JP2002003559A - Crosslinking resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition easily curable by radiation of a active energy ray, particularly quickly curing even by radiation of a ultraviolet ray, excellent in weather resistance of cured material obtained, having no problem of odor, and furthermore excellent in abrasion resistance of cured material and adhesion to base material. SOLUTION: This crosslinked resin composition is composed of polymer having a maleimide group and an ethylenically unsaturated group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crosslinkable resin composition containing a polymer having a maleimide group and an ethynylene unsaturated group. It has excellent properties and abrasion resistance, and can be used for coating agents, adhesives, binders, molded products and the like, and can be awarded in these technical fields.

[0002]

2. Description of the Related Art Active energy ray-curable compositions can rapidly reduce the energy and time required for drying as compared with conventional solvent-type resin compositions due to their fast-curing properties. Can save space because it is unnecessary, and since the composition requires only a small amount of solvent or does not need to use it at all, the amount of use increases year by year as a material that is friendly to the global environment. Is coming. In recent years, active energy ray-curable compositions have been used in a wider variety of fields, and the performance required in those fields is based on the combination of only oligomers and monomers conventionally used as raw materials. Then, there are some cases that cannot be achieved.

On the other hand, plastic molded articles manufactured from polymethyl methacrylate resin, polycarbonate resin and the like have various advantages such as light weight, excellent impact resistance, and easy molding processing. Used in many fields. However, since these plastic molded products have insufficient wear resistance on the surface, the surface is easily damaged, and improvement in wear resistance is desired. or,
These molded products are sometimes used outdoors for automobile parts and the like, and are strongly required to have weather resistance. In order to improve the abrasion resistance, a method of coating the surface of these plastic molded products with an ultraviolet-curable composition has been studied.
Abrasion resistance and adhesion to plastic may be insufficient, and even if these performances are satisfied to some extent, there is often a problem in weather resistance. That is, in the case of an ultraviolet-curable composition containing (meth) acrylate as a main component, which occupies most of the active energy ray-curable composition, in order to cure the composition with ultraviolet rays, light that generates active radicals by irradiation with ultraviolet rays is used. It is necessary to incorporate a polymerization initiator into the composition. However, since the photopolymerization initiator remains in the cured product after the composition is cured, it deteriorates the weather resistance of the obtained cured product, and causes coloring, fading, peeling of the coating film, cracks, and the like. Therefore, the ultraviolet curable composition is insufficient for applications requiring weather resistance. In addition, the decomposed product of the photoinitiator present in the cured product after curing sometimes causes odor of the cured product. Attempts have been made to improve the weather resistance by blending a weather resistance improver such as an ultraviolet absorber, a light stabilizer and an antioxidant, but the effect is insufficient and the weather resistance improver is hardened. In order to suppress the reaction, there is also a problem that the ultraviolet curability of the composition is reduced and the productivity is reduced.

Recently, it has been discovered that N-substituted maleimide compounds act as a photopolymerization initiator, and it has been reported that vinyl ethers and acrylates can be polymerized by ultraviolet rays without a photopolymerization initiator. [Sony J
Onsson et al., Radotech '95 Europe, Preliminary Collection (Academic Day), page 34]. The photopolymerization initiation function of this N-substituted maleimide compound is different from a conventional photopolymerization initiator and is excellent in that it is not curable in a thin film and does not suffer from polymerization inhibition by oxygen in the air. , Solid and high melting point, difficult to handle,
In order to use it in a liquid form, it is necessary to dissolve it in (meth) acrylate or the like. However, the maleimide compound may have low solubility in (meth) acrylate or the like. When the blending amount of was increased, there were cases where precipitation occurred. Therefore, only a composition having a limited composition can be produced, and when the composition of the composition is changed in accordance with the physical properties required for various uses, the desired physical properties may not be satisfied. Furthermore, when the maleimide compound is a low molecular weight compound, and is compounded as a component having a function as a photopolymerization initiator in the curable composition, if it remains without being bonded to the cured product, the properties of the cured product are reduced. There was also the problem of lowering.

The present inventors have found a composition comprising a polymer having a monomer unit of (meth) acrylate having a maleimide group as a composition for solving the above problems (WO98 / 58912). No.).

[0006]

However, the above composition may be unsatisfactory when a higher curing speed is required or when more excellent weather resistance and chemical resistance are required. Was. On the other hand, as a compound having excellent curability, a low molecular weight compound having a maleimide group and a vinyl ether group as an ethylenically unsaturated group is known (He
nrik Andersson et al., Journal of Coating Technology, V
ol. 69, No865, p91, 1997), and the resulting cured film has hardness,
It was inadequate in terms of adhesion to the substrate and resistance to water and chemicals.

According to the present invention, the composition can be easily cured by irradiation with active energy rays, particularly quickly even when irradiated with ultraviolet rays, and the resulting cured product has excellent weather resistance and has no problem of odor. The inventor conducted intensive studies to find a composition having excellent abrasion resistance and adhesion to a substrate of the cured product.

[0008]

The present inventors have made various studies and found that a composition containing a polymer having a maleimide group and an ethylenically unsaturated group solves the above-mentioned problems. And completed the present invention. Hereinafter, the present invention will be described in detail. In this specification, acrylate and / or methacrylate are referred to as (meth)
Acrylate, acrylic acid and / or methacrylic acid are called (meth) acrylic acid, and acryloyl and / or methacryloyl groups are called (meth) acryloyl groups.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Component 1-1. Maleimide group and ethylenically unsaturated group As the maleimide group in the polymer having the maleimide group and the ethylenically unsaturated group of the component (A) of the present invention, there are various maleimide groups, and those represented by the following formula (1) Is preferred.

[0010]

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[In the formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group,
It represents an alkenyl group or an aryl group, or R ¹ and R ² together represent a saturated or unsaturated hydrocarbon group forming a 5- or 6-membered ring. ]

The aryl group includes a phenyl group and the like.
be able to. Form a 5- or 6-membered ring
As the unsaturated or saturated hydrocarbon group to be formed,
CH _TwoCH_TwoCH_Two-, Group -CH = CHCH_Two-, Group -CH
_TwoCH_TwoCH_TwoCH_Two-, Group -CH_TwoCH = CHCH_Two-And
Group -CH = CHCH = CH- and the like.

R¹And R^TwoOne is a hydrogen atom and the other is
Is an alkyl group having 4 or less carbon atoms, R ¹And R^TwoBoth are charcoal
Alkyl groups with a prime number of 4 or less and each one
Saturated hydrocarbon groups that form carbocycles facilitate polymer
Manufacturable, excellent in solubility and storage stability, resulting composition
This is preferred in that the crosslinked coating film of the above is excellent in water resistance. In addition,
Of these, each forms a carbocyclic ring
More preferably a saturated hydrocarbon group, and particularly preferably a group-
CH_TwoCH_TwoCH_TwoCH_Two-. Specific examples of maleimide groups
Are shown in the following equations (2) to (7). Among these, dissolution
Formula (2) or (3) in terms of excellent stability and storage stability.
Maleimide groups are preferred.

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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There are various types of ethylenically unsaturated groups in the component (A) of the present invention, and examples thereof include a vinyl group, an allyl group and a (meth) acryloyl group.

1-2. Polymer As the component (A) in the present invention, polymers obtained by various methods can be used. As a production method, there are various methods, a method of preparing a prepolymer having a functional group and a maleimide group shown below, and reacting the prepolymer with a compound having a functional group capable of reacting with the functional group. It is preferable to prepare a prepolymer having a functional group and react a functional group capable of reacting with the functional group with a compound having a maleimide group. A method of adding a compound having an ethylenically unsaturated group and an isocyanate group (hereinafter referred to as an isocyanate-based unsaturated compound) to a maleimide group- and hydroxyl group-containing prepolymer. A method of adding a compound having an ethylenically unsaturated group and an epoxy group (hereinafter, referred to as an epoxy-based unsaturated compound) to a prepolymer containing a maleimide group and a carboxyl group. A method in which a compound having an ethylenically unsaturated group and a carboxyl group (hereinafter, referred to as a carboxyl unsaturated compound) is added to a prepolymer containing a maleimide group and an epoxy group. A method of adding a compound having an ethylenically unsaturated group and a hydroxyl group (hereinafter referred to as a hydroxyl-based unsaturated compound) to a prepolymer containing a maleimide group and an isocyanate group. A method of adding a hydroxyl-based unsaturated compound to a prepolymer containing a maleimide group and an acid anhydride group. A method of adding a compound having a maleimide group and a hydroxyl group and a hydroxyl-based unsaturated compound to an acid anhydride group-containing prepolymer. A method of adding a compound having a maleimide group and a carboxyl group and a carboxyl unsaturated compound to an epoxy group-containing prepolymer.

1-2-1. Method for Producing Prepolymer The method for producing a prepolymer having a maleimide group in the above-mentioned methods (1) to (4) includes a compound having an ethylenically unsaturated group and a maleimide group (hereinafter referred to as a maleimide-based unsaturated compound). Monomer) and a compound having a hydroxyl-based unsaturated compound, a carboxyl-based unsaturated compound, an epoxy-based unsaturated compound, an isocyanate-based unsaturated compound, and an ethylenically unsaturated group and an acid anhydride group (hereinafter referred to as acid anhydride). (Referred to as “system compound”) to obtain a prepolymer.

The maleimide-based unsaturated monomer is preferably a (meth) acrylate having a maleimide group, and can be produced by the methods described in the following literatures and patents. -Kiyoshi Kato et al., Journal of the Society of Synthetic Organic Chemistry, 30 (10), 89
7, (1972)-Javier de Abajo et al., Polymer, vol33.
(5), (1992)-JP-A-56-53119, JP-A-1-242569
issue

Preferred examples of the (meth) acrylate having a maleimide group are shown in the following formula (8).

[0025]

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[In the formula (8), R ¹ and R ² have the same meanings as described above.] R ³ represents a linear or branched alkylene group having 1 to 6 carbon atoms, R ⁴ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6. ]

Examples of the hydroxyl-based unsaturated compound include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.
Examples include acrylates and hydroxyalkyl vinyl ethers such as hydroxybutyl vinyl ether.

As the carboxyl unsaturated compound,
Oligomers of dimer or more which are the products of Michael addition of unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, (meth) acrylic acid, ω-carboxypolycaprolactone mono (meth) acrylate, phthalate Carboxyl group-containing (meth) acrylates such as monohydroxyethyl (meth) acrylate and monohydroxyethyl succinate (meth) acrylate;

Examples of the epoxy-based unsaturated compound include glycidyl (meth) acrylate and epoxy group-containing (meth) acrylate such as cyclohexene oxide group-containing (meth) acrylate represented by the following formula (9).

[0030]

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As the isocyanate-based unsaturated compound,
Examples include (meth) acryloyloxyethyl isocyanate and dimethyl-m-isopropenylbenzyl isocyanate represented by the following formula (10).

[0032]

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Examples of the acid anhydride unsaturated compound include maleic anhydride and itaconic acid.

In the above method, an acid anhydride unsaturated compound and, if necessary, other monomers are polymerized. In the above method, an epoxy unsaturated compound and, if necessary, A prepolymer can be obtained by polymerizing other monomers.

Other monomers can be copolymerized with the prepolymer, if necessary. For example, styrene, α-methylstyrene, (meth) acrylonitrile,
Examples include vinyl acetate and (meth) acrylate.
Specific examples of (meth) acrylate include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, and cyclohexyl. Alicyclic alkyl (meth) acrylates such as (meth) acrylate, substituted aryl (meth) acrylates such as benzyl (meth) acrylate, and alkoxy (such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate (Meth) acrylate, isobornyl (meth) acrylate, and (meth) acrylate containing an alkoxysilyl group. In addition to these monomers, macromonomer type monomers can be used. Thereby, the component (A) becomes a graft copolymer or a block copolymer. Examples of the macromonomer type monomer include those having a polysiloxane and those having a fluorine-based polymer chain.

In the present invention, particularly in applications requiring weather resistance, aromatic monomers such as styrene and α-methylstyrene are not used, or 20% by weight or less of all monomers. preferable.

As a method for producing the prepolymer, the prepolymer can be produced by polymerizing the monomer according to a conventional method such as a solution polymerization method, an emulsion polymerization method, and a high temperature continuous polymerization method. In the case of synthesizing by a solution polymerization method, it is obtained by dissolving a raw material monomer to be used in an organic solvent, adding a thermal polymerization initiator, and heating and stirring. In the case of synthesis by radical polymerization by a solution polymerization method, it is obtained by dissolving a raw material monomer to be used in an organic solvent, adding a thermal radical polymerization initiator, and stirring with heating. If necessary, a chain transfer agent can be used to adjust the molecular weight of the polymer. Examples of the thermal polymerization initiator to be used include peroxides, azo compounds, and redox initiators that generate radical species by heat. Examples of peroxides include benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide and the like. Examples of the azo compound include azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile and the like. Examples of redox initiators include hydrogen peroxide-iron (II) salt, peroxodisulfate-sodium bisulfite, cumene hydroperoxide-iron (II) salt and the like. Organic solvents used include benzene, toluene, ethyl acetate, methanol, dimethylformamide and the like. Examples of the chain transfer agent include dodecyl mercaptan, xanthate disulfide, diazothioether, 2-propanol and the like.

The prepolymer can be produced by high-temperature continuous polymerization, if necessary. According to the high-temperature continuous polymerization method, a prepolymer having a low viscosity and a low molecular weight can be obtained, and further, the polymerization method does not require the use of a thermal polymerization initiator, or a small amount even when a thermal polymerization initiator is used. Since a prepolymer of the desired molecular weight can be obtained by use,
The copolymer is preferable because it has a high purity and hardly contains impurities that generate radical species by heat or light, and provides stable physical properties. As the high-temperature continuous polymerization method, JP-A-57-502171, JP-A-59-6207,
A known method disclosed in, for example, JP-A-60-215007 may be used. For example, filling a pressurizable reactor with a solvent,
After setting to a predetermined temperature under pressure, a monomer mixture comprising a monomer and, if necessary, a polymerization solvent is supplied to the reactor at a constant supply rate, and an amount corresponding to the supply amount of the monomer mixture is supplied. A method of extracting the reaction solution may be used. Further, a thermal polymerization initiator may be added to the monomer mixture, if necessary. The reaction temperature is preferably from 150 to 350C. The pressure is
It depends on the reaction temperature and the boiling point of the monomer mixture and the solvent used and does not affect the reaction, but any pressure may be used as long as the reaction temperature can be maintained. The residence time of the monomer mixture is preferably 2 to 60 minutes.

1-2-3. Method for Producing Polymer In the above methods (1) to (4), a maleimide group-containing prepolymer having various functional groups is added to an isocyanate-based unsaturated compound, an epoxy-based unsaturated compound, and a carboxyl-based unsaturated compound, respectively. A polymer can be obtained by adding a compound and a hydroxyl-based unsaturated compound. Further, in the above method, a compound having a maleimide group and a hydroxyl group and a hydroxyl-based unsaturated compound are added to the acid anhydride group-containing prepolymer, and the maleimide group and the epoxy group-containing prepolymer are added in the above method. A polymer can be obtained by adding a compound having a carboxyl group and a carboxyl unsaturated compound.

Examples of the compound having an isocyanate-based unsaturated compound, an epoxy-based unsaturated compound, a carboxyl-based unsaturated compound, and a hydroxyl-based unsaturated compound include the same compounds as described above.

Examples of the compound having a maleimide group and a hydroxyl group in the above method include a compound represented by the following formula (11).

[0042]

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[However, in the formula (11), R ¹ and R ² have the same meaning as described above. R ⁵ represents a linear or branched alkylene group having 1 to 6 carbon atoms. ]

The carboxyl group-containing compound having a maleimide group used in the above method includes a compound represented by the following formula (12).

[0045]

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[However, in the formula (12), R ¹ and R ² have the same meanings as described above. R ⁵ represents a linear or branched alkylene group having 1 to 6 carbon atoms. ]

In any case, it can be produced by adding each compound to the prepolymer in an organic solvent, an aqueous medium or without a solvent. As the conditions of each addition reaction, a reaction temperature, a reaction time, and a catalyst may be selected according to each reaction.

The component (A) has a number average molecular weight of 1,000 to 1,
It is preferably 100,000, more preferably 10,000 to 5
100,000. If this value is less than 1000, the weather resistance becomes insufficient or the adhesion becomes insufficient.
If the amount exceeds one million, the stability of the solution may be impaired. In the present invention, the number average molecular weight is a value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter abbreviated as GPC) using tetrahydrofuran as a solvent with reference to the molecular weight of polystyrene.

The proportion of the maleimide group in the component (A) is preferably from 10 to 40% by weight of the monomer having a maleimide group, based on all the monomers used.
If this ratio is less than 10% by weight, the weather resistance may be insufficient, or curing or crosslinking (hereinafter simply referred to as “curing”) may be insufficient, resulting in insufficient hardness. When a thick film is cured, the cured film proceeds only on the surface, and the adhesion may be poor. The proportion of the ethylenically unsaturated group in the copolymer is preferably from 10 to 40% by weight of the monomer having an ethylenically unsaturated group based on all the monomers used. If this proportion is less than 10% by weight, the weather resistance will be insufficient or the curing will be insufficient, resulting in insufficient hardness, while if it exceeds 40% by weight, the adhesion will be poor. is there.

The composition of the present invention comprises the component (A) as an essential component, and may be in the form of a solution of the component (A) in an organic solvent, an aqueous dispersion of the component (A) and the component (A). Examples of the composition include the component (B) described below. In this case, the proportion of the component (A) is preferably 5 to 95% by weight in the case of an organic solvent solution, and 10 to 70% by weight in the case of an aqueous dispersion.
Is preferably, more preferably 20 to 60% by weight,
When used in combination with the component (B), it is as described below.

2. Component (B) In the present invention, for the purpose of adjusting the strength, flexibility and productivity of the coating film, if necessary, a compound having an ethylenically unsaturated group of the component (B) in the component (A) may be used. Can be used together. As the compound having an ethylenically unsaturated group,
Various substances other than the component (A) can be used, and both monomers and oligomers can be used.

2-1. Monomer Examples of the monomer include (meth) acrylate and vinyl ether. As the (meth) acrylate, 2-hydroxyethyl (meth) acrylate and 2
Hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate; acrylates of phenolic alkylene oxide adducts such as phenoxyethyl (meth) acrylate and halogen nucleus substitutes thereof; mono- or di (meth) acrylates of ethylene glycol Mono- or di (meth) acrylates of glycols, such as mono (meth) acrylate of methoxyethylene glycol, mono or di (meth) acrylate of tetraethylene glycol and mono or di (meth) acrylate of tripropylene glycol; trimethylolpropanetri (Meth) acrylate, trihydroxyethyl isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate Rate and (meth) acrylates of polyols such as dipentaerythritol hexaacrylate, and alkylene oxide adducts of these polyols (meth) acrylate.

Examples of the vinyl ether include triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, and hydroxyethyl vinyl ether.

Examples of other monomers include N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine, N-vinylformamide, N-vinylacetamide and the like.

2-2. Oligomers As oligomers, urethane (meth) acrylate,
Examples include polyester (meth) acrylate and epoxy (meth) acrylate. Examples of the urethane (meth) acrylate oligomer include a reaction product obtained by further reacting a hydroxyl group-containing (meth) acrylate with a polyol and an organic polyisocyanate reaction product. Here, examples of the polyol include a low molecular weight polyol, polyethylene glycol and polyester polyol. Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, cyclohexane dimethanol, and 3-methyl-1,5-pentanediol. Examples of the polyether polyol include polyethylene glycol and polypropylene glycol. Is a reaction product of these low molecular weight polyols and / or polyether polyols with an acid component such as dibasic acid such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid or anhydride thereof. . As organic polyisocyanate, tolylene diisocyanate, 4,4′-
Examples include diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

Examples of the polyester (meth) acrylate oligomer include a dehydration condensate of a polyester polyol and (meth) acrylic acid. As the polyester polyol, ethylene glycol, polyethylene glycol, cyclohexanedimethanol, 3-methyl-
Low molecular weight polyols such as 1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol and trimethylolpropane, and polyols such as alkylene oxide adducts thereof, and adipic acid, succinic acid, phthalic acid, A reaction product from a dibasic acid such as hexahydrophthalic acid and terephthalic acid or an acid component such as an anhydride thereof is exemplified.

Epoxy acrylate is obtained by adding (meth) acrylic acid to an epoxy resin and adding (meth) acrylate of bisphenol A type epoxy resin, (meth) acrylate of phenol or cresol novolac type epoxy resin and polyether of (meth) acrylate. Examples include diglycidyl ether with (meth) acrylic acid.

As the component (B), those having two or more (meth) acryloyl groups in one molecule are preferable because the resulting cured product has excellent hardness and abrasion resistance. As the component (B), it is preferable to use an aliphatic or alicyclic compound because it has better weather resistance and curability than a compound having an aromatic ring.

In this case, the proportion of the components (A) and (B) in the composition is based on the total amount of the components (A) and (B).
Component (A) is 5 to 95% by weight and component (B) is 95 to 5% by weight.
It is more preferable that the component (A) is 10
-90% by weight and 90-10% by weight. If the amount of the component (A) exceeds 95% by weight or the amount of the component (B) is less than 5% by weight, the hardness and abrasion resistance of the cured product may decrease, while the amount of the component (A) may be 5% by weight. Or less than (B) 95
If the amount is more than the weight percentage, the curability may be reduced.

3. Photopolymerization initiator The composition of the present invention is one that is cured by irradiation with active energy rays, and is cured without problems even in the case of curing by ultraviolet rays without the addition of a photopolymerization initiator. For the purpose, a photopolymerization initiator can be blended as long as the weather resistance is not impaired.

Examples of the photopolymerization initiator include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether and their alkyl ethers, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-. 2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexylphenylketone and 2-methyl-
Acetophenones such as 1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone Anthraquinone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,2
There are thioxanthone such as 4-diisopropylthioxanthone, ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone such as benzophenone, and xanthone. These photopolymerization initiators can be used alone or in combination with a benzoic acid-based or amine-based photopolymerization initiator. The preferred mixing ratio of these photopolymerization initiators is 5 parts by weight or less, more preferably 2 parts by weight or less based on 100 parts by weight of the composition.

4. Weather Resistance Improver The composition of the present invention may further contain one or more weather resistance improvers selected from UV absorbers, light stabilizers and antioxidants for the purpose of further improving weather resistance. .

Examples of the ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2
And benzotriazole-based ultraviolet absorbers such as-(3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole.

Examples of the light stabilizer include hindered amine and benzoate light stabilizers. As hindered amine light stabilizers, bis (1,2,2,2)
6,6-pentamethyl-4-piperidinyl) sebacate and bis (1,2,2,2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate)
6,6-pentamethyl-4-piperidyl) and the like. As benzoate light stabilizers, 2,4-di-
t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate and the like.

As the antioxidant, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-)
Hydroxylphenyl) propionate] and 1,6-
Hexanediol-bis [3,5-di-t-butyl-4
-Hydroxyphenyl) propionate] and the like.

The preferred mixing ratio of the weather resistance improver is 0.01 to 5 parts by weight based on 100 parts by weight of the composition. If the proportion is less than 0.01 part by weight, the effect of blending the weather resistance improving component will not be obtained, while if it exceeds 5 parts by weight, the curability of the composition will be reduced, The abrasion resistance of the cured product may decrease.

5. Method of Use Since the coating films and molded products obtained from the composition of the present invention have excellent weather resistance and abrasion resistance, they can be used for coating agents, adhesives, binders, molded products and the like. In addition, since the imide group portion of the component (A) component is highly polar, it has excellent adhesion to various plastics,
Further, since it is excellent in abrasion resistance and weather resistance, it can be preferably used in applications of plastic hard coats and in molding materials because of its excellent abrasion resistance and weather resistance.
In addition, since it has excellent UV curability, it can be used as a binder for various resist materials and coloring materials, and as a photosensitive resin for surface processing technology that has been made uneven or patterned by a photomechanical method.

For use of the composition of the present invention, for example, in the case of applications such as coating agents, adhesives and binders, the composition is applied to a substrate to be applied by a usual coating method, and then the ultraviolet light and For applications such as curing by irradiating active energy rays such as electron beams, or in the case of applications such as molding materials, the composition is injected into a prescribed mold and cured by irradiating it with active energy rays. A general method such as a method for causing the above to occur can be adopted. The method of irradiating the active energy ray may employ a general method conventionally known as a method of curing an active energy ray-curable composition.

[0069]

The present invention will be described more specifically with reference to the following examples. In the following,% means% by weight, and part means parts by weight. The abbreviations used are shown below. MMA: methyl methacrylate BA: butyl acrylate MAA: methacrylic acid GMA: glycidyl methacrylate HEA: hydroxyethyl acrylate MOI: methacryloxyethyl isocyanate AA: acrylic acid St: styrene ML: maleic anhydride HBVE: hydroxybutyl vinyl ether THPI-A: 3, 4,5,6-tetrahydrophthalimidoethyl acrylate

[0070]

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DMI-M: dimethylmaleimidoethyl methacrylate

[0072]

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CI-ETA: hydroxyethyl citracoimide

[0074]

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THPI-GL: carboxymethyltetrahydrophthalimide

[0076]

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Production Example 1 At room temperature, a flask equipped with a stirrer, thermometer and condenser
30 g of THPI-A, 14 g of MMA, 20 g of BA, 26 of MAA
g and 100 g of butyl acetate were charged, stirred and dissolved, and then 3 g of 2,2′-azobis (2-methylbutyronitrile) was charged and uniformly dissolved. Thereafter, the mixture was stirred at 85 ° C for 2 hours and further at 100 ° C for 1 hour under a nitrogen stream to obtain a prepolymer. To a solution of the obtained prepolymer was added 10 g of GMA and 0.5 g of triethylamine.
g and 0.1 g of hydroquinone were added and dissolved by stirring. The mixture was further heated and stirred at 100 ° C. for 5 hours to obtain a copolymer.
A-1 was obtained.

Production Example 2 In a flask similar to Production Example 1, 40 g of DMI-M
After 20 g of MA, 14 g of BA, 11 g of HEA and 100 g of butyl acetate were charged and stirred and dissolved, 3 g of 2,2′-azobis (2-methylbutyronitrile) was charged and uniformly dissolved. Thereafter, the mixture was heated and stirred under the same conditions as in Production Example 1 under a nitrogen stream to obtain a prepolymer. To the obtained prepolymer solution, 15 g of MOI, 0.1 g of dibutyltin laurate and 0.1 g of hydroquinone were added and dissolved by stirring. The mixture was further heated and stirred at 60 ° C. for 3 hours to obtain a copolymer A-2.

Production Example 3 A prepolymer was obtained by polymerization in the same manner as in Production Example 1, except that the starting materials used were changed to 20 g of THPI-A, 10 g of MMA, 11 g of BA and 39 g of GMA. Was. The reaction was carried out in the same manner as in Production Example 1 except that the amount of the starting material used was changed to 20 g of AA, to obtain a copolymer A-3.

Production Example 4 The starting materials used were 50 g of DMI-M, 20 g of MMA, and 7 g of BA.
Polymerization was carried out in the same manner as in Production Example 1 except that g and the MOI were changed to 13 g to obtain a prepolymer. The reaction was carried out in the same manner as in Production Example 2 except that the starting material used was changed to 10 g of HEA, to obtain a copolymer A-4.

Production Example 5 The starting materials used were 60 g of THPI-A, 5 g of MMA, and 2 g of MOI.
A prepolymer was obtained by polymerization in the same manner as in Production Example 1 except that the amount was changed to 0 g. Use HBVE 15g raw material
The reaction was carried out in the same manner as in Production Example 2, except that the copolymer A-5 was obtained, to obtain a copolymer A-5.

Production Example 6 The starting materials used were 30 g of DMI-M, 18 g of St, and 1 g of ML.
A prepolymer was obtained by polymerization in the same manner as in Production Example 1 except that the amount was changed to 7 g and 15 g of BA. Raw materials used
The reaction was carried out in the same manner as in Production Example 1 except that the amount of HEA was changed to 20 g, to obtain a copolymer A-6.

Production Example 7 The starting materials used were 20 g of St, 25 g of ML, and 20 g of BA.
Polymerization was carried out in the same manner as in Production Example 1 except that the prepolymer was changed to a prepolymer. The raw materials used are CI-ETA 20g and
The reaction was carried out in the same manner as in Production Example 1 except that the HEA was changed to 15 g, to obtain a copolymer A-4.

Production Example 8 A prepolymer was obtained in the same manner as in Production Example 1, except that the raw materials used were changed to 20 g of MMA and 40 g of GMA. Use 30g of THPI-GL and AA10
g, except that the reaction was carried out in the same manner as in Production Example 1.
Copolymer A-8 was obtained.

[0085]

[Table 1]

Comparative Production Example Under the same conditions as in the production of the prepolymer of Production Example 1, polymerization was carried out with the following composition to obtain C-1 and C-2.

[0087]

[Table 2]

Example 1 140 parts (solid content: 70 parts) of a solution of the copolymer A-1 obtained in Production Example 1 and 3 moles of modified ethylene oxide of trimethylolpropane [modified by Toagosei Co., Ltd.] , Aronix M-350] were mixed in a conventional manner to obtain an active energy ray-curable composition. The obtained composition was evaluated for curability, weather resistance, abrasion resistance and adhesion according to the following methods. Table 2 shows the results.

Curable Bonderite steel plate (Pippon Japan Test Panel Co., Ltd.)
B-144), and applying the obtained composition to a substrate to form a film having a thickness of 1
After coating at 0μ and drying at 50 ° C for 30 minutes, 120W
The sample was passed under a 10 cm / min condensing high-pressure mercury lamp (1 lamp) at a conveyor speed of 10 m / min, and evaluated by the number of passes until the surface was tacked by hand.

Weather resistance: A white PVC plate manufactured by Nippon Test Panel was used as a base material.
The obtained composition is applied on a substrate at a film thickness of 10 μm, dried at 50 ° C. for 30 minutes, and then conveyed at 10 m / min under a 120 W / cm condensing high-pressure mercury lamp (one light, height 10 cm). A specimen was passed at a speed and cured by touching with a hand until the tack on the surface was eliminated. Using a Suga Test Instruments Co., Ltd. Dew Panel Light Control Weather Meter DPWL-5R as an accelerated exposure acceleration tester,
The film was exposed to a wet condition (100% RH / 40 ° C.) for 6 hours and an irradiation condition (30 W / m 2/40 ° C.) for 6 hours. This was repeated alternately for 500 hours, and the visual change in appearance and discoloration by a color difference meter were evaluated. The color difference meter used was Sigma 80 manufactured by Nippon Denshoku. In Table 2, △, Δ, and × in the change in appearance have the following meanings. ：: no cracks occurred, △: slight cracks occurred,
×: Cracks occurred on the entire coating film

Abrasion resistance A polycarbonate plate manufactured by Japan Test Panel Co., Ltd. was used as a substrate, and the obtained composition was applied to the substrate at a film thickness of 10 μm.
After drying at 50 ° C for 30 minutes, it is passed under a condensing high-pressure mercury lamp of 120 W / cm (one lamp, height: 10 cm) at a conveyor speed of 10 m / min, and is cured by touching with hand until the tack on the surface is eliminated. Was used as a test specimen. # 000
Of steel wool is attached to the tip of a cylinder with a diameter of 25 mm,
It was brought into contact with the cured film of the test piece placed horizontally, rotated 5 times (20 rpm) under a load of 1.0 kg, and the degree of adhesion of the scratch was visually observed. ◎, ◎, Δ and × in Table 2 indicate the following meanings. ◎: The sample surface is not scratched, ○: The sample surface is slightly scratched, Δ: The sample surface is considerably scratched, ×: The scratched portion of the substrate surface is exposed

Adhesion: Use the same specimen as that used in the abrasion resistance test.
According to the test method of JISK-5400, cellophane tape was peeled off, and the remaining cells in 100 cells were evaluated in the following three grades. As a base material, a polycarbonate plate manufactured by Nippon Test Panel was used. ：: 90 or more, Δ: 10 to 90, ×: 10 or less

Examples 2 to 8 Compositions were prepared in the same manner as in Example 1 except that the components and amounts shown in Table 3 below were used. The obtained composition was evaluated in the same manner as in Example 1. Table 3 shows the results.

[0094]

[Table 3]

In Table 3, the numbers in the columns of the components (A) and (B) mean the number of copies. However, the component (A) was shown as a value converted to a solid content. The abbreviations in Table 3 have the following meanings. 1) M-350: Aronix M-3 manufactured by Toagosei Co., Ltd.
50, trimethylolpropane ethylene oxide 3 mol modified triacrylate 2) M-400: Alonix M-4 manufactured by Toagosei Co., Ltd.
00, a mixture of pentaacrylate (about 20% by weight) of dipentaerythritol and hexaacrylate (about 80% by weight) 3) DVE-3: rapicure DVE-3, triethylene glycol divinyl ether manufactured by ISP 4) Irg184: Ciba-Geigy ( Irgacure 184, hydroxycyclohexyl acetophenone (photopolymerization initiator)

Comparative Examples 1 and 2 A composition was prepared in the same manner as in Example 1 except that the components and amounts shown in Table 4 below were used. The obtained composition was evaluated in the same manner as in Example 1. Table 4 shows the results.

[0097]

[Table 4]

In Table 4, the numbers in the copolymer and the component (B) mean the number of parts. However, the copolymer component is shown by a value converted to a solid content. The abbreviations in Table 4 have the same meaning as described above.

[0099]

The composition of the present invention is rapidly cured by irradiation with active energy rays without the addition of a photopolymerization initiator, and the cured product has excellent weather resistance, abrasion resistance and Excellent adhesion.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C09J 155/00 C09J 155/00 157/06 157/06 (72) Inventor Kunihiko Mizutani 1 Funamicho, Minato-ku, Nagoya-shi, Aichi Prefecture No. 1 Toagosei Co., Ltd. Nagoya Research Institute F-term (reference) 4J011 QA03 QA08 QA12 QA13 QA22 QA23 QA24 QA32 QA33 QA34 QA39 QA45 QA46 QB03 QB14 QB19 QB20 QB22 QB24 SA02 SA14 SA16 SA17 SA18 SA18 SA22 SA63 SA64 TA02 UA01 UA03 WA01 WA02 WA06 WA07 4J027 AA02 AB10 AB15 AB16 AB18 AB19 AB23 AB24 AB25 AE02 AE03 AE04 AG03 AG04 AG09 AG13 AG14 AG23 AG24 AG27 AG33 BA04 BA07 BA08 BA13 BA15 BA17 BA19 BA20 BA23 BA24 CD10 CD10 FA012 FA062 FA112 FA142 FA152 FA171 FA172 FA231 FA252 FA262 FA282 GA01 GA03 GA06 GA07 GA08 GA11 KA03 NA03 NA11 PA17 4J040 FA012 FA062 FA111 FA132 FA162 FA172 FA231 FA232 FA262 FA272 FA292 GA01 GA05 GA07 GA11 GA20 JB07 KA13 LA06 LA07

Claims (4)

[Claims] 1. A crosslinkable resin composition comprising a polymer (A) having a maleimide group and an ethylenically unsaturated group. 2. The crosslinkable resin composition according to claim 1, comprising component (A) and a compound (B) having an ethylenically unsaturated group other than component (A). 3. The crosslinkable resin composition according to claim 2, wherein component (B) is a compound having two or more ethylenically unsaturated groups. 4. An active energy ray-crosslinkable resin composition comprising the composition according to any one of claims 1 to 3.