JP2012031361A - Acrylic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve performances of an acrylic resin composition used for a coating material, pressure-sensitive adhesive, adhesive, resist material, acrylic syrup, etc., such as radical polymerization curability by heating or UV irradiation; self-repairing capability to a wound or contamination; adhesiveness; tackiness; developability; and handleability.SOLUTION: The acrylic resin composition includes an acrylic resin comprising: (A) 0.002-1.5 wt.% multifunctional acrylic monomer having two or more acryloyl groups in the molecule; (B) 88.5-99.998 wt.% acrylic monomer having one acryloyl group in the molecule; and (C) 0.0-10.0 wt.% vinyl monomer having a radically polymerizable unsaturated group other than (meth)acryloyl group in the molecule.

Description

  The present invention relates to an acrylic resin composition used for paints, pressure-sensitive adhesives, adhesives, resist materials, acrylic syrup, and the like, and particularly relates to an acrylic resin composition that undergoes radical polymerization and curing by heating, ultraviolet irradiation, or the like.

  Furthermore, the present invention relates to an acrylic resin composition that can be used as a self-repairing paint having good scratch resistance and no fingerprint marks.

  Acrylic resins are abundant in the types of acrylic monomers that are used as raw materials, and the physical and chemical properties such as adhesion, adhesion, hardness, transparency, light resistance, weather resistance, and chemical resistance are optionally controlled. Because it can, optical coatings such as displays and lenses, optical film applications, adhesives and adhesives used in these, paints, sealing materials, paper strength enhancers, dental materials, adhesives for aircraft and automobile parts, baths, It is widely applied and used as acrylic syrup used for sheet molding compound (SMC) material for bulk water-based products such as washstands, bulk molding compound (BMC) material, etc.

  Acrylic resins generally generate a large amount of heat during polymerization and become more viscous as the polymerization progresses, so industrially compared heat removal such as solution polymerization, emulsion polymerization, and suspension polymerization using water or an organic solvent as a medium. It is often manufactured by an easy method. Also, when used for special purposes such as casting, it may be used as partially polymerized acrylic syrup.

  2,4-diphenyl-4-methyl-1-pentene (ie, α-methylstyrene dimer), an acrylic containing an ethylenically unsaturated compound (= acrylic monomer) having a methacryloyl group in the presence of a radical polymerization initiator There has been proposed a method for producing a block copolymer by radical polymerization of monomers (see Patent Document 1). In the technique proposed in Patent Document 1, the increase in the polymerization rate is slow, and a long time is required for production.

  In the technique shown in Patent Document 1, since the relationship between the amount of 2,4-diphenyl-4-methyl-1-pentene used (number of moles) and the amount of polymerization initiator used (number of moles) is not defined, Production efficiency is poor and only low molecular weight polymers can be produced.

  A multistage radical polymerization method of an ethylenically unsaturated compound containing a compound having two or more ethylenically unsaturated groups in one molecule and a method for producing a branched polymer are disclosed (see Patent Document 2). Patent Document 2 does not define the relationship between the amount of 2,4-diphenyl-4-methyl-1-pentene used (in moles) and the amount of polymerization initiator (in moles) used for multistage radical polymerization. The polymerization rate increases slowly and requires a long time for production.

  In the technique shown in Patent Document 2, since the relationship between the amount of 2,4-diphenyl-4-methyl-1-pentene used (number of moles) and the amount of polymerization initiator used (number of moles) is not defined, The branched polymer to be produced gels during production, and even if it can be produced, the gel fraction becomes high and cannot be practically used.

  High-performance, high-function IT devices such as multi-function copiers, RAS personal computers, ARA personal computers, mobile phones with large screens, sophisticated smartphones, and tablet computers are widely used. In particular, smartphones and tablet computers, which are expected to grow rapidly in the future, are easy to operate and highly functional, so the touch panel system is rapidly expanding.

  Generally, the outermost layer of the touch panel is provided with a hard coat layer to prevent damage. Although the hard coat is difficult to be scratched, once it was scratched, it did not return to its original state, and the dirt was attached to the wound, and the dirt spread from the scratch. In addition, fingerprints on the hard coat were likely to remain, and the display that most hates contamination was full of fingerprints and sebum.

  An ultraviolet curable undercoat (paint) having good adhesion to a polyolefin base material using a mixture of a chlorinated polyolefin and an acrylic copolymer has been proposed (see Patent Document 3). In the technique proposed in Patent Document 3, since the chlorinated polyolefin and acrylic copolymer to be used do not have ultraviolet curing properties, the chlorinated polyolefin and acrylic copolymer remain in an uncrosslinked state even after ultraviolet irradiation. It is. For this reason, even after ultraviolet irradiation, the cohesive energy of the film is small, and practical adhesive strength is not exhibited. At the same time, the solvent resistance and chemical resistance are not improved, so the durability is insufficient.

  A technique relating to a heat sealing agent for packaging materials in which a chlorinated polyolefin resin and a polyolefin resin or an acrylic resin are mixed and used has been proposed (see Patent Document 4). The technique proposed in Patent Document 4 improves the easy peel property so that a heat-sealed part such as a packaging bag can be opened manually. Therefore, the technique proposed in Patent Document 4 is not permanent bonding but relates to temporary bonding before use, and is not suitable for applications requiring a strong bonding force.

  An active energy ray-curable coating agent that has excellent self-repairability and scratch resistance has been proposed (see Patent Document 5). In Patent Document 5, since hard and brittle compounds such as epoxy resins, oxetane resins, and vinyl ester resins are often used, it is predicted that the hard coat material will perform as it is. There are doubts about the hurtability. Further, fingerprint marks are not taken into consideration at all, and even if the coating film has good transparency, there is no practical difference from the conventional one.

There has been proposed an ultraviolet curable electrodeposition coating for an electronic equipment exterior casing that has both high surface hardness and self-healing properties (see Patent Document 6). The technique proposed in Patent Document 6 is to crosslink and cure an acrylic resin having an ultraviolet curable (meth) acryloyl group in the molecular side chain with a polyfunctional acrylic monomer. The coating film is hard and brittle, and the self-repairing property is insufficient. In addition, fingerprint marks are not taken into consideration at all, and sufficient functions cannot be expected.

JP 2000-169531 A JP 2000-239334 A JP-A-6-279706 JP 2004-43536 A JP 2007-284613 A JP 2010-65168 A

CHEMISTRY LETTERS, pp. 1089-1092, 1993

  The present invention relates to an acrylic resin composition used for paints, pressure-sensitive adhesives, adhesives, resist materials, acrylic syrups, etc., radical polymerization curability by heating or ultraviolet irradiation, self-repairing property against scratches and contamination, adhesiveness, and adhesion. It is an object to improve main required performance such as property, developability and handling property.

  The present invention relates to 0.002 to 1.5% by weight of a polyfunctional acrylic monomer (A) having two or more acryloyl groups in the molecule, and an acrylic monomer having one acryloyl group in the molecule ( B) Acrylic resin comprising 88.5 to 99.998% by weight, vinyl monomer having radically polymerizable unsaturated group other than (meth) acryloyl group in the molecule (C) 0.0 to 10.0% by weight Is an acrylic resin composition.

  Since the acrylic resin composition of the present invention is non-colored to slightly colored, has high transparency, excellent weather resistance, and good adhesion and adhesion, it is preferably used as an exterior material for mobile phones, audios and the like. It is used as a polymer for improving impact resistance and flexibility of hard coats used in in-mold decoration (IMD) and the like, and is used as an adhesive and adhesive for high function filters such as PDP televisions and liquid crystal televisions.

  The acrylic resin composition of the present invention has high resistance to coating film scratches due to scratches and impacts, sebum, cosmetics, fingerprints, etc. (self-healing), beautiful initial appearance of coating film, and design Since the property can be maintained over a long period of time, it is used as a self-repairing paint for touch panels, tablet PCs, electronic paper, mobile phones, and other products and members that do not like scratches or pollution.

  The acrylic resin composition of the present invention is radically polymerized and cured by heating or ultraviolet irradiation, exhibits appropriate adhesive strength and adhesive strength depending on the application, and has good chemical resistance, weather resistance, etc. Used for pressure-sensitive adhesives, adhesives, etc. Used for pressure-sensitive adhesives, adhesives, etc. for laminate layers of laminate-type lithium ion secondary batteries, binders for carbon fibers, glass fibers, aramid fibers, etc., sizing agents, and fibers It can be used as an adhesive for reinforced composite materials.

  The present invention relates to 0.002 to 1.5% by weight of a polyfunctional acrylic monomer (A) having two or more acryloyl groups in the molecule, and an acrylic monomer having one acryloyl group in the molecule ( B) Acrylic resin comprising 88.5 to 99.998% by weight, vinyl monomer having radically polymerizable unsaturated group other than (meth) acryloyl group in the molecule (C) 0.0 to 10.0% by weight Is an acrylic resin composition.

In the present invention, the polyfunctional acrylic monomer (A) having two or more acryloyl groups in the molecule has two or more acryloyl groups in the molecule. The acrylic monomer (B) having one acryloyl group in the molecule has one acryloyl group in the molecule. The vinyl monomer (C) having a radically polymerizable unsaturated group other than a (meth) acryloyl group in the molecule is an acryloyl group (CH ₂ ═CH—C (O) —O—) in the molecule, or a methacryloyl group. (CH ₂ ═C (CH ₃ ) —C (O) —O—) is not included, and the molecule has a radical polymerizable unsaturated group other than the (meth) acryloyl group.

In the acrylic resin composition of the present invention, as a polyfunctional acrylic monomer (A) having two or more acryloyl groups (CH ₂ ═CH—C (O) O—) in the molecule, ethylene glycol diacrylate, diethylene glycol Diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, trimethylol Propane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, neopentyl glycol diacrylate Acrylic acid adduct of bisphenol A diglycidyl ether, ethylene oxide modified bisphenol A diacrylate, isocyanuric acid ethylene oxide modified diacrylate, and isocyanuric acid ethylene oxide-modified triacrylate, and the like. In the acrylic resin composition of the present invention, the polyfunctional acrylic monomer (A) may be used alone or in a mixture of two or more.

  In the acrylic resin composition of the present invention, among these polyfunctional acrylic monomers (A), isocyanuric acid ethylene oxide-modified diacrylate, 1,4-butanediol diacrylate, trimethylolpropane triacrylate, An acrylic acid adduct of bisphenol A diglycidyl ether and ethylene oxide-modified bisphenol A diacrylate are desirable, and there is a tendency that the curability and mechanical properties of the acrylic resin are balanced and improved. In the acrylic resin composition of the present invention, these polyfunctional acrylic monomers (A) can be arbitrarily selected from those on the market.

  In the acrylic resin composition of the present invention, the acrylic resin composition is preferably an isocyanuric acid ethylene oxide-modified diacrylate, an acrylic acid adduct of bisphenol A diglycidyl ether when used for an adhesive, an adhesive, and the like. The use of polyfunctional acrylic monomer (A) with a rigid cyclic structure in the molecule such as ethylene oxide-modified bisphenol A diacrylate is recommended, which increases the cohesive strength of the acrylic resin and dramatically improves the adhesiveness and adhesion. The tendency to do is seen. In the acrylic resin composition of the present invention, the polyfunctional acrylic monomer having a rigid skeleton such as isocyanuric acid ethylene oxide-modified diacrylate is preferably used when the acrylic resin composition is used for a photoresist, a paint or the like. (A) and the use of an aliphatic polyfunctional acrylic monomer (A) such as 1,4-butanediol diacrylate and trimethylolpropane triacrylate is recommended, and the intramolecular branching of the acrylic resin is suitably used. In addition, it can be controlled to be as large as possible, and there is a tendency that the curability and crosslinkability of the acrylic resin are improved, and the developability and coating workability are improved. Furthermore, if isocyanuric acid ethylene oxide-modified diacrylate is used, the rheology of the coating film is appropriately controlled, the resistance to scratching, fingerprint marks, etc. is improved, and self-repairability tends to be improved. .

  In the acrylic resin composition of the present invention, examples of the isocyanuric acid ethylene oxide-modified diacrylate include “Aronix M-215” (product of Toagosei Co., Ltd.), and 1,4-butanediol diacrylate is For example, “Fancryl FA-124AS” (product of Hitachi Chemical Co., Ltd.) and the like are exemplified, and trimethylolpropane triacrylate is exemplified by “Aronix M-309” (product of Toagosei Co., Ltd.), “ “Light acrylate TMP-A” (product of Kyoeisha Chemical Co., Ltd.) and the like, and acrylic acid adducts of bisphenol A diglycidyl ether are, for example, “epoxy ester 3000A” and “epoxy ester 3002A” (above, Kyoeisha Chemical Co., Ltd.). (Products from Co., Ltd.) Sphenol A diacrylate is, for example, “Fancryl FA-321A”, “Fancryl FA-324A” (product of Hitachi Chemical Co., Ltd.), “Aronix M-210” (Toagosei Co., Ltd.) Product).

  In the present invention, among the polyfunctional acrylic monomers (A), in particular, isocyanuric acid ethylene oxide-modified diacrylate is recommended, and the curability of paints, pressure-sensitive adhesives, adhesives, etc. is good, scratch resistance, fingerprint marks, etc. Stable and strong adhesion when joining polyolefins such as polyethylene and polypropylene to dissimilar materials such as aluminum alloy, stainless steel, and iron, etc. There is a tendency to demonstrate sex.

  In the acrylic resin composition of the present invention, the use of isocyanuric acid ethylene oxide-modified diacrylate improves the scratch resistance and non-contamination property of the self-healing paint, and maintains a beautiful appearance at the initial stage of coating for a long period of time. There is a tendency to continue.

  In the acrylic resin composition of the present invention, the self-healing paint has good scratch resistance of the coating film, and even if it is scratched, it recovers to a level where there is no practical problem (self-healing property). Is a self-healing paint with excellent anti-contamination property, and it is difficult for fingerprint marks, sweat, and sebum to adhere to the coating film.

  In the acrylic resin composition of the present invention, as isocyanuric acid ethylene oxide-modified diacrylate, for example, the following structural formula

And ethoxylated isocyanuric acid diacrylate represented by Examples of commercially available isocyanuric acid ethylene oxide-modified diacrylates include “Aronix M-215”, “Aronix M-313”, “Aronix M-315” (above, products of Toagosei Co., Ltd.), etc. Is exemplified.

  In the acrylic resin composition of the present invention, the polyfunctional acrylic monomer (A) is used in an amount of 0.002 to 1.5% by weight. In the acrylic resin composition of the present invention, when the amount of the acrylic monomer (A) used is less than 0.002% by weight, the intramolecular branching of the acrylic resin is insufficient, and the curability is deteriorated. The crosslinking density of the acrylic resin is insufficient, and the cohesive force, self-repairability, tackiness, and adhesiveness of the acrylic resin deteriorate. In the acrylic resin composition of the present invention, when the amount of the acrylic monomer (A) used exceeds 1.5% by weight, the acrylic resin has excessive intramolecular branching, and depending on the production conditions, crosslinking may occur during the production. The viscosity becomes too high and handling becomes worse from a practical viewpoint. In the acrylic resin composition of this invention, it may gelatinize during manufacture.

  In the acrylic resin composition of the present invention, the acrylic monomer (A) is preferably used in an amount of 0.002 to 1.2% by weight, more preferably 0.0025 to 0.8% by weight. . In the acrylic resin composition of the present invention, when the amount of the acrylic monomer (A) used is 0.002 to 1.2% by weight, the acrylic resin has good storage stability and the intramolecular branching is appropriately controlled. In addition, various properties such as handling properties, curability, self-healing properties of the coated film after curing, tackiness, and adhesiveness are balanced, and there is a tendency to be excellent.

In the acrylic resin composition of the present invention, as an acrylic monomer (B) having one acryloyl group (CH ₂ ═CH—C (O) O—) in the molecule, methyl acrylate, ethyl acrylate, acrylic N-butyl acid, tertiary butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, alkyl acrylates, isobornyl acrylate, benzyl acrylate Acrylic monomers having bulky substituents such as acrylic acid, acrylic monomers having a carboxyl group such as β-carboxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl Acrylic monomer containing hydroxyl group such as acrylate , Alkoxymethyl acrylates such as 2-methoxyethyl acrylate and 2-ethoxymethyl acrylate, epoxy group-containing acrylic monomers such as glycidyl acrylate, oxolane groups such as tetrahydrofurfuryl acrylate and acryloyloxypropyl-1,3-dioxolane -Containing acrylic monomer, dicyclopentyl group-containing methacrylic monomer such as dicyclopentenyloxyethyl acrylate, tetramethylpiperidinyl acrylate, pentamethylpiperidinyl acrylate, N, N-dimethylaminoethyl acrylate, acryloyloxyethyltrimethyl Examples include amino group-containing acrylic monomers such as ammonium chloride and acryloyloxyethyldimethylbenzylammonium chloride. In the acrylic resin composition of the present invention, the acrylic monomer (B) having one acryloyl group in the molecule may be used alone or in a mixture of two or more.

  In the acrylic resin composition of the present invention, among the acrylic monomers (B) having one acryloyl group in these molecules, the acrylic resin composition is preferably curable, adhesive, tacky, When used as a self-repairing paint, UV curable pressure-sensitive adhesive, adhesive or the like having good adhesiveness, an alkyl acrylate ester having 2 to 8 carbon atoms in the alkyl group, more preferably acrylic acid Acrylic acid alkyl ester having 4 to 9 carbon atoms in alkyl group such as isobutyl, 2-ethylhexyl acrylate, isobornyl acrylate, etc., carboxyl group-containing acrylic monomer such as acrylic acid, β-carboxyethyl acrylate, acrylic acid Hydroxyl-containing acrylic monomers such as 2-hydroxyethyl and 4-hydroxybutyl acrylate, dicyclopenes Dicyclopentyl group-containing acrylic monomers such as nyloxyethyl acrylate are recommended, and the acrylic resin composition is preferably used for photoresists, paints and the like having good developability and improved pigment dispersibility. Recommended amino group-containing acrylic monomers such as tetramethylpiperidinyl acrylate, pentamethylpiperidinyl acrylate, N, N-dimethylaminoethyl acrylate, acryloyloxyethyltrimethylammonium chloride, acryloyloxyethyldimethylbenzylammonium chloride When the acrylic resin composition is used as a functional acrylic rubber that preferably improves the flexibility, elongation, impact resistance, etc. of a hard coat having a high elastic modulus and excellent chemical resistance, a polyfunctional urethane Mixed with acrylate When used as a hard coat, an alkyl acrylate ester having 2 to 8 carbon atoms in the alkyl group, more preferably an alkyl group such as isobutyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, etc. Acrylic acid alkyl ester having 4 to 9 carbon atoms, acrylic acid, carboxyl group-containing acrylic monomer such as β-carboxyethyl acrylate, alkoxyethyl acrylate such as 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, etc. Recommended.

  In the present invention, UV curable self-healing paint having good self-healing properties such as adhesion, scratch resistance and non-staining properties, UV curable pressure-sensitive adhesive exhibiting controlled adhesion performance, polyethylene, polypropylene, polyester, nylon When used as an ultraviolet curable adhesive for bonding metals such as organic polymer materials such as aluminum alloys, zinc alloys and iron, among the acrylic monomers (B), isobutyl acrylate, acrylic acid 2 -Ethylhexyl and isobornyl acrylate are preferred.

  In the acrylic resin composition of the present invention, 88.5 to 99.998% by weight of the acrylic monomer (B) having one acryloyl group in the molecule is used. In the acrylic resin composition of the present invention, when the amount of the acrylic monomer (B) used is less than 88.5% by weight, the flexibility and flexibility of the acrylic resin are lost, and the tenacity decreases. Self-healing, tackiness, and adhesiveness are not fully exhibited. In the acrylic resin composition of the present invention, when the amount of the acrylic monomer (B) used exceeds 99.998% by weight, the acrylic resin has insufficient intramolecular branching, and the acrylic resin is heated or irradiated with ultraviolet rays. The radical polymerization curability and crosslinkability of the resin deteriorate.

  In the acrylic resin composition of the present invention, the acrylic monomer (B) is preferably used in an amount of 88.8 to 99.798% by weight, more preferably 89.2 to 96.9957% by weight. .

In the acrylic resin composition of the present invention, in addition to the polyfunctional acrylic monomer (A) having two or more acryloyl groups in the molecule and the acrylic monomer (B) having one acryloyl group in the molecule. The vinyl monomer (C) having a radically polymerizable unsaturated group other than the (meth) acryloyl group in the molecule can be used in an amount of 0.0 to 10.0% by weight. In the acrylic resin composition of the present invention, the (meth) acryloyl group includes an acryloyl group (CH ₂ ═CH—C (O) —O—), a methacryloyl group (CH ₂ ═C (CH ₃ ) —C (O) — Any one of O-). In the acrylic resin composition of the present invention, the radical polymerizable unsaturated group other than the (meth) acryloyl group is preferably an amide group (CH ₂ ═CH—C (O) —N <), a vinyl group (CH ₂ = CH-), vinyl ether group _{(CH 2 = CH-O-)} , an allyl group _{(CH 2 = CH-CH 2} -) are exemplified.

  In the acrylic resin composition of the present invention, acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, vinyl monomer having a radical polymerizable unsaturated group other than (meth) acryloyl group in the molecule, Acrylamide compounds such as N- (2-hydroxyethyl) acrylamide, N, N-dimethylaminopropylacrylamide, acryloylmorpholine, acrylonitrile, N-vinyl-2-pyrrolidone, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (methylethylketone) Oximes) Vinyl compounds such as silane, styrene and vinyl acetate, carboxylic acids such as itaconic acid, maleic acid and maleic anhydride, epoxy group-containing compounds such as vinyl benzyl glycidyl ether, n-butyl vinyl Ether, vinyl ether compounds such as cyclohexyl vinyl ether are exemplified. In the acrylic resin composition of the present invention, the vinyl monomer (C) having a radical polymerizable unsaturated group other than the (meth) acryloyl group in the molecule may be used alone or in a mixture of two or more. May be.

  In the acrylic resin composition of the present invention, in the vinyl monomer (C) having a radical polymerizable unsaturated group other than the (meth) acryloyl group in these molecules, the acrylic resin composition is preferably cured. N- (2-hydroxyethyl) acrylamide when used as a heat- or UV-curable coating, self-healing coating, adhesive, adhesive, etc. Such as N-alkylolacrylamide, N-vinyl-2-pyrrolidone and the like, or compounds having hetero atoms in the molecule, or heterocyclic compounds, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (methylethylketoneoxime) silane, etc. Alkoxysilane group-containing compounds are recommended, and acrylic resin compositions are preferred. In the case where it is used for a photoresist or paint having good wettability and affinity to an adherend, an acrylamide compound such as acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, or vinylbenzyl glycidyl ether. Epoxy group-containing compounds such as are recommended.

  In the acrylic resin composition of the present invention, 0.0 to 10.0% by weight of the vinyl monomer (C) having a radical polymerizable unsaturated group other than the (meth) acryloyl group in the molecule is used. In the acrylic resin composition of the present invention, when the amount of the vinyl monomer (C) used exceeds 10.0% by weight, when the acrylic resin composition is used for a photoresist, paint, etc., the water resistance, Chemical properties deteriorate, developability and moisture adhesion resistance deteriorate.

  In the acrylic resin composition of the present invention, the vinyl monomer (C) is preferably 0.2 to 10.0% by weight, more preferably 3.0 to 10.0% by weight, and still more preferably 3%. It is desirable to use 0.0 to 8.0% by weight. In the acrylic resin composition of the present invention, if the amount of the vinyl monomer (C) used is 0.2 to 10.0% by weight, the cohesive force of the acrylic resin composition is appropriately controlled. There is a tendency that the wettability and affinity to polyolefins such as polyethylene and polypropylene are improved, and adhesion, tackiness, and adhesion are improved and improved.

In the acrylic resin composition of the present invention, it is desirable that an acrylic monomer having a methacryloyl group (CH ₂ ═C (CH ₃ ) —C (O) O—) in the molecule is not used. In the acrylic resin composition of the present invention, when an acrylic monomer having a methacryloyl group in the molecule is used in the production of the acrylic resin, the increase in the polymerization rate tends to be slow, and the acrylic resin is produced. There is a tendency that production efficiency deteriorates because a long time is required. The use of an acrylic monomer having a methacryloyl group tends to cause a decrease in molecular weight as the polymerization rate increases, and the intended acrylic resin composition may not be designed and manufactured.

  In the acrylic resin composition of the present invention, when the acrylic resin composition is used as an ultraviolet curable paint, a pressure-sensitive adhesive, or an adhesive, it is preferable that a polyfunctional acrylic unit having two or more acryloyl groups in the molecule. A monomer (A), an acrylic monomer (B) having one acryloyl group in the molecule, and a vinyl monomer (C) having a radical polymerizable unsaturated group other than the (meth) acryloyl group in the molecule. The acrylic monomer (D) to be contained can be used for performance adjustment such as viscosity adjustment, adhesion, tackiness, adhesiveness, and self-healing property for improving coating workability and coating workability.

  In the acrylic resin composition of the present invention, the acrylic monomer (D) is preferably 5 to 60% by weight, more preferably 10 to 55, in the acrylic polymer concentration of the ultraviolet curable paint, pressure-sensitive adhesive, and adhesive. It is desirable to use it in an amount of 15% by weight, more preferably 15 to 55% by weight. When the acrylic polymer concentration is from 5 to 60% by weight, the ultraviolet curability is good, and various performances such as self-repairability, adhesion, tackiness, and adhesiveness tend to be improved.

  In the acrylic resin composition of the present invention, the acrylic polymer concentration is determined by measuring the heating residue of the ultraviolet curable paint, the pressure-sensitive adhesive, and the adhesive according to JIS K 5407: 1997, and setting the heating residue as the acrylic polymer concentration. .

  The acrylic resin composition of the present invention preferably has a gel fraction of less than 3%. In the acrylic resin composition of the present invention, when the gel fraction exceeds 3%, the viscosity of the acrylic resin increases, and the fluidity deteriorates when processed by coating work, molding, etc., and the finished surface is good. There is a tendency that new products cannot be manufactured. In the acrylic resin composition of the present invention, when the gel fraction exceeds 3%, the acrylic resin is, for example, an acrylic monomer (B) such as isobutyl acrylate, 2-ethylhexyl acrylate, acrylic It is diluted with polyfunctional acrylic monomer (A) such as isobornyl acid, for example, isocyanuric acid ethylene oxide-modified diacrylate, acrylic acid adduct of bisphenol A diglycidyl ether, or dissolved to form an acrylic resin composition. When used in adhesives, adhesives, photoresists, acrylic syrups, etc., the solubility is poor, bubbles tend to be involved, and the handling tends to deteriorate. In the acrylic resin composition of the present invention, the gel fraction is more preferably less than 1%, and still more preferably 0%.

  In the acrylic resin composition of the present invention, the photopolymerization initiator is preferably contained in an amount of 0.2 to 15% by weight with respect to 100% by weight of the total amount of the acrylic resin composition and the acrylic monomer (D). desirable.

  In the acrylic resin composition of the present invention, as a photopolymerization initiator, benzyl dimethyl ketal, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one (“IRGACURE 651” manufactured by BASF Corporation) ), Α-hydroxyalkylphenone, such as 1-hydroxy-cyclohexyl-phenyl-ketone (such as “IRGACURE 184” manufactured by BASF Corporation), 2-hydroxy-2-methyl-1-phenyl-propane-1- ON (such as “IRGACURE 1173” manufactured by BASF Corporation), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (BASF Corporation ) "IRGACURE 2959" manufactured by the company), 2-hydroxy-1- {4- [4- (2-hydroxy) Cy-2-methyl-propionyl) benzyl] -phenyl} -2-methyl-propane (such as “IRGACURE 127” manufactured by BASF Corp.), α-aminoalkylphenone, such as 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropan-1-one (such as "IRGACURE 907" manufactured by BASF Corporation), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butanone-1 (such as “IRGACURE 369” manufactured by BASF Corporation), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1 -ON (such as “IRGACURE 379” manufactured by BASF Corporation), acylphosphine oxide type, such as 2,4,6-to Limethylbenzoyl-diphenyl-phosphine oxide (such as “DAROCURE TPO” manufactured by BASF Corporation), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF Corporation “ IRGACURE 819 "etc.) etc. In the acrylic resin composition of the present invention, these photopolymerization initiators may be used alone or in a mixture of two or more.

  In the acrylic resin composition of the present invention, among the photopolymerization initiators, preferably, benzyl methyl ketal, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF Corporation) “IRGACURE 651”), α-hydroxyalkylphenones such as 1-hydroxy-cyclohexyl-phenyl-ketone (“IRGACURE 184” manufactured by BASF Corporation), 2-hydroxy-2-methyl-1-phenyl, etc. -Propan-1-one (such as “IRGACURE 1173” manufactured by BASF Corporation), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1- ON (such as “IRGACURE 2959” manufactured by BASF Corporation), 2-hydroxy-1- {4- [4- Acylphosphine oxide photopolymerization initiators such as (2-hydroxy-2-methyl-propionyl) benzyl] -phenyl} -2-methyl-propane (such as “IRGACURE 127” manufactured by BASF Corporation) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (such as “DAROCURE TPO” manufactured by BASF Corporation), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (BASF Corporation) ) “IRGACURE 819” manufactured by the company) is recommended, and the surface curability and deep curability of self-healing paints, adhesives, and adhesives tend to be improved and improved.

  In the acrylic resin composition of the present invention, the photopolymerization initiator is preferably used in an amount of 0.5 to 15% by weight, more preferably 0.5 to 12% by weight. If the photopolymerization initiator is used in an amount of 0.5 to 15% by weight, even if the coating film is thin, the surface curability is improved, a tack-free scratch-resistant, anti-staining and beautiful coating film is formed. The tendency to be seen is seen. Moreover, deep part sclerosis | hardenability improves, the cohesive force of an adhesive and an adhesive improves, and the tendency for adhesive strength and adhesive strength to improve further is seen.

  In the acrylic resin composition of this invention, the tendency which the sclerosis | hardenability and storage stability of an acrylic resin composition improve is further seen, for example by mix | blending a hindered amine compound with an acrylic resin composition. In the acrylic resin composition of the present invention, the hindered amine compound is preferably 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl). Sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine- 2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] and the like Is done. In the pressure-sensitive adhesive composition of the present invention, the hindered amine compound may be used alone or in a mixture of two or more.

  In the pressure-sensitive adhesive composition of the present invention, the hindered amine compound can be arbitrarily selected from those on the market. For example, “Sanol LS-744” (product of Sankyo Lifetech Co., Ltd., 4-benzoyloxy-2,2,6,6-tetramethylpiperidine), “Sanol LS-770” (Sankyo Lifetech ( Product), bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate), "Sanol LS-765" (Sankyo Lifetech Co., Ltd. product, bis (1,2,2) , 6,6-pentamethyl-4-piperidyl) sebacate), “Sanol LS-944” (product of Sankyo Lifetech Co., Ltd., poly [{6- (1,1,3,3-tetramethylbutyl) amino- 1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4- Piperidyl Imino}]), and the like.

  In the acrylic resin composition of the present invention, among the hindered amine compounds, the following structural formula

4-benzoyloxy-2,2,6,6-tetramethylpiperidine (“Sanol LS-744” (product of Sankyo Lifetech Co., Ltd.) is recommended, and self-healing paints, adhesives, adhesives, etc. Storage stability and UV curability are good, and there is a tendency to exhibit good adhesion, tackiness, and adhesion.

  In the acrylic resin composition of the present invention, the compound having a reducing action such as a hindered amine compound is preferably 0.2 to 10% by weight, more preferably 0.5 to 100% by weight with respect to 100% by weight of the acrylic resin composition. It is desirable to use 5% by weight, more preferably 0.5 to 3% by weight.

  In the acrylic resin composition of the present invention, it is recommended that the hindered amine compound is used in an amount of 0.02 to 3% by weight based on 100% by weight of the acrylic resin composition. The properties are dramatically improved, the curability under UV irradiation is sharpened quickly, and the weather resistance of cured coatings, pressure-sensitive adhesives, adhesives and the like tends to be excellent.

  In the acrylic resin composition of the present invention, when the acrylic resin composition is used as a heating or ultraviolet curable paint, pressure-sensitive adhesive, or adhesive, the adherend is made to be a hardly adhesive adherend, such as polyethylene and polypropylene. In the case of polyolefins, it is recommended to use chlorinated polyolefins mixed with acrylic resin compositions. In the acrylic resin composition of the present invention, as a chlorinated polyolefin that is preferably used, “Harden 13LLP” (chlorine content 26% by weight), “Harden 14LLB” (chlorine content 27% by weight), “Harden DX-526P” (Chlorine content 26% by weight), “Hardren DX-530P” (chlorine content 30% by weight) (the product of Toyobo Co., Ltd.) and the like. In the acrylic resin composition of the present invention, the chlorinated polyolefin may be used alone or in a mixture of two or more.

  In the acrylic resin composition of the present invention, the chlorine content of the chlorinated polyolefin is preferably 23 to 33% by weight, more preferably 23 to 30% by weight, and still more preferably 25 to 30% by weight. desirable. If the chlorine content is 23 to 33% by weight, the storage stability when mixed with an acrylic resin composition is good, and the adhesion, adhesion, and adhesion to difficult-to-adhere substrates such as polyethylene and polypropylene are good. There is a tendency to improve.

  In the acrylic resin composition of the present invention, the coating film is less likely to have scratches or fingerprint marks by adding chlorinated polyolefin to the acrylic resin composition and using it as a heat- or UV-curable paint, adhesive, or adhesive. There is a tendency to improve self-repairability. Moreover, the tendency which exhibits favorable performance as an adhesive agent etc. of the unstretched polypropylene which is a laminate layer (exterior) material of a laminate-type lithium ion secondary battery, and aluminum foil is seen.

  In the acrylic resin composition of the present invention, the chlorinated polyolefin is preferably 1 to 25% by weight, more preferably 1 to 18% by weight, and still more preferably 1.100% by weight with respect to 100% by weight of the acrylic resin composition. It is desirable to use 5 to 12% by weight. When 1 to 25% by weight of chlorinated polyolefin is used, various performances such as adhesion, adhesiveness, and self-repairability are improved and improved.

  In the acrylic resin composition of the present invention, the acrylic resin may be produced by any method as long as the acrylic resin can be produced, such as solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization. In the acrylic resin composition of the present invention, the acrylic resin production method is preferably selected and applied in accordance with the application in which the acrylic resin composition is used. In the acrylic resin composition of the present invention, when the acrylic resin composition is used for, for example, an ultraviolet curable paint or a photoresist, preferably, solution polymerization is applied, and a heating or ultraviolet curable adhesive, When used for adhesives, solution polymerization, emulsion polymerization, and bulk polymerization are preferably applied and used for molding materials such as sheet molding compound (SMC) and bulk molding compound (BMC). In some cases, it is preferable to apply bulk polymerization. In the acrylic resin composition of the present invention, when a coil coating is applied to the coating method as an ultraviolet curable paint, a pressure-sensitive adhesive, or an adhesive, an ester such as ethyl acetate having a low boiling point and easily vaporizing, a ketone such as methyl ethyl ketone It is desirable to produce by solution polymerization using an aromatic solvent such as toluene.

  The acrylic resin composition of the present invention preferably uses 0.05 to 1.0 mol of a polymerization initiator with respect to 1.0 mol of α-methylstyrene dimer and has two or more acryloyl groups in the molecule. Polyfunctional acrylic monomer (A) 0.002 to 1.5% by weight, acrylic monomer having one acryloyl group in the molecule (B) 88.5 to 99.998% by weight, It is desirable to produce 0.0 to 10.0% by weight of a vinyl monomer (C) having a radical polymerizable unsaturated group other than a (meth) acryloyl group by radical polymerization.

  In the acrylic resin composition of the present invention, the α-methylstyrene dimer is preferably 2,4-diphenyl-4-methyl-1-pentene, and is an odorless chain transfer agent (for example, used in the production of ABS resin). It is well known as a polymerization degree modifier.

  In the acrylic resin composition of the present invention, α-methylstyrene dimer produced and sold by NOF Corporation, Mitsui Chemicals, Goi Kasei Co., Ltd., etc. can be used. In the method for producing an acrylic copolymer of the present invention, in order to increase the production efficiency of the acrylic resin and suppress the coloring of the acrylic resin, the purity of the α-methylstyrene dimer, that is, in the commercially available α-methylstyrene dimer, The 2,4-diphenyl-4-methyl-1-pentene content is preferably 93.0% or more, more preferably 97.0% or more, and further preferably 99.0% or more. . In the acrylic resin composition of the present invention, as the 2,4-diphenyl-4-methyl-1-pentene content in the α-methylstyrene dimer is higher, the acrylic resin is less colored and the curability of the acrylic resin tends to be improved. Is seen.

  In the acrylic resin composition of the present invention, an organic azo polymerization initiator and an organic peroxide are preferably exemplified as the polymerization initiator used when the acrylic resin is produced.

  In the acrylic resin composition of the present invention, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) is preferably used as an organic azo polymerization initiator. “V-70”; melting point 50 to 96 ° C., 10 hour half-life 30 ° C.), 2,2′-azobis (2,4-dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.) Melting point 45 to 70 ° C., 10 hour half-life 51 ° C., 2,2′-azobis (2-methylpropionitrile) (“V-60” manufactured by Wako Pure Chemical Industries, Ltd .; melting point 100 to 103 C, 10-hour half-life 65 ° C.), 2,2′-azobis (2-methylbutyronitrile) (“V-59” manufactured by Wako Pure Chemical Industries, Ltd.); melting point 48-52 ° C., 10-hour half-life 67 ° C.), dimethyl 2,2′-azobis (2-methylpropionate) (“V-601” manufactured by Wako Pure Chemical Industries, Ltd .; melting point 22-28 ° C., 10 hour half-life 66 ° C.), etc. In the acrylic resin composition of the present invention, these organic azo polymerizations are used. The initiator may be used alone or in a mixture of two or more.

  In the acrylic resin composition of the present invention, among the organic azo polymerization initiators that are preferably used, the 10-hour half-life temperature is preferably 30 to 80 ° C, more preferably 30 to 75 ° C, and still more preferably. An organic azo polymerization initiator at 30 to 67 ° C is desirable. In the acrylic resin composition of the present invention, the use of an organic azo polymerization initiator having a 10-hour half-life temperature of 30 to 80 ° C. tends to improve the production efficiency of the acrylic resin and shorten the production time. It can be seen. Further, the polymerization temperature can be easily controlled, and the acrylic resin can be produced more safely.

  In the acrylic resin composition of the present invention, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) is preferably used as the organic azo polymerization initiator having a 10-hour half-life temperature of 30 to 80 ° C. (“V-70” manufactured by Wako Pure Chemical Industries, Ltd .; melting point 50 to 96 ° C., 10 hour half-life 30 ° C.), 2,2′-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd.) "V-65" manufactured by Co., Ltd .; melting point 45-70 ° C, 10 hour half-life 51 ° C), 2,2'-azobis (2-methylpropionitrile) (manufactured by Wako Pure Chemical Industries, Ltd. “V-60”; melting point 100 to 103 ° C., 10 hour half-life 65 ° C.), 2,2′-azobis (2-methylbutyronitrile) (“V-59” manufactured by Wako Pure Chemical Industries, Ltd.); Mp 48-52 ° C., 10 hour half-life 67 ° C.), dimethyl 2,2′-azobi (2-methylpropionate) (Wako Pure Chemical Industries Co., Ltd. of "V-601"; mp 22 to 28 ° C., 10-hour half-life 66 ° C.) and the like are exemplified.

  In the acrylic resin composition of the present invention, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane (“Perhexa” manufactured by NOF Corporation) is preferably used as the organic peroxide. TMH ”and the like; 10-hour half-life temperature 86.7 ° C., 1,1-bis (t-hexylperoxy) cyclohexane (“ Perhexa HC ”manufactured by NOF Corporation), etc .; 10-hour half-life temperature 87. 1 ° C), 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane (such as “Perhexa 3M-95” manufactured by NOF Corporation; 10-hour half-life temperature 90.0 ° C.) 1,1-bis (t-butylperoxy) cyclododecane (“Perhexa CD” manufactured by NOF Corporation, etc .; 10 hour half-life temperature 95.0 ° C.), 1,1,3,3-tetramethyl Butyl hydroperoxa Do (Nippon Co., Ltd. “Perocta H”, etc .; 10-hour half-life temperature 152.9 ° C.), t-hexyl hydroperoxide (Nichio Co., Ltd. “Perhexyl H”, etc .; 10 hours half Period temperature 159.5 ° C.), t-butylcumyl peroxide (“Perbutyl C” manufactured by NOF Corporation), 10-hour half-life temperature 119.5 ° C., di-t-butyl peroxide (NOF ( "Perbutyl D" manufactured by the company; 10-hour half-life temperature 123.7 ° C), lauroyl peroxide (such as "Perroyl L" manufactured by NOF Corporation; 10-hour half-life temperature 61.6 ° C), bis (4-t-butylcyclohexyl) peroxydicarbonate (“Perroyl TCP” manufactured by NOF Corporation; 10 hour half-life temperature 40.8 ° C.), 1,1,3,3-tetramethylbutylperoxy -2-E Ruhexanoate (such as “Perocta O” manufactured by NOF Corporation; 10-hour half-life temperature 65.3 ° C.), t-hexylperoxy-2-ethylhexanoate (“Perhexyl O manufactured by NOF Corporation) Etc .; 10-hour half-life temperature 69.9 ° C.), t-butyl peroxy-2-ethylhexanoate (“Perbutyl O” manufactured by NOF Corporation; 10-hour half-life temperature 72.1 ° C.) , T-hexylperoxyisopropyl monocarbonate (“Perhexyl I” manufactured by NOF Corporation; 10 hour half-life temperature 95.0 ° C.), t-butylperoxy-3,5,5-trimethylhexano Eat (“Nippon Oil Co., Ltd.” “Perbutyl 355”, etc .; 10-hour half-life temperature 97.1 ° C.), t-butyl peroxylaurate (“Nippon Co., Ltd.“ Perbutyl L ”, etc.); Seasonal temperature 98 .3 ° C.), t-butyl peroxyisopropyl monocarbonate (“Perbutyl I” manufactured by NOF Corporation; 10-hour half-life temperature 98.7 ° C.), t-butyl peroxy-2-ethylhexyl mono Carbonate (such as “Perbutyl E” manufactured by NOF Corporation; 10-hour half-life temperature 99.0 ° C.), t-hexyl peroxybenzoate (such as “Perhexyl Z” manufactured by NOF Corporation); 10 Time half-life temperature 99.4 ° C.), t-butyl peroxybenzoate (“Perbutyl Z” manufactured by NOF Corporation; 10-hour half-life temperature 104.3 ° C.), and the like. In the acrylic resin composition of the present invention, these organic peroxides may be used alone or in a mixture of two or more.

  In the acrylic resin composition of the present invention, among the organic peroxides, 10% of the organic peroxide is used to facilitate control of the polymerization temperature during the production of the acrylic resin composition and to improve the storage stability of the acrylic resin composition. An organic peroxide having a time half-life temperature of preferably 30 to 90 ° C, more preferably 50 to 80 ° C is desirable.

  In the acrylic resin composition of the present invention, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane (NOF) is used as the organic peroxide having a 10-hour half-life temperature of 30 to 90 ° C. "Perhexa TMH" manufactured by Co., Ltd .; 10 hour half-life temperature 86.7 ° C, 1,1-bis (t-hexylperoxy) cyclohexane ("Perhexa HC" manufactured by NOF Corporation, etc.); 10-hour half-life temperature 87.1 ° C.), 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane (“Perhexa 3M-95” manufactured by NOF Corporation, etc.); Period temperature 90.0 ° C.), lauroyl peroxide (“PAROIL L” manufactured by NOF Corporation; 10-hour half-life temperature 61.6 ° C.), bis (4-t-butylcyclohexyl) peroxydicarbonate ( Day “Perloyl TCP” manufactured by Co., Ltd .; 10 hour half-life temperature of 40.8 ° C., 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (manufactured by NOF Corporation) “Perocta O” and the like; 10-hour half-life temperature 65.3 ° C., t-hexylperoxy-2-ethylhexanoate (“Perhexyl O” manufactured by NOF Corporation); 10-hour half-life temperature 69 .9 ° C.), t-butyl peroxy-2-ethylhexanoate (“Perbutyl O” manufactured by NOF Corporation, etc .; 10 hour half-life temperature 72.1 ° C.) and the like.

  In the acrylic resin composition of the present invention, preferably, 0.05 to 1.0 mol of a polymerization initiator is used with respect to 1.0 mol of α-methylstyrene dimer, and the acrylic resin is produced by radical polymerization. There is a tendency that the production efficiency of acrylic resin is improved and the production time can be shortened. In the acrylic resin composition of the present invention, as the polymerization rate increases, the number average molecular weight of the acrylic resin tends to increase. Therefore, it is possible to design an acrylic resin having any number average molecular weight and weight average molecular weight. In the acrylic resin composition of the present invention, the polymerization temperature can be set in a relatively low temperature range of 50 to 100 ° C., such as methyl acrylate (boiling point 80 ° C.) and ethyl acrylate (boiling point 99 ° C.). Copolymerization of low-boiling acrylate monomers is also possible, and there is a tendency that the energy intensity related to production such as thermal energy can be greatly improved.

  In the acrylic resin composition of the present invention, the polymerization temperature control is very easy, and there is a tendency that sudden and large heat generation, viscosity increase, runaway reaction, etc. are eliminated during production. Therefore, in the acrylic resin composition of the present invention, the acrylic resin can be produced by any method such as solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, etc., and is optimal in accordance with the use of the acrylic resin composition. A manufacturing method can be selected.

  An example of a method for producing an acrylic resin composition by bulk polymerization in the acrylic resin composition of the present invention is shown below.

  A polymerization apparatus having a stirrer, a condenser, a thermometer, a nitrogen gas inlet, and a heating / cooling apparatus includes trimethylolpropane triacrylate, 2-ethylhexyl acrylate, β-carboxyethyl acrylate, N-vinyl-2-pyrrolidone, “ AMSD-GRU ”(α-methylstyrene dimer manufactured by Goi Kasei Co., Ltd., 2,4-diphenyl-4-methyl-1-pentene content 99.0% or more), 2,2′-azobis (2,4 -Dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd .; melting point 45 to 70 ° C., 10 hour half-life 51 ° C.) (“AMSD-GRU” 0.05 mol per 1.0 mol) ~ 1.0 mol) is charged and nitrogen gas bubbling is performed for 30 minutes. The temperature rise is started and the temperature is raised to 50 ° C in 30 minutes. Polymerization is carried out at 50 ° C. for 2 hours. The bubbling of nitrogen gas is changed to blowing, the temperature increase is started and the temperature is increased to 85 ° C. in 30 minutes. Polymerization is performed, for example, for about 3 to 16 hours until the predetermined polymerization rate or molecular weight is reached at 85 ° C. Cool to room temperature to produce an acrylic resin composition.

  In the acrylic resin composition of the present invention, it is desirable that the production process of the acrylic resin composition is divided into multistage production processes as seen from the polymerization temperature as in the above example. In the acrylic resin composition of the present invention, by dividing the production process into multiple stages, the production efficiency is improved, the production time is shortened, and the molecular weight of the acrylic resin tends to be easily controlled. In the acrylic resin composition of the present invention, the first step in the production of the acrylic resin composition is preferably near the 10-hour half-life temperature of the polymerization initiator, more preferably, the 10-hour half-life temperature ± 10 ° C., More preferably, it is recommended that the polymerization is carried out at a temperature of 10 hours half-life temperature ± 5 ° C. for about 30 minutes to 300 minutes. In the acrylic resin composition of the present invention, the second step in the production of the acrylic resin composition is preferably the 10-hour half-life temperature of the polymerization initiator to the 10-hour half-life temperature of the polymerization initiator + 30 ° C., more preferably. It is recommended that the acrylic resin composition be produced at a 10-hour half-life temperature of the polymerization initiator + 10 to a 10-hour half-life temperature of the polymerization initiator + 25 ° C.

  In the acrylic resin composition of the present invention, paints, pressure-sensitive adhesives, adhesives and the like using the acrylic resin composition can be manufactured according to a manufacturing method generally practiced in the industry. If necessary, paint additives such as pigment dispersants and leveling agents, and diluting solvents such as ethyl acetate and methyl ethyl ketone can be used.

  Hereinafter, the present invention will be described in detail with reference to examples.

  Prior to describing the details of the present invention in Examples, test methods and evaluation methods will be described. Further, unless otherwise specified, the amount used represents parts (g) and the composition represents% by weight.

1. Polymerization rate (%):
The ideal heating residue (X) when all the acrylic monomers used for acrylic resin production are polymerized, and the actual heating residue (Y), when polymerization rate (%) = Y / X × 100 Calculated. The heating residue was measured by heating at 140 ° C. for 60 minutes in accordance with JIS K 5407: 1997.

2. Acid value (mgKOH)
Measured according to JIS K 5407: 1997.

3. Gel fraction (%)
Using a Soxhlet extractor, the soluble component was extracted for 6 hours under reflux conditions of acetone / methanol = 1/1 (weight ratio), and after removing the soluble component, the gel fraction (%) = (Soxhlet The amount of acrylic resin remaining after extraction / the amount of acrylic resin before the Soxhlet test) × 100.

  Soxhlet extractors are: (1) Warming water tank (MODEL BS-44 manufactured by Yamato Scientific Co., Ltd.), (2) Reflux cooler (glass rubbing part size $ 34/45), (3) Extractor (glass (4) 150 mL round bottom flask (glass rubbing part size $ 24/40) (hereinafter also referred to as round bottom flask), extracted Cellulose cylindrical filter paper (hereinafter also referred to as “cylindrical filter paper”) used for the test was an inner diameter of 28 mm × length of 100 mm and a thickness of 1 mm. As the cylindrical filter paper, for example, “cellulose cylindrical filter paper” published in “2007-2008 Scientific Instrument General Catalog” p619 of Tokyo Glass Instrument Co., Ltd. was used.

  The water tank was filled with water until the lower half of the round bottom flask was immersed. The test was performed while water was injected appropriately so that the amount of water did not decrease due to water evaporation. An acrylic resin sample for measuring the gel fraction was placed in a cylindrical filter paper and set in an extractor. About 100 mL of extraction solvent methanol / acetone = 1/1 (weight ratio) and boiling stone were put in a round bottom flask, and a reflux condenser, an extractor and a round bottom flask were set and fixed with a clamp. The temperature of the water tank was raised and the water temperature was kept at 80 to 85 ° C. When the temperature of the extraction solvent rose and reached the boiling point, the extraction solvent in the round bottom flask began to evaporate and condensed in the reflux condenser. This was used as a signal when the extraction was started, and extraction was performed for 6 hours thereafter.

  The test sample was weighed to 4 digits after the decimal point using a precision balance. The weight of acrylic resin before extraction (= A) and the weight of cylindrical filter paper (= B) were measured. After the extraction test, the cylindrical filter paper was vacuum-dried at 23 ° C. for 8 hours using a vacuum dryer. After drying, the weight (= C) of the cylindrical filter paper and the acrylic resin was measured. Gel fraction (%) = (acrylic resin weight after test (CB)) / (acrylic resin weight before test (A)) × 100.

4). Molecular weight:
Weight average molecular weight (hereinafter also referred to as Mw), number average molecular weight (hereinafter also referred to as Mn), molecular weight distribution (hereinafter also referred to as d) = Mw / Mn is the “HLC-8220 GPC” system of Tosoh Corporation. It was measured.

  The polymerization rate and molecular weight were measured by sampling at a predetermined time after the second stage production process. Moreover, it sampled after cooling and measured the final polymerization rate and molecular weight.

5. Alkaline aqueous solution developability when used as an ultraviolet curable resist:
A resist material using the acrylic resin of Example or Comparative Example was prepared. A resist material using an acrylic resin was applied to a glass plate so that the film thickness after curing was 5 μm, and dried at 100 ° C. for 1 minute.

A portion of the coating was masked with a light-shielding film, a high-pressure mercury lamp with an illuminance of 120 W / cm was used, the lamp height was 10 cm, and the conveyor speed was 2 m / min. The resist material was cured by irradiating with ultraviolet rays at an irradiation amount of 840 mJ / cm ² under the irradiation conditions described above. The UV-irradiated part and the UV-irradiated part were showered for 1 minute in an aqueous caustic soda solution having a pH (25 ° C.) of 8.5 ± 0.5 to evaluate the solubility of the coating film. The case where the coating film in the ultraviolet irradiation part was insoluble and the coating film in the non-ultraviolet irradiation part was dissolved was regarded as acceptable.

6). Tensile shear strength test of radical curable adhesive A radical curable adhesive containing an acrylic resin composition was applied to a 2 mm thick polypropylene plate to a thickness of 50 μm, and a high pressure mercury lamp with an illuminance of 120 W / cm was used. Lamp height 10cm, conveyor speed 2m / min. Under the irradiation conditions, the adhesive layer was cured by irradiating with ultraviolet rays at an irradiation amount of 840 mJ / cm ² .

  10 g of 3-aminopropyltrimethoxysilane was mixed with 100 g of “Cotax TE-111” (acrylic resin manufactured by Toray Fine Chemical Co., Ltd.) to prepare a coating for an aluminum plate. The prepared paint was applied to an aluminum plate (JIS A-2017P: 1999) having a thickness of 2 mm so that the dry film thickness was 5 μm, and dried at 120 ° C. for 5 minutes.

  The polypropylene plate to which the adhesive was applied and the aluminum plate to which the paint was applied were crimped twice back and forth using a manual crimping device at room temperature in accordance with JIS Z 0237.

  After curing at 23 ° C. for 24 hours, the tensile shear strength (MPa) was measured according to JIS K 6850: 1999. A tensile shear strength of 5 MPa or more was deemed acceptable.

7). 90 ° Peel Test of Radical Curing Adhesive “Hardlen 14LLB” (product of Toyobo Co., Ltd.) was applied to a 2 mm thick polypropylene plate to a dry film thickness of 20 μm and dried at 120 ° C. for 1 minute. After applying a radical curable adhesive containing an acrylic resin composition to a dry film thickness of 50 μm, drying at 100 ° C. for 1 minute, using a high-pressure mercury lamp with an illuminance of 120 W / cm, a lamp height of 10 cm and a conveyor speed 2 m / min. Under the irradiation conditions, the adhesive layer was cured by irradiating with ultraviolet rays at an irradiation amount of 840 mJ / cm ² .

Acrylic resin composition used in producing radical curable adhesive, “light ester P-1A” (2-acryloyloxyethyl phosphate, product of Kyoeisha Chemical Co., Ltd.), “Aronix M-215” (isocyanur) Acid ethylene oxide-modified diacrylate, a product of Toagosei Co., Ltd.) was mixed at a solid content weight ratio of 80/10/10. 1% by weight of a photopolymerization initiator 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (“DAROCUR TPO”, a product of BASF Corporation) was added thereto. Furthermore, it adjusted so that solid content might be about 5 to 50% with ethyl acetate, and the adhesion promotion and anticorrosion primer for aluminum were produced. The prepared primer was applied to an aluminum foil with a thickness of 40 μm so that the dry film thickness was 0.05 to 20 μm, dried at 100 ° C. for 1 minute, and then a high-pressure mercury lamp with an illuminance of 120 W / cm was used. Height 10cm, conveyor speed 2m / min. Under the irradiation conditions, an ultraviolet ray was irradiated at an irradiation amount of 840 mJ / cm ² to form an adhesive and corrosion-resistant layer on aluminum.

  The polypropylene plate to which the adhesive was applied and the aluminum foil to which the primer was applied were crimped twice back and forth at room temperature using a manual crimping device in accordance with JIS Z 0237. After curing at 23 ° C. for 24 hours, the 90 ° peel strength (N / 15 mm) was measured in accordance with JIS K 6854-1: 1999 (adhesive-peeling adhesion strength test method). It was set as the pass at 5N / 15mm or more.

8). Evaluation of anti-fingerprint resistance as a self-healing paint of acrylic resin composition The acrylic resin composition was applied to a glass plate so as to have a film thickness of 20 μm and dried at 100 ° C. for 1 minute. Thereafter, a high-pressure mercury lamp with an illuminance of 120 W / cm was used, the lamp height was 10 cm, and the conveyor speed was 2 m / min. Under the above irradiation conditions, the self-recoverable coating layer was cured by irradiating with ultraviolet rays at an irradiation amount of 840 mJ / cm 2.

  The top of the coating film was pressed with a thumb at room temperature, and the appearance of fingerprints and the disappearance of fingerprint marks were visually determined. Those with no fingerprints or those with no fingerprint marks within a few tens of minutes had good fingerprint mark resistance and were accepted. Otherwise it was rejected.

9. Evaluation of scratch resistance of the acrylic resin composition as a self-healing paint The acrylic resin composition was applied to a glass plate to a film thickness of 20 μm and dried at 100 ° C. for 1 minute. Thereafter, a high-pressure mercury lamp with an illuminance of 120 W / cm was used, the lamp height was 10 cm, and the conveyor speed was 2 m / min. Under the above irradiation conditions, the self-recoverable coating layer was cured by irradiating with ultraviolet rays at an irradiation amount of 840 mJ / cm 2.

  The top of the coating film was pressed with the circumference of a 10-yen coin to make a dent mark on the coating film. A dent mark disappeared within 300 minutes, and it was judged that there was no difference from the initial state by visual observation, the self-repairing property was good, and the test was accepted. Otherwise it was rejected.

Example 1
In a 300 mL flask equipped with a stirrer, condenser, nitrogen gas inlet, heating and cooling device, thermometer, 0.050 g of acrylic acid adduct of bisphenol A diglycidyl ether, 91.8 g of 2-ethylhexyl acrylate, β- Nitrogen gas was charged with 0.2 g of carboxyethyl acrylate, 8.0 g of N-vinyl-2-pyrrolidone, 0.238 g of α-methylstyrene dimer and 0.050 g of 2,2′-azobis (2,4-dimethylvaleronitrile). Bubbling started.

  The temperature increase was started and the temperature was increased to 50 ° C. in 30 minutes. Thereafter, polymerization was carried out at 50 ° C. for 120 minutes. The temperature increase was started and the temperature was increased to 72 ° C. in 60 minutes. Thereafter, polymerization was carried out at 72 ° C. for 8 hours to produce an acrylic resin AC-1 of Example 1. During the production of the acrylic resin AC-1, there was no sudden and large heat generation and no increase in viscosity, and the polymerization temperature control was easy, and it was possible to produce it safely and safely. The acrylic resin AC-1 had a polymerization rate of 52.3% and a gel fraction of 0.0%. Table 1 shows details of composition, manufacturing method, characteristic values, and the like.

In Table 1, (1) indicates a polyfunctional acrylic monomer (A), (2) indicates an acrylic monomer (B), and (3) does not have a (meth) acryloyl group in the molecule. Vinyl monomer (C),
(4) shows α-methylstyrene dimer as a chain transfer agent, (5) shows 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, and (6) shows acrylic resin production conditions. The polymerization temperature and the production time of the first step and the second step are shown, and (7) shows the characteristic value of the produced acrylic resin. In Table 1, “epoxy ester 3002A” (product of Kyoeisha Chemical Co., Ltd.) is used as the acrylic acid adduct of bisphenol A diglycidyl ether, and ethylene oxide-modified bisphenol A diacrylate is “funcryl FA-324A” (Hitachi). Kasei Kogyo Co., Ltd. product) was used.

  Table 2 shows the relationship between the polymerization rate during the production of acrylic resin AC-1 and the change in molecular weight. In the acrylic resin AC-1 production, the molecular weight increased as the polymerization rate increased. Further, since the molecular weight distribution is increased with the increase in the polymerization rate and the gel fraction is 0.0%, it is presumed that the acrylic resin AC-1 is a non-crosslinked multi-branched polymer.

Examples 2-4
Acrylic resins AC-2 to AC-4 of Examples 2 to 4 were produced in the same manner as the acrylic resin AC-1 of Example 1 except that the composition, production method, and the like were changed as shown in Table 1. Table 1 shows characteristic values of the acrylic resins AC-2 to AC-4. During the production of the acrylic resins AC-2 to AC-4, there was no sudden and large heat generation and no increase in viscosity, and the polymerization temperature could be controlled easily and safely and safely.

  Table 2 shows the relationship between the polymerization rate and the molecular weight change during the production of the acrylic resins AC-2 to AC-4. As can be seen from Table 2, in the production of acrylic resins AC-1 to AC-4, the molecular weight increased as the polymerization rate increased. Further, since the molecular weight distribution is increased with the increase in the polymerization rate and the gel fraction is 0.0%, it is presumed that the acrylic resins AC-2 to AC-4 are non-crosslinked multi-branched polymers. The

Examples 5-10
Acrylic resins AC-5 to AC-10 of Examples 5 to 10 were produced in the same manner as the acrylic resin AC-1 of Example 1 except that the composition, production method, and the like were changed as shown in Table 3. Table 3 shows characteristic values of acrylic resins AC-5 to AC-10. During the production of the acrylic resins AC-5 to AC-10, there was no sudden and large heat generation and no increase in viscosity, and the polymerization temperature could be controlled easily and safely.

  Table 4 shows the relationship between the polymerization rate and the molecular weight change during the production of the acrylic resins AC-5 to AC-10. As can be seen from Table 4, in the production of acrylic resins AC-5 to AC-10, the molecular weight increased as the polymerization rate increased. Further, since the molecular weight distribution is increased with the increase in the polymerization rate and the gel fraction is 0.0%, it is presumed that the acrylic resins AC-5 to AC-10 are non-crosslinked hyperbranched polymers. The

Example 11
In a 300 mL flask equipped with a stirrer, condenser, nitrogen gas inlet, heating / cooling device, thermometer, 142.4 g of polymerization solvent propylene glycol methyl ether acetate, 0.500 g of 1,4-butanediol diacrylate, isobornyl acrylate Charge 59.5 g, ethyl acrylate 30.0 g, acrylic acid 10.0 g, α-methylstyrene dimer 7.126 g, 2,2′-azobis (2,4-dimethylvaleronitrile) 0.50 g, and nitrogen gas bubbling Started.

  The temperature increase was started and the temperature was increased to 50 ° C. in 30 minutes. Thereafter, polymerization was carried out at 50 ° C. for 120 minutes. The temperature increase was started and the temperature was increased to 72 ° C. in 60 minutes. Thereafter, polymerization was carried out at 72 ° C. for 8 hours to produce an acrylic resin AC-11 of Example 11. During the production of the acrylic resin AC-11, there was no sudden and large heat generation and no increase in viscosity, and the polymerization temperature could be controlled easily, safely and with peace of mind. The acrylic resin AC-11 had a heating residue of 40.3%, a polymerization rate of 100.0%, an acid value of 77.9 mgKOH, and a gel fraction of 0.0%. Table 5 shows details of composition, manufacturing method, characteristic values, and the like.

  In Table 5, (1) indicates the solvent used for the polymerization, (2) indicates the polyfunctional acrylic monomer (A), (3) indicates the acrylic monomer (B), and (4) indicates A vinyl monomer (C) having no (meth) acryloyl group in the molecule is shown, (5) is a chain transfer agent α-methylstyrene dimer, and (6) is a polymerization initiator 2,2 ′. -Indicates azobis (2,4-dimethylvaleronitrile), (7) indicates acrylic resin production conditions, polymerization temperature and production time for the first and second steps, and (8) indicates the characteristic value of the produced acrylic resin. Etc.

  Table 6 shows the relationship between the polymerization rate during the production of the acrylic resin AC-11 and the molecular weight change. In the acrylic resin AC-11 production, the molecular weight increased as the polymerization rate increased. Further, since the molecular weight distribution is increased with the increase in the polymerization rate and the gel fraction is 0.0%, it is presumed that the acrylic resin AC-11 is a non-crosslinked multi-branched polymer.

Examples 12-14
Acrylic resins AC-12 to AC-14 of Examples 12 to 14 were produced in the same manner as the acrylic resin AC-11 of Example 11 except that the composition, production method, and the like were changed as shown in Table 5. Table 5 shows characteristic values of acrylic resins AC-12 to AC-14. During the production of the acrylic resins AC-12 to AC-14, there was no sudden and large heat generation and no increase in viscosity, and the polymerization temperature could be controlled easily and safely.

  Table 6 shows the relationship between the polymerization rate and the change in molecular weight during the production of the acrylic resins AC-12 to AC-14. As seen in Table 6, in the production of acrylic resins AC-12 to AC-14, the molecular weight increased as the polymerization rate increased. Further, since the molecular weight distribution is increased with the increase in the polymerization rate and the gel fraction is 0.0%, it is presumed that the acrylic resins AC-12 to AC-14 are non-crosslinked hyperbranched polymers. The

Example 15
In a 300 mL flask equipped with a stirrer, condenser, nitrogen gas inlet, heating / cooling device, thermometer, 100.0 g of polymerization solvent ethyl acetate, polyfunctional acrylic monomer (A) isocyanuric acid ethylene oxide modified diacrylate 0 0.030 g, 94.8 g of acrylic monomer (B) isobutyl acrylate, 0.2 g of β-carboxyethyl acrylate, 5.0 g of N-vinyl-2-pyrrolidone of vinyl monomer (C), chain transfer agent 0.238 g of α-methylstyrene dimer and 0.050 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator were charged, and nitrogen gas bubbling was started.

  The temperature increase was started and the temperature was increased to 62 ° C. in 30 minutes. Thereafter, polymerization was carried out at 62 ° C. for 120 minutes. The temperature increase was started and the temperature was increased to 82 ° C. in 60 minutes. Thereafter, polymerization was carried out at 82 ° C. for 6 hours to produce an acrylic resin AC-15 of Example 15. During the production of the acrylic resin AC-15, there was no sudden and large heat generation and no increase in viscosity, and the polymerization temperature control was easy, and it was possible to produce it safely and safely. The acrylic resin AC-15 had a heating residue of 49.4%, a polymerization rate of 98.8%, and a gel fraction of 0.0%. Table 7 shows details of the composition, manufacturing method, characteristic values, and the like.

  In Table 7, (1) indicates the solvent used for the polymerization, (2) indicates the polyfunctional acrylic monomer (A), (3) indicates the acrylic monomer (B), and (4) indicates A vinyl monomer (C) having no (meth) acryloyl group in the molecule is shown, (5) is a chain transfer agent α-methylstyrene dimer, and (6) is a polymerization initiator 2,2 ′. -Indicates azobis (2,4-dimethylvaleronitrile), (7) indicates acrylic resin production conditions, polymerization temperature and production time for the first and second steps, and (8) indicates the characteristic value of the produced acrylic resin. Etc.

  Examples 16 to 18 Acrylic resins AC-16 to AC-18 of Examples 16 to 18 were produced in the same manner as the acrylic resin AC-15 of Example 15 except that the composition, production method, and the like were changed as shown in Table 7. did. Table 7 shows characteristic values of the acrylic resins AC-16 to AC-18. During the production of the acrylic resins AC-16 to AC-18, there was no sudden and great heat generation and no increase in viscosity, and the polymerization temperature could be controlled easily, safely and with peace of mind.

Examples 19-22
Acrylic resins AC-19 to AC-22 of Examples 19 to 22 were produced in the same manner as the acrylic resin AC-15 of Example 15 except that the composition, production method, and the like were changed as shown in Table 8. Table 8 shows the characteristic values of the acrylic resins AC-19 to AC-22. During the production of the acrylic resins AC-19 to AC-22, there was no sudden and great heat generation and no increase in viscosity, and the polymerization temperature control was easy, and it was possible to produce it safely and safely.

  In Table 8, (1) indicates the solvent used for the polymerization, (2) indicates the polyfunctional acrylic monomer (A), (3) indicates the acrylic monomer (B), and (4) indicates A vinyl monomer (C) having no (meth) acryloyl group in the molecule is shown, (5) is a chain transfer agent α-methylstyrene dimer, and (6) is a polymerization initiator 2,2 ′. -Indicates azobis (2,4-dimethylvaleronitrile), (7) indicates acrylic resin production conditions, polymerization temperature and production time for the first and second steps, and (8) indicates the characteristic value of the produced acrylic resin. Etc.

Comparative Example 1
In a 300 mL flask equipped with a stirrer, condenser, nitrogen gas inlet, heating / cooling device and thermometer, 142.4 g of propylene glycol methyl ether acetate as a polymerization solvent, 57.0 g of isobornyl acrylate, 30.0 g of ethyl acrylate, acrylic 10.0 g of acid, 3.0 g of N- (2-hydroxyethyl) acrylamide, 7.126 g of α-methylstyrene dimer, and 0.50 g of 2,2′-azobis (2,4-dimethylvaleronitrile) are charged with nitrogen gas Bubbling started.

  The temperature increase was started and the temperature was increased to 50 ° C. in 30 minutes. Thereafter, polymerization was carried out at 50 ° C. for 120 minutes. The temperature increase was started and the temperature was increased to 72 ° C. in 60 minutes. Thereafter, polymerization was carried out at 72 ° C. for 8 hours to produce an acrylic resin AC-23 of Comparative Example 1. During the production of the acrylic resin AC-23, there was no sudden and large heat generation and no increase in viscosity, and the polymerization temperature control was easy, and it was possible to produce it safely and with peace of mind. The acrylic resin AC-23 had a heating residue of 40.5%, a polymerization rate of 100.0%, an acid value of 77.9 mgKOH, and a gel fraction of 0.0%. Table 9 shows details of composition, manufacturing method, characteristic values, and the like.

  In Table 9, (1) indicates the solvent used for the polymerization, (2) indicates the polyfunctional acrylic monomer (A), (3) indicates the acrylic monomer (B), and (4) indicates A vinyl monomer (C) having no (meth) acryloyl group in the molecule is shown, (5) is a chain transfer agent α-methylstyrene dimer, and (6) is a polymerization initiator 2,2 ′. -Indicates azobis (2,4-dimethylvaleronitrile), (7) indicates acrylic resin production conditions, polymerization temperature and production time for the first and second steps, and (8) indicates the characteristic value of the produced acrylic resin. Etc.

  Table 10 shows the relationship between the polymerization rate and the molecular weight change during the production of the acrylic resin AC-23. In the production of acrylic resin AC-23, the molecular weight increased as the polymerization rate increased.

Comparative Examples 2-4
Acrylic resins AC-24 to AC-26 of Comparative Examples 2 to 4 were produced in the same manner as the acrylic resin AC-23 of Comparative Example 1 except that the composition, production method, and the like were changed as shown in Table 9. Table 7 shows characteristic values of the acrylic resins AC-24 to AC-26. During the production of the acrylic resin AC-25, there was no sudden and large heat generation and no increase in viscosity, and the polymerization temperature control was easy, and it was possible to produce it safely and safely. Acrylic resins AC-24 and AC-26 using a large amount of 1,4-butanediol diacrylate and trimethylolpropane triacrylate, which are polyfunctional acrylic monomers (A), could not be produced because they gelled during the production.

  Table 10 shows the relationship between the polymerization rate and the change in molecular weight during the production of the acrylic resin AC-25. As can be seen from Table 10, in the acrylic resin AC-25 production, the molecular weight increased as the polymerization rate increased.

Comparative Examples 5-8
Acrylic resins AC-27 to AC-30 of Comparative Examples 5 to 8 were produced in the same manner as the acrylic resin AC-1 of Example 1 except that the composition, production method, and the like were changed as shown in Table 11. Table 11 shows characteristic values of the acrylic resins AC-27 to AC-30. In Table 11, the acrylic acid adduct of bisphenol A diglycidyl ether represents “epoxy ester 3002A” (product of Kyoeisha Chemical Co., Ltd.).

  Table 12 shows the relationship between the polymerization rate and the molecular weight change during the production of the acrylic resins AC-27 to AC-30. As seen in Table 12, in the production of acrylic resins AC-27 to AC-30, the molecular weight increased as the polymerization rate increased. On the other hand, in the acrylic resin AC-30 production in which n-butyl methacrylate having a methacryloyl group in the molecule was used, the molecular weight was greatly reduced as the polymerization rate increased.

  Using the acrylic resin compositions produced in Examples and Comparative Examples, they were tested as resist materials, radical curable adhesives, and self-healing paints. Details are shown below.

[Testing and evaluation as resist materials]
Tables 13 and 14 show production examples and test results of resist materials using acrylic resins AC-11 to AC-14 of Examples 11 to 14, acrylic resins AC-23 and AC-25 of Comparative Examples 1 and 3, respectively. .

  In Tables 13 and 14, (1) indicates the acrylic resin used for the resist material, (2) indicates the polyfunctional acrylic monomer as a crosslinking agent, and (3) indicates the photopolymerization initiator “IRUGACURE 651”. (Photopolymerization initiator, product of BASF Corporation).

  The resist material RE-1 using the acrylic resin AC-11 of the embodiment will be described as an example. 100 g of acrylic resin AC-11, 2.0 g of trimethylolpropane trimethacrylate, and 0.4 g of 2,2-dimethoxy-1,2-diphenylethane-1-one are taken in a container and mixed until uniform to form a resist material RE-1 was produced.

  Using the resist materials RE-2 to RE-8 produced in the same manner, alkaline aqueous solution developability was tested and evaluated. As shown in Tables 13 and 14, the resist materials RE-1 to RE-6 using the acrylic resins AC-11 to AC-14 of Examples showed good developability. Moreover, as can be seen from the test results of the resist materials RE-5 and RE-6, the resist material using the acrylic resin of the example shows ultraviolet curability without using a photopolymerization initiator. It is clear that it performs well. As a resist material, improvement in storage stability, formation of fine patterning, and the like are expected.

  The resist materials RE-7 and RE-8 using the acrylic resins AC-23 and AC-25 of the comparative examples could not be used as resist materials because the coating film was dissolved in an alkaline developer regardless of the presence or absence of ultraviolet irradiation. .

[Test / Evaluation as Radical Curing Adhesive Using Acrylic Resin in Examples (Tensile Shear Strength)]
Production Examples and Test Results of Radical Curing Adhesives Using Acrylic Resins AC-1 to AC-10 and AC-15 to 18 of Examples 1 to 10 and Examples 15 to 18 are shown in Tables 15, 16, and 17. It was shown to.

  In Table 15, Table 16, and Table 17, the acrylic acid adduct of bisphenol A diglycidyl ether which is a polyfunctional acrylic monomer (A) uses “epoxy ester 3002A” (product of Kyoeisha Chemical Co., Ltd.) The isocyanuric acid ethylene oxide modified diacrylate uses “Aronix M-215” (product of Toagosei Co., Ltd.), and the photopolymerization initiator 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide is “ DAROCUR TPO "(product of BASF Corporation) was used. As the chlorinated polyolefin resin, “Hardylene 14LLB” (product of Toyobo Co., Ltd.) is used, and the hindered amine compound is “Sanol LS-744” (4-benzoyloxy-2,2,6,6-tetramethylpiperidine) (Sankyo). Lifetech Co., Ltd. product) was used.

  Radical curable adhesives SE-1 to SE-10 using the acrylic resin compositions AC-1 to AC-10 of the examples are polypropylene (organic polymer material) -aluminum whose adherend is a difficult-to-adhere substrate (aluminum) In spite of the adhesion between different materials having different properties such as coefficient of thermal expansion (non-ferrous metal), both showed strong tensile shear strength by so-called bonding after curing. In any of the radical curable adhesives SE-1 to SE-10 using the acrylic resin composition of the example, the adhesive failure was cohesive failure, and a good adhesion state was exhibited. Moreover, since the hindered amine compound “Sanol LS-744” (4-benzoyloxy-2,2,6,6-tetramethylpiperidine) (product of Sankyo Lifetech Co., Ltd.) is used, the curability is good. there were.

  Radicals using acrylic resin compositions AC-2 and AC-4, in which an acrylic acid adduct of bisphenol A diglycidyl ether, which is a polyfunctional acrylic monomer (A), and ethylene oxide-modified bisphenol A diacrylate are often used The curable adhesives SE-2 and SE-4 exhibited a tensile shear strength of 20 MPa or more that can be used as a structural adhesive.

  Radical curable adhesive SE-7 using an acrylic resin composition AC-7 in which a large amount of N-vinyl-2-pyrrolidone is used, and acrylic resin composition AC-10 in which a large amount of vinyltriethoxysilane is used. The radical curable adhesive SE-10 thus produced exhibited a tensile shear strength of 20 MPa or more that can be used as a structural adhesive.

[Test / Evaluation as Radical Curing Adhesive Using Acrylic Resin of Examples (90 Degree Peeling Test)]
The functional acrylic resin adhesives SE-11 to SE-14 using the acrylic resin compositions AC-15 to AC-18 of the examples are composed of isocyanuric acid ethylene oxide-modified diacrylate as the polyfunctional acrylic monomer (A). Since it was used, all exhibited high level adhesion performance despite the 90 degree peel test. In addition, the adhesive strength tended to increase as the amount of isocyanuric acid ethylene oxide-modified diacrylate used in the acrylic resin composition used in the adhesive increased. It is presumed that this is a material and adhesive suitable for packaging materials containing aluminum, polypropylene, and the like, solar battery backsheet applications, and the like.

[Test and evaluation as a radical curable adhesive using acrylic resin of comparative example (tensile shear strength)]
Table 18 shows production examples and test results of radical curable adhesives using acrylic resins AC-27 to AC-30 of Comparative Examples 5 to 8.

  The radical curable adhesive using the acrylic resin compositions AC-27 to AC-30 of the comparative examples does not exhibit a tensile shear strength that can withstand practical use even when a chlorinated polyolefin or a hindered amine compound is used. It was.

[Testing and evaluation as self-healing paint using acrylic resin of Example]
Self-healing paints were produced using the acrylic resin compositions of Examples 19 to 22, and tested and evaluated. The paint composition, test results, etc. are shown in Table 19. In Table 19, “Aronix M-215” (product of Toagosei Co., Ltd.) was used as the isocyanuric acid ethylene oxide-modified diacrylate. As the photopolymerization initiator 1-hydroxy-cyclohexyl-phenyl-ketone, “IRGACURE 184” (product of BASF Corp.) was used.

  As seen in Table 19, the self-healing paint using the acrylic resin composition of the example exhibited excellent performance in self-healing property, non-staining property and the like.

  As described above, the acrylic resin composition of the present invention exhibits good and well-balanced performance in a wide variety of applications such as photoresists, radical curable adhesives, and self-recoverable coating amounts. .

Claims (4)

0.002 to 1.5% by weight of a polyfunctional acrylic monomer (A) having two or more acryloyl groups in the molecule, and an acrylic monomer (B) having one acryloyl group in the molecule 88. Acrylic resin containing 5 to 99.998% by weight of acrylic resin comprising 0.0 to 10.0% by weight of vinyl monomer (C) having a radical polymerizable unsaturated group other than (meth) acryloyl group in the molecule Composition. A polyfunctional acrylic monomer (A) having two or more acryloyl groups in the molecule is an acrylic acid adduct of 1,4-butanediol diacrylate, trimethylolpropane triacrylate, bisphenol A diglycidyl ether, ethylene oxide The acrylic resin composition according to claim 1, which is at least one polyfunctional acrylic monomer selected from a modified bisphenol A diacrylate and an isocyanuric acid ethylene oxide-modified diacrylate. The acrylic resin composition according to claim 1 or 2, wherein the polyfunctional acrylic monomer (A) having two or more acryloyl groups in the molecule is an isocyanuric acid ethylene oxide-modified diacrylate. The acrylic resin composition according to claim 1 or 2, wherein the gel fraction of the acrylic resin composition is less than 3%.