JPH06329738A - Photocurable resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition excellent in operation, quickly curable upon irradiation with light and capable of giving a cured product excellent in stain resistance and solvent resistance by mixing a reactive oligomer with a specified reactive monomer and a photopolymerization initiator. CONSTITUTION:The composition is prepared by mixing a reactive oligomer (A) having a radical-polymerizable unsaturated double bond in the molecule with benzyl alcohol/alkyleneoxide-modified (meth)acrylate (B) as a reactive monomer of the formula wherein R1 and R2 are each hydrogen or methyl; and n is an integer of 1-5 and a photopolymerization initiator (C). The amounts of use are 5-59 pts.wt. and 95-5 pts.wt. based on 100 pts.wt. total of components A and B for components A and B, respectively, and the amount of component C is 0.1-10 pts.wt. per 100 pts.wt. total of components A and B.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention comprises an alkylene oxide-modified (meth) acrylate of benzyl alcohol, which has a low viscosity, a low odor, a large diluting effect and an excellent curability, as a main constituent component, and has excellent operability and light irradiation. The present invention relates to a novel photocurable resin composition which is rapidly cured by and gives a cured product excellent in stain resistance and solvent resistance.

[0002]

2. Description of the Related Art A photocurable resin composition is an acrylic resin composition as a radical crosslinkable resin, an unsaturated polyester resin composition, a polyene-thiol resin composition, an epoxy resin composition as a cationic polymerization type. The acrylic resin composition is used as a coating agent, an adhesive, an ink, and the like.

[0003]

The photo-curing resin is generally a one-component type and can be solvent-free because it generally has a short curing time of the resin composition and can be cured at a low temperature. It has the advantages of becoming a resource-based resin and reducing environmental pollution. However, the oligomers used for these photocurable resins generally have extremely high viscosity, and it is difficult to treat them alone as a photocurable resin. By mixing a low viscosity reactive diluent having a double bond, the operability of the resulting photocurable resin composition is improved. As the reactive diluent used here, many compounds such as acrylic monomers and other vinyl monomers are known. Among them, acrylic monomers are generally excellent in photo-curability, but on the other hand, they have strong odor and skin irritation, and are a cause of impairing the working environment for handling the resin composition containing acrylic monomers. Attempts have been made to reduce the odor and skin irritation by modifying acrylic monomers with alkylene oxide, caprolactone, etc., and have been successful. However, as a result, there has been a problem that the rapid curing property due to light irradiation, which is a feature of the resin composition containing acrylate, is impaired.

[0004]

Therefore, the present inventors have
Operability of a photocurable resin composition is improved by using an alkylene oxide-modified (meth) acrylate of benzyl alcohol, which has a low viscosity, a low odor and a large diluting effect on the resin composition and is excellent in photocurability It has been found that a novel photocurable resin composition that gives a cured product having excellent fast-curing properties, stain resistance, and solvent resistance is obtained, and has completed the present invention. Is (1) A component comprising a reactive oligomer having a radically polymerizable unsaturated double bond in the molecule, and (2) alkylene oxide modification of benzyl alcohol which is a reactive monomer represented by the structural formula [2]. B component consisting of (meth) acrylate, and

[Chemical 2] (3) The present invention relates to a novel photocurable resin composition comprising a C component composed of a photopolymerization initiator and combining them in a specific amount ratio.

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 and polyisocyanate, and hydroxyl group-containing (meth) acrylate Urethane poly (meth) acrylate obtained by the reaction of, and polysiloxane poly (meth) obtained by the reaction of the polysiloxane and the (meth) acrylic acid compound
Examples thereof include acrylates and polyamide poly (meth) acrylates obtained by reacting a polyamide with a (meth) acrylic acid compound.

Among the above oligomers, examples of the saturated or unsaturated carboxylic acid which constitutes the polyester (meth) acrylate include oxalic acid, malonic acid, succinic acid,
Methylsuccinic acid, 2,3-dimethylsuccinic acid, hexylsuccinic acid, glutaric acid, 2,2-dimethylglutaric 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 the above acids. Examples thereof include acid halides and alkyl ester derivatives. As the alkyl polyol, 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, 1,9-decanediol, 1,
4-cyclohexanediol, 1,4-dimethylolcyclohexane, 2,2-diethylpropane-1,3-diol, 2,2-dimethylpropane-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-hydroxypropionate, and 2 -Butene-1,4-diol and the like can be mentioned.

Specific examples of the polyisocyanate constituting the polyurethane (meth) acrylate include triethylene diisocyanate, ethylene diisocyanate and 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, 2,6-diisocyanate hexanoate, etc. Of polyisocyanate monomer,
Examples thereof include dimers and trimers of these polyisocyanates, and adducts of these isocyanates and polyols. Specific examples of the polyol used for making this adduct include, but are not limited to, ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, trimethylolpropane, polytriethylene. Methylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerin and other alcohols and polyether polyols, polyester polyols synthesized from polyhydric alcohols and polybasic acids, polyester polyols such as polycaprolactone polyols, and the like. To be

Specific examples of the hydroxyl group-containing (meth) acrylate used for producing polyurethane (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate. Chloro-2-hydroxypropyl (meth) acrylate, 3-bromo-2-hydroxypropyl (meth) acrylate, 2-chloro-1- (hydroxymethyl) ethyl (meth) acrylate, 2-bromo-1- (hydroxymethyl) Examples thereof include ethyl (meth) acrylate.

Alkylene oxide modification (meth) of benzyl alcohol which is a reactive monomer used as the component B
Acrylate is produced by adding an arbitrary number of moles of alkylene oxide such as ethylene oxide or propylene oxide to benzyl alcohol to prepare a compound represented by the chemical formula [3], and reacting this compound with (meth) acrylic acid. However, the addition number n of the alkylene oxide is in the range of 1 to 5, and when the number of n is 6 or more, the curability of the obtained reactive monomer is impaired.

[Chemical 3]

A component and B constituting the resin composition of the present invention
The composition ratio of the components can be any mixing ratio within the range of 5/95 to 95/5 (part by weight ratio) in 100 parts by weight of the total amount of the components A and B.

The photopolymerization initiator used in the present invention can be arbitrarily selected from known ones and used. Specific examples thereof include
2,2-Dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthfluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, benzoinpropyl ether, benzoin ethyl ether, benzyl Dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1
-One, 2-hydroxy-2-methyl-1-phenylpropane
-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.

In the resin composition of the present invention, if necessary, a photosensitizer, a photoaccelerator, a polymerization inhibitor, a matting agent, a coloring pigment,
Dyes, defoamers, leveling agents, dispersants, plasticizers, non-reactive polymers and the like can be added. The resin composition of the present invention is cured by irradiation with light, and as a light source, a sun ray, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp or the like is used.

The resin composition of the present invention can be used as a photo-curing type coating agent, adhesive, ink binder and the like, and is characterized by low odor and low skin irritation.

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

[Synthesis Example of Reactive Oligomer] 400 parts of polyethylene glycol (average molecular weight: 400), 666 parts of isophorone diisocyanate and 464 parts of hydroxyethyl acrylate were reacted at 60 ° C. for 10 hours to obtain urethane acrylate A.

[0016]

Example 1 80 parts of urethane acrylate A, acrylate obtained by adding 1 mol of ethylene oxide to benzyl alcohol
20 parts, photopolymerization initiator (Darocur 1173: E, manufactured by Merck)
3 parts were mixed at room temperature to prepare a resin composition.

[0017]

Example 2 Urethane acrylate A 60 parts, acrylate obtained by adding 1 mol of ethylene oxide to benzyl alcohol
40 parts, photopolymerization initiator (Darocur 1173: E, manufactured by Merck)
3 parts were mixed at room temperature to prepare a resin composition.

[0018]

Comparative Example 1 80 parts of urethane acrylate A, 20 parts of phenoxyethyl acrylate, photopolymerization initiator (Darocur 11
73: E, manufactured by Merck & Co., Inc.) was mixed at room temperature to prepare a resin composition.

[0019]

Comparative Example 2 60 parts of urethane acrylate A, 40 parts of phenoxyethyl acrylate, a photopolymerization initiator (Darocur 11
73: E, manufactured by Merck & Co., Inc.) was mixed at room temperature to prepare a resin composition.

[0020]

Comparative Example 3 80 parts of urethane acrylate A, 20 parts of ethyl carbitol acrylate (Biscoat # 190: manufactured by Osaka Organic Chemical Industry), and 3 parts of a photopolymerization initiator (Darocur 1173: E, manufactured by Merck) were mixed at room temperature, A resin composition was prepared.

[0021]

[Comparative Example 4] 60 parts of urethane acrylate A, 40 parts of ethyl carbitol acrylate (biscoat # 190: manufactured by Osaka Organic Chemical Industry), and 3 parts of a photopolymerization initiator (Darocur 1173: E, manufactured by Merck) were mixed at room temperature, A resin composition was prepared.

Table 1 shows the evaluation results of the resin compositions of Examples 1 and 2 and Comparative Examples 1 to 4.

[0023]

[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 so as to have a film thickness of about 80 μm, and then lamped with a high pressure mercury lamp of 80 W / cm. The height was set to 20 cm, the conveyor speed was set to 15 m / min, and UV curing was performed. The cured product obtained in this manner was subjected to the following tests to evaluate coating film performance, and shown in Table 1. Table 1
From the results shown in, the resin composition of the present invention is excellent in photocurability, the obtained cured product is excellent in coating properties such as hardness and stain resistance, and the resin composition has a low It was confirmed that it had odor and low skin irritation.

[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.

[Table 1]

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[Procedure amendment]

[Submission date] July 13, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0001

[Correction method] Change

[Correction content]

[0001]

BACKGROUND OF THE INVENTION The present invention comprises an alkylene oxide-modified (meth) acrylate of benzyl alcohol, which has a low viscosity, a low odor, a large diluting effect and an excellent curability, as a main constituent component, and has excellent operability and light irradiation. The present invention relates to a novel photocurable resin composition which is rapidly cured by and gives a cured product excellent in stain resistance.

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

Table 1 shows the evaluation results of the resin compositions of Examples 1 and 2 and Comparative Examples 1 to 4.

[Table 1]

Claims (1)

[Claims] 1. A component A comprising a reactive oligomer having a radically polymerizable unsaturated double bond in the molecule, and (2) an alkylene of benzyl alcohol which is a reactive monomer represented by the structural formula [1]. B component consisting of oxide-modified (meth) acrylate, and (3) Consist of C component consisting of photopolymerization initiator, 5 to 95 parts by weight of A component, and B in 100 parts by weight of total amount of A component and B component
A photocurable resin composition, characterized in that the component C is contained in a proportion of 95 to 5 parts by weight, and the composition ratio of the component C is 0.1 to 10 parts by weight with respect to 100 parts by weight of the mixture of the components A and B.