the constituent units.
In the above resin compound, the second vinyl monomer having an alkyl group having 8 to 14 carbon atoms is preferably a (meth) acrylic acid monomer.

In the above resin compound, the graft chain is preferably a graft chain having a third vinyl monomer having a polar group as one of the constituent units.
In the above resin compound, the third vinyl monomer having a polar group is preferably at least one of tetrahydrofurfuryl acrylate and N-vinyl pyrrolidone.

In order to achieve the above object, the resin composition of one embodiment of the present invention is a resin composition containing the above resin compound and a curing agent.

According to the present invention, it is possible to obtain a resin compound and a resin composition with a wide range of application that exhibit suitable adhesion to various molded products of different materials.

Hereinafter, embodiments embodying the present invention will be described.
The resin compound is obtained by graft polymerization of the vinyl monomer (B) to the acid-modified polyolefin (A).

The acid-modified polyolefin (A) is a compound in which a carboxyl group is introduced into a polyolefin.
A conventionally well-known thing can be used as said polyolefin. Specific examples thereof include polyolefins obtained by homopolymerization or copolymerization of α-olefin monomers such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, and ethylene-propylene copolymers. Α-olefin copolymers such as polymers, propylene-butene copolymers, and α-olefin-diene terpolymers such as ethylene-propylene-diene terpolymers and propylene-butene-diene terpolymers. A polymer can be mentioned. Here, the α-olefin preferably has 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms.

The carboxyl group of the acid-modified polyolefin (A) is introduced by reacting the polyolefin with a carboxylic acid.
Examples of the carboxylic acids include conventionally known carboxylic acids such as monocarboxylic acids or dicarboxylic acids, and anhydrides thereof. For example, α, β-unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, aconitic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, and their anhydrides, or acrylic acid, methacrylic acid, Mention may be made of crotonic acid, isocrotonic acid, α-ethylacrylic acid and their anhydrides.

Examples of a method for introducing a carboxyl group into a polyolefin include a method in which a carboxylic acid is grafted to a polyolefin in the presence of a polymerization initiator. Specifically, a method of grafting by dissolving a polyolefin in an organic solvent, adding a carboxylic acid and a polymerization initiator and stirring with heating, heating and melting the polyolefin, the carboxylic acid and polymerization into the melt Examples thereof include a method of grafting by adding an initiator and heating and stirring, or a method of grafting while supplying each component to an extruder and heating and kneading.

The blending amount of the carboxylic acids is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the polyolefin. By setting the content of carboxylic acids to 0.1 parts by mass or more, the adhesion of the resin compound is improved. Moreover, the unreacted substance by grafting of polyolefin and carboxylic acids decreases by making content of carboxylic acids into 30 mass parts or less.

Examples of polymerization initiators used for grafting of polyolefins and carboxylic acids include conventionally known organic peroxides and azo compounds. Examples of the organic peroxide include peroxydicarbonate, dialkyl peroxide, hydroperoxide, peroxyketal, and peroxyester. Examples of the azo compound include 2,2′-azoisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 4,4′-azobis (4-cyanovaleric acid), 2 2,2'-azobis (methylpropionic acid) and the like.

Also, when grafting is performed in the presence of an organic solvent, a conventionally known organic solvent can be used. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, aliphatic hydrocarbon solvents such as hexane, heptane, octane and decane, and halogenated carbonization such as trichloroethylene, perchlorethylene, chlorobenzene and o-dichlorobenzene Examples thereof include hydrogen-based solvents.

Examples of commercially available products corresponding to the acid-modified polyolefin (A) include Auroren (registered trademark) series manufactured by Nippon Paper Chemical Co., Ltd., Sumifit (registered trademark) series manufactured by Sumika Chemtex Co., Ltd., and Uni manufactured by Mitsui Chemicals, Inc. Examples include Stall (registered trademark) series or Admer (registered trademark) series, Surflen (registered trademark) series manufactured by Mitsubishi Chemical Corporation, Aronmelt (registered trademark) series manufactured by Toagosei Co., Ltd., and the like.

The acid-modified polyolefin (A) can be used alone or in combination of two or more. Moreover, the weight average molecular weight is not specifically limited, What is necessary is just to select suitably. The weight average molecular weight of the acid-modified polyolefin (A) is preferably in the range of 10,000 to 200,000, and more preferably in the range of 50,000 to 100,000.

As the vinyl monomer (B), the first vinyl monomer (B1) having a hydroxyl group is used. The vinyl monomer (B) includes a first vinyl monomer (B1) having a hydroxyl group and a second vinyl monomer (B2) having an alkyl group having 8 to 14 carbon atoms. It is preferable to use together. In this case, the application range of the object for obtaining the adhesion is widened, and the adhesion to the object is improved.

Furthermore, a first vinyl monomer (B1) having a hydroxyl group, a second vinyl monomer (B2) having an alkyl group having 8 to 14 carbon atoms, and a third vinyl monomer having a polar group. It is more preferable to use the monomer (B3) in combination. In this case, the application range of the object for obtaining the adhesion is further expanded, and the adhesion to the object is further improved.

Moreover, you may use together another vinyl-type monomer (B4) as a vinyl-type monomer (B).
Examples of the vinyl monomer (B1) having a hydroxyl group include conventionally known acrylic acid esters and methacrylic acid esters having a hydroxyl group. The hydroxyl group of the acrylic acid ester or methacrylic acid ester having a hydroxyl group here is a hydroxyl group bonded to a carbon atom. In the description of the present invention, (meth) acrylic acid is used as a name including both acrylic acid and methacrylic acid, and (meth) acrylate is used as a name including both acrylate and methacrylate.

Examples of the (meth) acrylic acid ester having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5 (Meth) acrylic acid such as hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 7-hydroxyheptyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 9-hydroxynonyl (meth) acrylate And a monoesterified product of a dihydric alcohol, a ε-caprolactone modified product of the monoesterified product of the (meth) acrylic acid and a dihydric alcohol, polyethylene glycol (meth) acrylate, polypropylene glycol (meta Esterified products of polyalkylene glycol having a polyoxyalkylene chain whose molecular terminal is a hydroxyl group, such as acrylate, and (meth) acrylic acid, monohydroxyethyl (meth) acrylate oxalate, monohydroxyethyl (meth) acrylate tetrahydrophthalate , Tetrahydrophthalate monohydroxypropyl (meth) acrylate, 5-methyl-1,2-cyclohexanedicarboxylic acid monohydroxyethyl (meth) acrylate, phthalate monohydroxyethyl (meth) acrylate, phthalate monohydroxypropyl (meth) acrylate , Monohydroxyethyl (meth) acrylate maleate, hydroxypropyl (meth) acrylate maleate, monohydroxybutyl (meth) acrylate tetrahydrophthalate, etc. I can get lost.

The carbon chain bonded to the oxygen atom of the ester group of (meth) acrylate is not particularly limited, but preferably has 3 to 30 carbon atoms.
Among the exemplified (meth) acrylic acid esters, a polyalkylene glycol ester of (meth) acrylic acid is preferable, and a polyether constituting the polyalkylene glycol more preferably contains propylene glycol. When the (meth) acrylic acid ester having a polypropylene glycol structure is graft-polymerized to the acid-modified polyolefin (A), a resin compound having excellent adhesion can be obtained. Further, even if the (meth) acrylic acid ester has a polyethylene glycol structure and does not have a polypropylene glycol structure, the number of repeating structures derived from ethylene glycol is preferably 5 or less. In this case, the hydrophilicity of the whole molecule is lowered, the compatibility with the solvent is improved, and a resin compound having excellent adhesion can be obtained.

From the viewpoint of good reactivity with an isocyanate compound as a curing agent, the hydroxyl group of the vinyl monomer (B1) having such a hydroxyl group is a primary hydroxyl group when applied to a paint or the like as a resin composition. Preferably there is. When the hydroxyl group of the vinyl monomer is a primary hydroxyl group, the reactivity with the isocyanate compound tends to be higher than in the case of a secondary hydroxyl group or a tertiary hydroxyl group, and sufficient adhesion of the resin composition is obtained. Cheap. The hydroxyl group is preferably a primary hydroxyl group, but a secondary hydroxyl group or a tertiary hydroxyl group may be present.

The vinyl monomer (B1) having a hydroxyl group can be used alone or in combination of two or more.
Examples of the vinyl monomer (B2) having an alkyl group having 8 to 14 carbon atoms include conventionally known acrylic acid esters and methacrylic acid esters. The alkyl group may be linear or branched.

Examples of the (meth) acrylic acid ester having an alkyl group having 8 to 14 carbon atoms include octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (Meth) acrylate, tetradecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like.

The vinyl monomer (B2) having an alkyl group having 8 to 14 carbon atoms can be used alone or in combination of two or more.
Examples of the vinyl monomer (B3) having a polar group include N-vinylpyrrolidone, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, N -Methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, butoxymethyl (meth) acrylamide, isobutoxymethyl (meth) acrylamide, methoxyethyl (meth) acrylamide , Ethoxyethyl (meth) acrylamide, ethoxypropyl (meth) acrylamide, methoxybutyl (meth) acrylamide, butoxymethyl (meth) acrylamide, butoxyethyl (meth) acrylic Mido, allyl (meth) acrylamide, 2-ethylhexyl (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-methylol (meth) acrylamide, pN, N-dimethylaminophenyl (meth) acrylamide, pN, N-diethylaminophenyl (meth) acrylamide, pN, N-dipropylaminophenyl (meta Acrylamide, pN, N-dibutylaminophenyl (meth) acrylamide, pN-laurylaminophenyl (meth) acrylamide, pN-stearylaminophenyl (meth) acrylamide, pN, N-dimethylaminobenzyl ( (Meth) acrylamide, pN, N-diethylaminobenzyl (meth) acrylamide, pN, N-dipropylaminobenzyl (meth) acrylamide, pN, N-dibutylaminobenzyl (meth) acrylamide, pN- Laurylaminobenzyl (meth) acrylamide, pN-stearylaminobenzyl (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidone, N- (meth) acryloylpiperidine, N- (meth) acryloyl Pylori Amide group-containing monomers such as gin and N- (meth) acryloyl-4-piperidone, sulfonic acid-containing monomers such as 2-acrylamido-2-methylpropane sulfonic acid and 2-sulfoethyl (meth) acrylate, tetrahydrofurfuryl ( (Meth) acrylate, 2-butoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, octafluoropentyl (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, methoxypolypropylene glycol mono (Meth) acrylate, ethoxypolyethylene glycol mono (meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, octoxypolyethylene glycol mono (meth) Acrylate, Octoxy polypropylene glycol mono (meth) acrylate, Lauroxy polyethylene glycol mono (meth) acrylate, Lauroxy polypropylene glycol mono (meth) acrylate, Stearoxy polyethylene glycol mono (meth) acrylate, Stearoxy polypropylene glycol mono (meth) Ether group-containing monomers such as acrylate and ethoxyethoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, morpholinoethyl Amino group-containing monomers such as (meth) acrylate and epoxies such as glycidyl (meth) acrylate Or group-containing monomers, methacrylamide propyl trimethyl ammonium chloride, and a methacryloyloxyethyl trimethyl ammonium chloride ammonium salt-containing monomers such as chloride.

The vinyl monomer having a polar group and having a hydroxyl group bonded to a carbon atom is included in the vinyl monomer having a hydroxyl group (B1). And

The vinyl monomer (B3) having a polar group can be used alone or in combination of two or more.
The other vinyl monomer (B4) is a vinyl monomer having no hydroxyl group, alkyl group having 8 to 14 carbon atoms, or polar group, and conventionally known monomers. For example, monoethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid and isocrotonic acid, and monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, crotonic acid, isocrotonic acid, itaconic acid and mesaconic acid Acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate , N-hexyl (meth) acrylate, n-heptyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxypropyl (meth) acrylate, methoxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate (Meth) acrylates such as relate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, 3-methacryloyloxypropyl Examples thereof include vinyl monomers such as trimethoxysilane and 3-methacryloyloxypropyltriethoxysilane, acrylonitrile and vinyl acetate.

The other vinyl monomers (B4) can be used alone or in combination of two or more.
The reaction of graft-polymerizing the vinyl monomer (B) onto the acid-modified polyolefin (A) can be performed by a conventionally known method. For example, there can be mentioned a method in which the acid-modified polyolefin (A), the vinyl monomer (B) and the like are dissolved in an organic solvent, a polymerization initiator is added, and the polymerization reaction is performed by heating and stirring.

The compounding amount of the vinyl monomer (B) with respect to the acid-modified polyolefin (A) is 20 to 150 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin (A). Preferably there is. By setting the total amount of the vinyl monomer (B) to 20 parts by mass or more, the vinyl monomer (B) is sufficiently graft polymerized with the acid-modified polyolefin (A). Many graft chains are formed with respect to the polyolefin (A). As a result, the adhesion of the resin compound is improved. Moreover, the unreacted substance of the vinyl-type monomer (B) in a resin compound decreases by making the total amount of a vinyl-type monomer (B) into 150 mass parts or less. As a result, the adhesion of the resin compound is improved.

The compounding amount of the vinyl monomer (B1) having a hydroxyl group is preferably 10 to 30 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin (A). When the vinyl monomer (B2) having an alkyl group having 8 to 14 carbon atoms is used in combination, the blending amount is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin (A). . When the vinyl monomer (B3) having a polar group is used in combination, the blending amount is preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin (A). Furthermore, the blending amount of the other vinyl monomer (B4) is preferably 65 to 134.5 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin (A).

Examples of the polymerization initiator used in the reaction for graft polymerization of the vinyl monomer (B) to the acid-modified polyolefin (A) include conventionally known organic peroxides and azo compounds. Examples of the organic peroxide include diacyl such as diisobutyl peroxide, dilauroyl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, di (3-methylbenzoyl) peroxide, and dibenzoyl peroxide. Peroxy such as peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxycarbonate, di (2-ethylhexyl) peroxydicarbonate Dicarbonate, di-o-methylbenzoyl peroxide, di-p-methylbenzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3 -Bis (t-butylperoxyisop Pyr) benzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 and other dialkyl peroxides, p-methane Hydroperoxides such as hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and t-butyl peroxyneodeca Noate, t-hexylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, cumylperoxyneodecanoate, t-butylperoxyneoheptanoate, t-Butylperoxy-2ethylhexanoate, t-hexyl Peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-butylpermaleic acid, t-butylperoxy-3,5,5- Trimethylhexanoate, t-butyl peroxyisopropyl monocarbonate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxylaurate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5- Peroxyesters such as di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate; n-butyl-4,4-di- (t-butylperoxy) valerate, 2,2-di -(T-butylperoxy) butane, 2,2-di (4,4-di- (t-butylperoxy) ) Cyclohexyl) propane, 1,1-di (t-hexylperoxy) -3,5,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1, Examples include peroxyketals such as 1-di (t-butylperoxy) cyclohexane and 1,1-di (t-hexylperoxy) cyclohexane. These organic peroxides can be used alone or in combination of two or more.

As the solvent used in the reaction for graft polymerization of the vinyl monomer (B) to the acid-modified polyolefin (A), a conventionally known solvent can be used and is not particularly limited. For example, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, aliphatic hydrocarbon solvents such as normal hexane, 2-methylhexane, normal butane, ethyl acetate, normal butyl acetate, isobutyl acetate, Acetic ester solvents such as normal propyl acetate, isopropyl acetate and amyl acetate, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and acetone, alcohols such as methanol, ethanol, isopropyl alcohol, t-butyl alcohol and benzyl alcohol Solvent, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol monoethyl ether, ethylene glycol Glycol ether solvents such as Bruno ether, acetate-based solvents such as methyl cellosolve acetate, toluene, xylene, and aromatic hydrocarbon solvents ethylbenzene. These solvents can be used alone or in combination of two or more.

The polymerization reaction system includes an acid-modified polyolefin (A), a vinyl monomer having a hydroxyl group (B1), a vinyl monomer having an alkyl group having 8 to 14 carbon atoms (B2), and a vinyl group having a polar group. In addition to the monomer (B3), other vinyl monomers (B4), organic peroxides, and solvents, chain transfer agents, surfactants, flame retardants, fillers, reinforcing agents, softening, as necessary Additives such as a colorant, a colorant, an antifoaming agent, an inorganic or organic antibacterial agent, and a lubricant can be appropriately added.

The polymerization reaction temperature is preferably in the range of 50 to 150 ° C., and more preferably in the range of 70 to 130 ° C.
As described above, the resin compound obtained by graft polymerization of the vinyl monomer (B) to the acid-modified polyolefin (A) has a main chain composed of the acid-modified polyolefin (A) and a polyolefin skeleton of the main chain. It is a resin compound having a graft chain made of a vinyl polymer graft-polymerized to carbon atoms constituting it.

The weight average molecular weight of the resin compound is preferably in the range of 10,000 to 200,000, more preferably in the range of 20,000 to 150,000. Although the weight average molecular weight of a resin compound can be measured by a conventionally well-known method, it can be calculated | required as a value converted into polystyrene based on the gel permeation chromatography measurement, for example.

The resin compound is appropriately mixed with a curing agent (C), a solvent, etc. (resin composition), and various paints and adhesive layers such as primer paint, base coat paint, top coat paint, one coat paint, Applied to interference layer and so on.

In addition, the resin compound may be configured as a single compound having a main chain made of acid-modified polyolefin (A) and a graft chain made of a vinyl polymer, and in a state where unreacted materials by polymerization reaction are mixed. It may be configured.

Examples of the curing agent (C) include an isocyanate curing agent, an epoxy curing agent, an aziridine curing agent, a carboxyl group curing agent, a polyol curing agent, and a polyamine curing agent. Among these, a polyisocyanate curing agent is preferable from the viewpoint that the reactivity with the vinyl monomer (B1) having a hydroxyl group is high and the adhesion of the resin composition is improved.

A conventionally well-known thing can be used as a polyisocyanate type hardening | curing agent. For example, lower aliphatic polyisocyanates such as ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, m-phenylene diisocyanate P-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, triphenylmethane triisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, etc. Aromatic diisocyanates, and adducts of these polyisocyanate compound and a polyol compound such as trimethylolpropane, biuret or isocyanurate, etc. These polyisocyanate compounds.

Examples of commercially available products of these isocyanate-based curing agents include BASF Basonate (registered trademark) series, Tosoh Corporation Coronate (registered trademark) series, Sumika Covestro Urethane Co., Ltd. Death Module (registered trademark) series, Examples include Duranate (registered trademark) series manufactured by Asahi Kasei Chemicals Corporation and Takenate (registered trademark) series manufactured by Mitsui Chemicals.

When an isocyanate curing agent is blended as the curing agent (C), the blending amount is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin compound. By setting the blending amount of the isocyanate curing agent to 1 part by mass or more, a sufficient crosslinked structure is formed between the graft chains of the vinyl monomer (B). As a result, the adhesiveness of the resin composition is improved. Moreover, the unreacted substance in a resin composition decreases by making a compounding quantity into 10 mass parts or less.

A hardening agent (C) can also be used individually by 1 type, and can also use 2 or more types together. When two or more types are used in combination, not only the polyisocyanate curing agent, but also an epoxy curing agent, an aziridine curing agent, a carboxyl group curing agent, a polyol curing agent, a polyamine curing agent, etc. .

As the solvent for mixing the resin compound, conventionally known solvents can be used and are not particularly limited. What was mentioned as a solvent used for the above-mentioned reaction which graft-polymerizes a vinyl-type monomer (B) to acid-modified polyolefin (A) can be illustrated.

The resin composition may contain an additive in addition to the solvent and the curing agent (C). Examples thereof include an antifoaming agent, a viscosity modifier, a light resistance stabilizer, a weather resistance stabilizer, a heat resistance stabilizer, an ultraviolet absorber, an antioxidant, a leveling agent, a pigment, and a pigment dispersant.

Applicable objects of the obtained resin compound and resin composition as paints include polyamide (PA) resin, polybutylene terephthalate (PBT) resin, nylon resin, polycarbonate (PC) resin, acrylonitrile butadiene styrene (ABS) Synthetic resin such as resin, polystyrene resin, acrylic resin, polypropylene resin, ethylene-propylene resin, epoxy resin, polyester resin, polyallyl ether ketone (PAEK) resin, glass fiber reinforced resin in which glass fiber is impregnated with these resins, Metals such as tinplate and aluminum are listed.

When the resin composition is used as a paint, it can be applied by various coating methods applied to ordinary paints. For example, it can be applied to methods such as spray coating, roll coating, curtain coating, brush coating, electrostatic coating, anion electrodeposition coating, cationic electrodeposition coating, and dipping.

According to the embodiment, the following effects can be achieved.
(1) The resin compound of the present embodiment is a resin compound having a main chain composed of acid-modified polyolefin (A) and a graft chain composed of a vinyl polymer, and the graft chain is a vinyl-based unit having a hydroxyl group. It is a graft chain having the monomer (B1) as one of the structural units, and the hydroxyl group is a hydroxyl group bonded to a carbon atom. This resin compound exhibits suitable adhesion to various molded products of different materials. Therefore, it is effective as a primer paint, adhesive, etc. with a wide application range.

(2) The resin compound of this embodiment is excellent in solubility in not only aromatic solvents but also non-aromatic solvents. Therefore, when a non-aromatic solvent is used, the working environment is improved as compared with the case where an aromatic solvent is used.

(3) The resin compound of the present embodiment is a resin compound having a main chain made of acid-modified polyolefin (A) and a graft chain made of a vinyl polymer, and the graft chain is a vinyl-based unit having a hydroxyl group. It is a graft chain having a monomer (B1) and a vinyl monomer (B2) having an alkyl group having 8 to 14 carbon atoms as one of the structural units. This resin compound is further improved in adhesion as compared with a resin compound not containing a vinyl monomer (B2) having an alkyl group having 8 to 14 carbon atoms. The conventional resin composition has excellent adhesion to engineering plastics, metal materials and the like for which adhesion is difficult to obtain.

(4) The resin compound of the present embodiment is a resin compound having a main chain composed of acid-modified polyolefin (A) and a graft chain composed of a vinyl polymer, and the graft chain is a vinyl-based unit having a hydroxyl group. It is a graft chain having a monomer (B1), a vinyl monomer (B2) having an alkyl group having 8 to 14 carbon atoms, and a vinyl monomer (B3) having a polar group monomer as one of the structural units. . This resin compound is further improved in adhesion as compared with a resin compound not containing the vinyl monomer (B3) having a polar group monomer.

(5) The resin composition of the present embodiment includes a curing agent (C). When the resin composition is used, a cross-linked structure derived from the curing agent is formed, so that a resin composition with further improved adhesion can be obtained.

The technical idea that can be grasped from the above embodiment will be described below.
(A) A resin compound having a main chain composed of an acid-modified polyolefin and a graft chain composed of a vinyl polymer, wherein the graft chain is a graft composed of a vinyl monomer having a hydroxyl group as one of the constituent units. A resin composition in which the hydroxyl group is a chain and is a hydroxyl group bonded to a carbon atom, and 20 to 150 parts by mass of the vinyl monomer is graft-polymerized with respect to 100 parts by mass of the acid-modified polyolefin.

(B) A resin composition having a main chain composed of an acid-modified polyolefin and a graft chain composed of a vinyl polymer, wherein the graft chain includes a vinyl monomer having a hydroxyl group as one of the constituent units. The hydroxyl group is a hydroxyl group bonded to a carbon atom, and 10 to 30 parts by mass of the vinyl monomer having the hydroxyl group is graft-polymerized with respect to 100 parts by mass of the acid-modified polyolefin. Resin composition.

Next, examples and comparative examples of the present invention will be described, but the present invention is not limited thereto.
<Test 1>
First, as a test 1, for a resin compound having a main chain composed of an acid-modified polyolefin (A) and a graft chain composed of a vinyl polymer, the adhesion and solvent solubility when a hydroxyl group is introduced into the graft chain are evaluated. did.

<Example 1>
In a 1 L flask under nitrogen atmosphere, 224.0 g of methylcyclohexane, 56.0 g of acid-modified polyolefin (A) (manufactured by Nippon Paper Industries Co., Ltd., Auroren (registered trademark) 350S), polypropylene glycol monomethacrylate (B1) 11.2 g of Bremermer (registered trademark) PP-1000), 13.4 g of methyl methacrylate (B4), 21.8 g of butyl methacrylate (B4), 0.6 g of methacrylic acid (B4), and ethyl acrylate (B4) 9. 0 g was added, and these were completely dissolved while heating to 90 ° C. After reaching 90 ° C., 0.3 g of t-butyl peroxy-2-ethylhexanoate (manufactured by NOF Corporation, Perbutyl O (registered trademark)) was added.

The flask was stirred while maintaining the internal temperature at 90 ° C., 0.3 g of perbutyl O was added after 1.5 hours, and 0.3 g of perbutyl O was further added after 3 hours. After adding perbutyl O, the mixture was further reacted at 90 ° C. for 6 hours. Thereafter, the reaction solution was cooled to obtain a resin compound having a main chain composed of acid-modified polyolefin (A) and a graft chain composed of a vinyl polymer.

Here, infrared absorption spectra of the acid-modified polyolefin (A) (in Example 1, Aurolen (registered trademark) 350S) and the resin compound obtained after the graft reaction were measured. As a result, there was no change in the absorption spectrum of the carboxyl group (around 1780 cm ⁻¹ ) before and after the graft polymerization. Thereby, the graft chain is not bonded to the carboxyl group derived from the carboxylic acid in the acid-modified polyolefin (A), but is bonded to the carbon atom of the polyolefin in the acid-modified polyolefin (A). It was judged.

Resin compound 30 g was dissolved in 80 ml of a solvent (methylcyclohexane / methylisobutylketone / methylethylketone = 3/5/2) to obtain a resin solution. This resin solution was applied to a base material (size 50 mm × 100 mm, thickness 2 mm) made of various materials by air spray so as to have a film thickness of 10 μm, and dried and cured by heat treatment at 80 ° C. for 30 minutes. As the base material, polyamide 6 (PA6) resin, polybutylene terephthalate (PBT) resin, and tinplate were used.

On the dried and cured resin composition, an ultraviolet curable one-component type acrylic paint (manufactured by NATCO Corporation, NTI-2) was applied by air spray so as to have a film thickness of 15 μm. The acrylic paint was dried by heat treatment at 70 ° C. for 5 minutes, and UV cured at 650 mJ / cm ² was used as a test piece.

<Comparative Examples 1 and 2>
In Comparative Example 1, a resin compound was obtained in the same manner as in Example 1 except that graft polymerization was performed without adding the vinyl monomer (B1) component having a hydroxyl group. In Comparative Example 2, the vinyl monomer (B1) component having a hydroxyl group was not added, and as the other vinyl monomer (B4) component, P— which is a vinyl monomer having a phosphate group was used. A resin compound was obtained in the same manner as in Example 1, except that 1M (2-methacryloxyethyl acid phosphate) was added and graft polymerization was performed. The blended components and blending amounts are as shown in Table 1. Test pieces were prepared in the same manner as in Example 1.

In Example 1 and Comparative Examples 1 and 2, each used material was described by weight. However, in Table 1, the acid-modified polyolefin (A) is 100 parts by mass, and relative to other compound parts based on this. The amount is stated in parts by mass. The same applies to the description of each example and the descriptions of Tables 3 and 5.

Each component described in the table is as follows. Here, for convenience, each component described in Tables 3 and 5 is also shown.

350S; acid-modified polyolefin (Aurolen (registered trademark) 350S manufactured by Nippon Paper Industries Co., Ltd.)
353S; acid-modified polyolefin (Auroren (registered trademark) 353S manufactured by Nippon Paper Industries Co., Ltd.)
B1401-S03; acid-modified polyolefin (Sumifit (registered trademark) CMX B1401-S03 manufactured by Sumika Chemtex Co., Ltd.)
P-501; acid-modified polyolefin (Mitsui Chemicals Unistar (registered trademark) P-501)
PP-1000; polypropylene glycol monomethacrylate (Blenmer (registered trademark) PP-1000 manufactured by NOF Corporation)
50 PEP-300; polyethylene glycol polypropylene glycol monomethacrylate (Blenmer (registered trademark) 50 PEP-300 manufactured by NOF Corporation)
HEMA; 2-hydroxyethyl methacrylate HA; 2-ethylhexyl acrylate ID; isodecyl methacrylate (Kyoeisha Chemical Co., Ltd. light ester ID)
LMA; lauryl methacrylate MMA; methyl methacrylate EA; ethyl acrylate EMA; ethyl methacrylate BMA; butyl methacrylate MAA; methacrylic acid NVP; N-vinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd.)
THFA: Tetrahydrofurfuryl acrylate (Hankuri FA-THFA manufactured by Hitachi Chemical Co., Ltd.)
DEAA: Diethylacrylamide (manufactured by KJ Chemicals)
MT-1000; oxazolidone acrylate (Aronix (registered trademark) MT-1000 manufactured by Toa Gosei Co., Ltd.)
ACMO; acryloylmorpholine (manufactured by KJ Chemicals)
GBLMA; γ-butyrolactone methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
P-1M; 2-methacryloylethyl acid phosphate (Light Ester P-1M manufactured by Kyoeisha Chemical Co., Ltd.)
HI100: Isocyanurate-modified form of hexamethylene diisocyanate (BASON manufactured by Basonate (registered trademark) HI100)
About each resin compound of Example 1 and Comparative Examples 1 and 2, adhesiveness and solvent solubility were evaluated. Each evaluation test is described below.

<Adhesion evaluation test>
Evaluation of adhesion was performed by a cross-cut tape method according to JIS K5400 8.5.2 (1990). A specific method is described below.

First, incisions that penetrate the coating film applied to the test piece and reach the base material of the base material are made in a grid pattern at intervals of 1 mm, and a total of 100 squares of 10 × 10 in length and width are made. A cellophane adhesive tape (Cello Tape (registered trademark) 24 mm width, industrial use, manufactured by Nichiban Co., Ltd.) is attached to the 100 squares, and then the tape is peeled off vigorously. The adhesion state of the coating film after peeling the tape was visually observed, and the number of cells remaining without peeling of the coating film was used as an evaluation criterion for adhesion.

The test specimens obtained in Example 1 and Comparative Examples 1 and 2 and the specimens immersed in boiling water at 98 ° C. for 30 minutes and dried were subjected to tests. The results are shown in Table 2.
Evaluation of the test piece after the test was performed according to the following classification.

A: No peeling is observed in all 100 squares.
○: Chipping and floating are observed in a part of 100 squares.
Δ: Peeling is observed in a part of 100 squares.

X: Peeling is observed in all 100 squares.
<Solvent solubility test>
The resin solutions obtained in each Example and each Comparative Example were further diluted with methylcyclohexane to give a 20% solution, and various solvents were added to prepare a 10% diluted solution. These 10% dilutions were allowed to stand at room temperature for 2 days and the appearance was observed. Solvents used in the solvent solubility test are toluene, n-hexane, ethyl acetate, methyl ethyl ketone (MEK), propylene glycol 1-monoethyl ether 2-acetate (PGMAc).

Evaluation was performed according to the following classification.
○: Turbidity is not observed.
Δ: Turbidity is observed.

X: Separated into two layers.
The results are shown in Table 2.

From Test 1, the following can be said.

Comparative Example 1 does not include a vinyl monomer (B1) having a hydroxyl group as the vinyl monomer (B) graft-polymerized to the acid-modified polyolefin (A). In Comparative Example 1, the adhesion was poor on any of the base materials of PA6 resin, PBT resin, and tinplate, whereas in Example 1 containing the vinyl monomer (B1) having a hydroxyl group, Good adhesion was also exhibited with respect to the substrate. Among them, the adhesion to the PBT resin was excellent. Moreover, it was excellent in compatibility with various solvents.

In Comparative Example 2, a vinyl monomer having a phosphate group is included as the vinyl monomer (B). In Comparative Example 2, the adhesion to any of the PA6 resin, PBT resin, and tin plate was poor, whereas in Example 1 in which a vinyl monomer having a phosphate group was not included, Good adhesion was exhibited with respect to any of the substrates. In Example 1, compared with the conventional primer coating as disclosed in Patent Document 1, it had better adhesion.

Further, the resin compound solution of Comparative Example 2 had low compatibility with each solvent other than toluene used in the solvent solubility test, and was separated into two layers. On the other hand, Example 1 showed excellent compatibility with any solvent.

<Test 2>
Next, as test 2, the change in adhesion due to the presence or absence of the curing agent (C) was evaluated.
<Example 2>
To 100 parts by mass of the resin compound obtained in Example 1, 5 parts by mass of an isocyanurate modified form of hexamethylene diisocyanate (Basonate (registered trademark) HI100 manufactured by BASF) as a curing agent (C) was mixed with the resin composition. did. 30 g of this resin composition was dissolved in 80 ml of the same solvent as in Example 1 to obtain a resin solution, and a test piece was prepared in the same manner as in Example 1.

The adhesion and solvent solubility of the resin compound of Example 1 and the resin composition of Example 2 were evaluated in the same manner as in Test 1.
The amount of each component in Examples 1 and 2 is as shown in Table 3. The evaluation results of adhesion and solvent solubility are as shown in Table 4.

From Test 2, the following can be said.

In Example 2, adhesion was improved compared to Example 1. In particular, the adhesion to PA6 resin was improved. It is thought that the adhesiveness of the resin composition is improved by the isocyanate-based curing agent forming a crosslinked structure.

<Test 3>
Next, as a test 3, a vinyl monomer (B1) having a hydroxyl group in the graft chain with respect to a resin compound part having a main chain composed of the acid-modified polyolefin (A) and a graft chain composed of a vinyl polymer, In addition, the change in adhesion was evaluated when a vinyl monomer (B2) having an alkyl group having 8 to 14 carbon atoms was introduced. Further, the vinyl monomer (B1) having a hydroxyl group in the graft chain, the vinyl monomer (B2) having an alkyl group having 8 to 14 carbon atoms, and the vinyl monomer (B3) having a polar group. The change in adhesiveness was evaluated in the case of introducing.

<Example 17>
In a 1 L flask, 224.0 g of methylcyclohexane, acid-modified polyolefin (A) (manufactured by Nippon Paper Industries Co., Ltd., 56.0 g of Aurolen (registered trademark) 350S), polypropylene glycol monomethacrylate (B1) (manufactured by NOF Corporation, Blemmer) (Registered trademark) PP-1000) 11.2 g, methyl methacrylate (B4) 7.84 g, butyl methacrylate (B4) 14.0 g, methacrylic acid 0.56 g, lauryl methacrylate (B2) 21.84 g, N-vinylpyrrolidone ( B3) 0.56 g was added and completely dissolved while raising the temperature to 90 ° C. After reaching 90 ° C., 0.3 g of t-butyl peroxy-2-ethylhexanoate (manufactured by NOF Corporation, Perbutyl O (registered trademark)) was added.

In this example as well, as in Example 1, the graft chain was determined to be bonded to the carbon atoms constituting the polyolefin backbone of the main chain.
A resin composition was prepared by mixing 5 parts by mass of an isocyanurate modified form of hexamethylene diisocyanate (Basonate (registered trademark) HI100 manufactured by BASF) as a curing agent (C) with 100 parts by mass of the obtained resin compound. 30 g of this resin composition was dissolved in 80 ml of the same solvent as in Example 1 to obtain a resin solution, and a test piece was prepared in the same manner as in Example 1. In addition to polyamide 6 (PA6) resin, polybutylene terephthalate (PBT) resin and tinplate, a polyallyl ether ketone (PAEK) resin and an aluminum plate (JIS H 4000 A5052P) were used as the base material on which the resin solution was applied. .

<Examples 3 to 16, 18 to 22>
A resin composition was obtained in the same manner as in Example 17. In this example as well, as in Example 1, the graft chain was determined to be bonded to the carbon atoms constituting the polyolefin backbone of the main chain.

Further, each resin composition was dissolved in 80 ml of the same solvent as in Example 1 to obtain a resin solution, and a test piece was prepared. The compounding amounts of the components for each example are as shown in Table 5. The evaluation results of adhesion and solvent solubility are as shown in Table 6.

From Test 3, the following can be said.

Examples 2 to 13 are resin compositions in which a vinyl monomer (B1) having a hydroxyl group in the graft chain is introduced, and Examples 14 to 16 are vinyl monomers (B1) having a hydroxyl group in the graft chain, And a resin composition into which a vinyl monomer (B2) having an alkyl group having 8 to 14 carbon atoms is introduced, Examples 17 to 22 are a vinyl monomer (B1) having a hydroxyl group in the graft chain, A resin composition into which a vinyl monomer (B2) having 8 to 14 alkyl groups and a vinyl monomer (B3) having a polar group are introduced.

In a resin composition in which a vinyl monomer (B2) having an alkyl group having 8 to 14 carbon atoms is introduced in addition to a vinyl monomer (B1) having a hydroxyl group in the graft chain, PA6 resin, PBT resin, tinplate Adhesion to was improved. In addition, it showed good adhesion to PAEK, which is an engineering plastic that could not be obtained with the conventional primer coating, and aluminum.

In addition to the vinyl monomer (B1) having a hydroxyl group in the graft chain and the vinyl monomer (B2) having an alkyl group having 8 to 14 carbon atoms, a vinyl monomer (B3) having a polar group is further added. With the introduced resin composition, the adhesion was further improved. In particular, Example 17 in which NVP was introduced as a vinyl monomer (B3) having a polar group, and Example 18 in which THFA was introduced showed excellent adhesion to any of the substrates subjected to the test. It was.

In addition, the resin compositions obtained in each example were all excellent in compatibility with the solvent.

Claims

A resin compound having a main chain composed of an acid-modified polyolefin and a graft chain composed of a vinyl polymer bonded to a carbon atom constituting the polyolefin skeleton of the main chain,
The graft chain is a graft chain having one of the constituent units of the first vinyl monomer having a hydroxyl group,
The resin compound, wherein the hydroxyl group is a hydroxyl group bonded to a carbon atom.
The resin composition according to claim 1, wherein the first vinyl monomer having a hydroxyl group is a (meth) acrylic acid monomer.
The resin compound according to claim 2, wherein the (meth) acrylic acid monomer is a polyalkylene glycol ester of (meth) acrylic acid.
The resin compound according to any one of claims 1 to 3, wherein the graft chain is a graft chain having a second vinyl monomer having an alkyl group having 8 to 14 carbon atoms as one of the constituent units. .
The resin compound according to claim 4, wherein the second vinyl monomer having an alkyl group having 8 to 14 carbon atoms is a (meth) acrylic acid monomer.
The resin compound according to claim 4, wherein the graft chain is a graft chain having a third vinyl monomer having a polar group as one of the constituent units.
The resin compound according to claim 6, wherein the third vinyl monomer having a polar group is at least one of tetrahydrofurfuryl acrylate and N-vinylpyrrolidone.
A resin composition comprising the resin compound according to any one of claims 1 to 7 and a curing agent.