JPH0718037A - Photocuring resin composition - Google Patents

Abstract

PURPOSE:To obtain the composition which can be rapidly cured into a product of excellent staining resistance by irradiation with light, by mixing a radical- polymerizable, ethylenically unsaturated reactive oligomer with a specified reactive diluent and a photopolymerization initiator. CONSTITUTION:The composition is prepared by mixing a radical-polymerizable ethylenically unsaturated reactive oligomer (A) with a 4-t-butylcyclohexyl (meth) acrylate (B) of the formula (wherein R is H or CH3) and a photopolymerization initiator (C). The mixing ratio is such that 5-95 pts.wt. component A is combined with 95-5 pts.wt. component B to form 100 pts.wt. mixture, and component C is added in an amount of 0.1-10 pts.wt. to 100 pts.wt. total of components A and B. This composition is lowly volatile and lowly odorous, can be rapidly cured by irradiation with light to provide a product excellent in surface hardness and staining resistance, and is useful as a coating agent, an adhesive or an ink binder.

Description

Detailed Description of the Invention

[0001]

The present invention is capable of forming a resin having low volatility and a high glass transition temperature, and further,
A resin composition containing 4-t-butylcyclohexyl (meth) acrylate, which is excellent in photocurability, as a main component, and the resin composition is rapidly cured by irradiation of light to give a cured product excellent in stain resistance. The present invention relates to a novel photocurable resin composition.

[0002]

2. Description of the Related Art Conventionally known photocurable resins include radical polymerization type acrylic resins, unsaturated polyester type resins, polyene-thiol type resins and cationic polymerization type epoxy resins. In particular, radical polymerization acrylic resin compositions are usefully used as coating agents, adhesives, inks and the like.

[0003]

The photocurable resin generally has a short curing time and can be cured at a low temperature. Since it is a one-component type and can be solventless, it saves resources and pollutes the environment. Has the advantage of being able to reduce However,
The oligomers used in these photocurable resins are generally extremely high in viscosity, and it is difficult to treat them as a paint or as an adhesive by themselves. Usually, radical polymerizable unsaturated double bonds are used. The operability is enhanced by mixing a low-viscosity reactive diluent having
Many of these reactive diluents that have been conventionally used are known, such as acrylic monomers and vinyl monomers. Among them, acrylates are generally excellent in photocurability, but on the other hand, since they have strong odor and strong skin irritation, photocurable resins containing the monomer have the drawback of impairing their working environment. is doing. Although these acrylate monomers have been developed by modifying them with alkylene oxide or ε-caprolactone to reduce odor and skin irritation, this modified acrylate has a reduced curing rate and hardness of the cured product. Had the drawback of.

[0004]

As a result of intensive studies, the inventors of the present invention have found that 4-t-butylcyclohexyl (meth) capable of forming a cured product having a low glass volatility and a high glass transition temperature and being excellent in photocurability. By using an acrylate as a reactive diluent, it has been found that a novel photocurable resin having excellent curability and excellent stain resistance can be obtained, which has led to the present invention. The component A is composed of a reactive oligomer having a radical-polymerizable unsaturated double bond in the molecule, and 4-t-butylcyclohexyl (meth) which is a reactive monomer represented by the structural formula [2]. ) B component consisting of acrylate,

[Chemical 2] Also, the present invention relates to a novel photocurable resin composition comprising a C component composed of a photopolymerization initiator.

The component A used in the present invention is a reactive oligomer having a radical-polymerizable unsaturated double bond in the molecule, and examples thereof include a saturated or unsaturated polycarboxylic acid, an alkylpolyol and ( Polyester poly (meth) acrylate obtained by reaction with (meth) acrylic acid, epoxy poly (meth) acrylate obtained by reaction with epoxy resin and (meth) acrylic acid, polyol, polyisocyanate and hydroxyl group-containing (meth) acrylate Urethane poly (meth) acrylate obtained by the reaction of, polysiloxane poly (meth) acrylate obtained by the reaction of polysiloxane and a (meth) acrylic acid compound, and polyamide obtained by the reaction of a polyamide and a (meth) acrylic acid compound And poly (meth) acrylate .

Examples of the saturated or unsaturated carboxylic acid constituting the above oligomer include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, 2,3-dimethylsuccinic acid, hexylsuccinic acid, glutaric acid, 2,2 -Dimethyl glutaric acid,
3,3-Dimethylglutaric acid, 3,3-Diethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4 -Cyclohexanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, maleic acid, fumaric acid, aconitic acid, itaconic acid, citraconic acid, mesaconic acid, muconic acid and dihydromuconic acid And acid halides of the above acids, alkyl derivatives, and the like.

Examples of the alkyl polyol constituting the above oligomer include, for example, ethylene glycol, 1,3-propanediol, propylene glycol, 2,3-butanediol, 1,4-butanediol, 2-ethylbutane-1,4- Diol, 1,5-pentanediol, 1,6-hexanediol,
1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane, 2,2-
Diethylpropane-1,3-diol, 3-methylpentane-
1,4-diol, 2,2-diethylbutane-1,3-diol,
4,5-nonanediol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol, glycerin, pentaerythritol, erythritol, sorbitol, mannitol, trimethylolpropane, methylolethane, 2,2-dimethyl-3-
Examples include hydroxypropyl-2,2-dimethyl-3-hydroxypropionate, and 2-butene-1,4-diol.

Specific examples of the polyisocyanate constituting the above oligomer include triethylene diisocyanate, ethylene diisocyanate, 1,2-diisocyanate propane, 1,3-diisocyanate propane, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, Tetramethylxylylene diisocyanate, hexamethylene diisocyanate, lysine isocyanate, 4,4′-methylenebis (cyclohexyl) isocyanate, methylcyclohexane-2,4-diisocyanate,
Methylcyclohexane-2,6-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, dimer acid diisocyanate, 2-isocyanatoethyl-2,6-
Examples thereof include polyisocyanate monomers such as diisocyanate hexanoate, dimers and trimers of these isocyanates, and adducts of these isocyanates and polyols.

Specific examples of the polyol used in the adduct are not particularly limited, but ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, trimethylolpropane, polytriol. Methylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerin and other alcohols and polyether polyols, polyester polyols synthesized from polyhydric alcohols and polybasic acids, polyhydric alcohols and caprolactone Examples thereof include polyester polyols such as caprolactone polyol.

Specific examples of the hydroxyl group-containing (meth) acrylate constituting the above oligomer include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, 3-bromo-2-hydroxypropyl acrylate, 3-bromo-2-hydroxypropyl Methacrylate,
2-chloro-1- (hydroxymethyl) ethyl acrylate, 2-chloro-1- (hydroxymethyl) ethyl methacrylate, 2-bromo-1- (hydroxymethyl) ethyl acrylate, 2-bromo-1- (hydroxymethyl) ethyl Methacrylate etc. can be mentioned.

4- which is a reactive monomer constituting the B component
t-Butylcyclohexyl (meth) acrylate can be obtained by reacting 4-t-butylcyclohexanol represented by the structural formula [3] with (meth) acrylic acid.

[Chemical 3]

B composed of these reactive monomers is used.
The components are used in the range of 5 to 95 parts by weight in 100 parts by weight of the photocurable resin composition. A resin composition containing less than 5 parts by weight of component B has poor curability in air, and a resin composition containing more than 95 parts by weight of component B has poor photocurability. Becomes

The photopolymerization initiator used in carrying out the present invention can be arbitrarily selected from known ones and used. Specific examples thereof include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone and xant. Fluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-
Diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2
-Methylpropan-1-one, 2-hydroxy-2-methyl-1
-Phenylpropan-1-one, 4-oxanthone, camphorquinone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and the like can be mentioned.
A photopolymerization initiator having at least one (meth) acryloyl group in the molecule can also be used. These photopolymerization initiators can be used alone or as a mixture of two or more kinds, and the amount thereof is 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight with respect to 100 parts by weight of the mixture of the components A and B. Parts by weight.

Further, the resin composition of the present invention contains the component A,
In addition to B component and C component, if necessary, photosensitizer, photoaccelerator, polymerization inhibitor, matting agent, coloring pigment, dye, defoaming agent, leveling agent, dispersant, plasticizer, non-reactive A polymer or the like can be added.

The resin composition of the present invention is cured by irradiation with ultraviolet rays, and as the ultraviolet ray source, sun rays, low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps and the like are used.

The resin composition of the present invention is combined in the proportion of 5 to 95 parts by weight of the component A and 95 to 5 parts by weight of the component B in a ratio of 100 parts by weight in total, and the component C is combined with the components A and B. Total amount
It can be adjusted by blending in a proportion of 0.1 to 10 parts by weight with respect to 100 parts by weight, and can be a photocurable resin composition having low volatility, low odor, low skin irritation and excellent environmental resistance properties. The cured product has excellent weather resistance, surface hardness, and stain resistance, and can be effectively used as a coating agent, an adhesive, and a binder for ink.

The present invention will be described below with reference to synthesis examples, examples and comparative examples, but the present invention is not limited thereto.

[Synthesis Example 1] 400 parts of polyethylene glycol (average molecular weight: 400) and isophorone diisocyanate
666 parts and 464 parts of hydroxyethyl acrylate,
Urethane acrylate A was obtained by reacting at 60 ° C. for 10 hours.

[0019]

Example 1 Urethane Acrylate A Made in Synthesis Example 1
80 parts, 20 parts of 4-t-butylcyclohexyl acrylate and 3 parts of a photopolymerization initiator (Darocur 1173: E, manufactured by Merck & Co., Inc.) were mixed at room temperature to prepare a resin composition.

[0020]

Example 2 Urethane Acrylate A Made in Synthesis Example 1
A resin composition was prepared by mixing 60 parts, 40 parts of 4-t-butylcyclohexyl acrylate and 3 parts of a photopolymerization initiator (Darocur 1173: E, manufactured by Merck) at room temperature.

[0021]

Comparative Example 1 Urethane Acrylate A Made in Synthesis Example 1
80 parts, phenoxyethyl acrylate (POA: Kyoeisha Yushi-Kagaku Kogyo Co., Ltd.) 20 parts, photopolymerization initiator (Darocur 117
3: E, manufactured by Merck & Co., Inc.) was mixed at room temperature to prepare a resin composition.

[0022]

Comparative Example 2 Urethane Acrylate A Made in Synthesis Example 1
60 parts, phenoxyethyl acrylate (POA: manufactured by Kyoeisha Yushi Kagaku Kogyo) 40 parts, photopolymerization initiator (Darocur 117
3: E, manufactured by Merck & Co., Inc.) was mixed at room temperature to prepare a resin composition.

[0023]

Comparative Example 3 Urethane Acrylate A Made in Synthesis Example 1
80 parts, ethyl carbitol acrylate (viscoat #
190: manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 20 parts of a photopolymerization initiator (Darocur 1173: E, manufactured by Merck & Co.) were mixed at room temperature to prepare a resin composition.

[0024]

Comparative Example 4 Urethane Acrylate A Made in Synthesis Example 1
60 parts, ethyl carbitol acrylate (viscoat #
190: Osaka Organic Chemical Industry) 40 parts and a photopolymerization initiator (Darocur 1173: E, manufactured by Merck & Co.) 3 parts were mixed at room temperature to prepare a resin composition.

[0025]

[Test Example] The resin compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 4 were applied to a hard vinyl chloride plate using a bar coater (# 40), and then the coated plate was subjected to a high pressure of 80 W / cm. With a mercury lamp (UV-2503 manufactured by Mitsubishi Rayon Engineering), the conveyor speed is set to 15 m / min, and the distance from the lamp is 20 cm.
The film was repeatedly passed through the above position until it became tack-free, and UV cured. The cured product obtained in this manner was subjected to the following tests to evaluate coating film performance. The evaluation results are shown in Table 1.

[0026]

[Table 1]

[Test Items] 1) Pencil hardness: According to JIS K-5400 "pencil scratch test". 2) Contamination resistance: 1 cm square of the coating film was painted with black and red magic, and after 24 hours, the degree of contamination remaining when wiped off with ethanol-soaked gauze was evaluated on a scale of 5. The higher the number, the less pollution.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 24, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

The resin composition of the present invention is combined in the proportion of 5 to 95 parts by weight of the component A and 95 to 5 parts by weight of the component B at a ratio of 100 parts by weight in total, and the component C is combined with the components A and B. It can be prepared by blending at a ratio of 0.1 to 10 parts by weight with respect to 100 parts by weight in total, and can be a photocurable resin composition having low volatility, low odor and excellent operability,
In addition, the cured product has excellent surface hardness and stain resistance and can be effectively used as a coating agent, an adhesive, and a binder for ink.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

[0026]

[Table 1]

Claims (1)

[Claims] 1. A component consisting of a reactive oligomer having a radically polymerizable unsaturated double bond in the molecule, and 4-t-butylcyclohexyl (meth) acrylate which is a reactive monomer represented by the structural formula [1]. B component consisting of And a photocurable resin composition comprising a C component composed of a photopolymerization initiator as a main constituent, wherein the A component is 5 to 95 parts by weight and the B component is 95 to 100 parts by weight in total of 100 parts by weight. A photocurable resin composition comprising 5 parts by weight of component C and 0.1 to 10 parts by weight per 100 parts by weight of a mixture of components A and B.