JPH072962A - Photo-curable resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition which can rapidly be cured by light irradiation to give a cured product excellent in staining resistance and solvent resistance and has excellent handleability by mixing a specified reactive oligomer with a specified norbornyl (meth)acrylate and a specified photopolymerization initiator in a specified mixing ratio. CONSTITUTION:The resin composition comprises 5-95 pts.wt. reactive oligomer having a radical-polymerizable double bond in the molecule (e.g. urethane acrylate made from polyethylene glycol, isophorone diisocyanate and hydroxyethyl acrylate), 95-5 pts.wt. (the total of both being 100 pts.wt.) norbornyl (meth)acrylate being a reactive monomer of the formula (wherein R is H or CH3) and 0.1-10 pts.wt. photopolymerization initiator (e.g. Darocure 1173, a product of merck & Co., Inc.).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition containing norbornyl (meth) acrylate as a constituent, which has a low viscosity, a large dilution effect, and an excellent photocurability.
In particular, the present invention relates to a novel photocurable resin composition which is excellent in handling operability of the composition, is rapidly cured by irradiation of light, and gives a cured product excellent in stain resistance and solvent resistance.

[0002]

2. Description of the Related Art Acrylic resins, unsaturated polyester resins, polyene-thiol resins, epoxy resins as cationic polymerization resins, etc. are known as photocurable resins, as radical crosslinkable resins. Resin compositions are used for coating agents, adhesives, inks and the like.

[0003]

A photocurable resin is generally a short-time curing, can be cured at a low temperature, and can be a solvent-free one-component type, so that it is a resource-saving resin. And has the advantage of reducing environmental pollution. However, the oligomers used in these photocurable resins generally have extremely high viscosity,
It is difficult to handle as a photocurable resin alone, and usually, a resin composition obtained by mixing a low-viscosity reactive diluent having a radically polymerizable unsaturated double bond with the oligomer is prepared. It is increasing the nature. As these reactive diluents, many polymerizable monomers such as acrylic monomers, methacrylic monomers, and other vinyl monomers are known, and acrylic monomers are particularly excellent in curability. Among them, aliphatic acrylate is
Generally, it has a large diluting effect on oligomers and contributes to the improvement of the operability of the obtained resin composition, but on the other hand, it has the drawback of being highly odorous and irritating to the skin and impairing the working environment. Aromatic acrylates have low volatility, but have a small dilution effect on oligomers.
It has a defect that the cured product of this composition has poor weather resistance.

[0004]

Therefore, the present inventors have
By preparing a resin composition in which norbornyl (meth) acrylate, which has a large diluting effect on the oligomer and is excellent in curability, is mixed with the oligomer as a reactive diluent, the operability and curability of the resin composition are excellent, and the stain resistance, It was found that a novel photocurable resin that gives a cured product having excellent solvent resistance can be obtained, and the present invention has been achieved. The gist of the present invention is that (1) a radical-polymerizable unsaturated double bond. A component composed of a reactive oligomer having a bond in the molecule,
(2) B component composed of norbornyl (meth) acrylate which is a photoreactive monomer represented by the structural formula [2],

[Chemical 2] And (3) a C component consisting of a photopolymerization initiator,
The present invention relates to a novel photocurable resin composition in which a component, a component B and a component C are blended in a specific 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 (meth). ) Polyester poly (meth) acrylate obtained by reaction with acrylic acid, epoxy poly (meth) acrylate obtained by reaction with epoxy resin and (meth) acrylic acid, polyol with polyisocyanate and hydroxyl group-containing (meth) acrylate Urethane poly (meth) acrylate obtained by reaction, polysiloxane poly (meth) acrylate obtained by reaction of polysiloxane and (meth) acrylic acid compound, polyamide poly obtained by reaction of polyamide and (meth) acrylic acid compound (Meth) acrylate etc. are mentioned.

Among the above oligomers, examples of the saturated or unsaturated carboxylic acid which is a constituent of the polyester (meth) acrylate include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, 2,3-dimethylsuccinic acid, Hexyl succinic acid, glutaric acid, 2,2-dimethyl glutaric acid, 3,
3-dimethyl glutaric acid, 3,3-diethyl glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexane Dicarboxylic 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, or alkyl ester derivatives. Examples of the alkyl polyol include ethylene glycol, 1,3-propanediol, propylene glycol, 2,3-butanediol, 1,4-butanediol, 2-ethylbutane-1,4-diol, and 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, trimethylolethane, 2,2-dimethyl-3--
Examples thereof include hydroxypropionate, 2-butene-1,4-diol and the like.

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-diisocyanate ethyl, 2,6- Polyisocyanate monomers such as diisocyanate hexanoate, dimers and trimers of these isocyanates, There can be mentioned adducts of these isocyanate and polyol.

Specific examples of the polyol used in the adduct include, but are not limited to, ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, trimethylolpropane, and polytriethylene. 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 polycaprolactones. Examples thereof include polyester polyols such as caprolactone polyol.

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

The norbornel (meth) acrylate which is the reactive monomer which is the component B is obtained by adding (meth) acrylic acid to the norbornene which is a bicyclic olefin represented by the structural formula [3] in the presence of an acid catalyst. can get.

[Chemical 3]

The component C photopolymerization initiator can be arbitrarily selected from known ones and used. Specific examples thereof include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthfluorenone, benzaldehyde, and the like. Anthraquinone, 3-methylacetophenone,
4-chlorobenzophenone, 4,4'-diaminobenzophenone, benzoinpropyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy -2-Methyl-1-phenylpropane-1-
On, 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 are alone,
Or it can be used as a mixture of two or more kinds,
The amount used is 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on the total amount of the components A and B.

Further, the resin composition of the present invention contains the component A,
In addition to B component and C component, if necessary, a photosensitizer, a photo accelerator, a polymerization inhibitor, an extender pigment, a matting agent, a coloring pigment, a dye,
An antifoaming agent, a leveling agent, a dispersant, a plasticizer 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, etc. 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 odor, low skin irritation and excellent environmental resistance properties, and 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] Polyethylene glycol (average molecular weight: 400) 400 parts and isophorone diisocyanate 6
66 parts and 464 parts of hydroxyethyl acrylate, 60 parts
The reaction was carried out at 0 ° C for 10 hours to obtain urethane acrylate A.

[0017]

Example 1 80 parts of urethane acrylate A, 20 parts of norbornyl acrylate, a photopolymerization initiator (Darocur 1173:
E, manufactured by Merck & Co., Inc.) was mixed at room temperature to prepare a resin composition.

[0018]

Example 2 60 parts of urethane acrylate A, 40 parts of norbornyl acrylate, a photopolymerization initiator (Darocur 1173:
E, manufactured by Merck & Co., Inc.) was mixed at room temperature to prepare a resin composition.

[0019]

Comparative Example 1 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.

[0020]

Comparative Example 2 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.

[0021]

[Comparative Example 3] 80 parts of urethane acrylate A, phenoxyethyl acrylate (POA: manufactured by Kyoeisha Yushi-Kagaku Kogyo)
20 parts, photopolymerization initiator (Darocur 1173: E, manufactured by Merck)
3 parts were mixed at room temperature to prepare a resin composition.

[0022]

[Comparative Example 4] 60 parts of urethane acrylate A, phenoxyethyl acrylate (POA: manufactured by Kyoeisha Yushi Kagaku Kogyo)
40 parts, photopolymerization initiator (Darocur 1173: E, manufactured by Merck)
3 parts were mixed at room temperature to prepare a resin composition.

[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 using a bar coater (# 10), and the coated plate was subjected to a high pressure of 80 W / cm. Using one mercury lamp, the conveyor speed was set to 15 m / min, and light was hardened by repeatedly passing a position 20 cm from the lamp until tack-free. 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. From these results, the resin composition of the present invention has low odor, low viscosity, low skin irritation, excellent curability, and a cured product excellent in hardness, stain resistance, and solvent resistance can be obtained. I understood.

[0024]

[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 remaining contamination level was evaluated on a scale of 5 when wiped with gauze soaked with ethanol. The higher the number, the less pollution. 3) Solvent resistance: The number of times until the coating film is dissolved and the substrate is exposed by rubbing the coating film with gauze soaked with ethanol and methyl ethyl ketone.

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[Procedure amendment]

[Submission date] November 24, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0014

[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. The photocurable resin composition can be prepared by blending it in an amount of 0.1 to 10 parts by weight based on 100 parts by weight in total, and can be a photocurable resin composition having low odor and excellent operability, and a cured product thereof. Has excellent solvent resistance, 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

[Name of item to be corrected] 0024

[Correction method] Change

[Correction content]

[0024]

[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) norbornyl (meth) which is a reactive monomer represented by the structural formula [1]. B component consisting of acrylate, And (3) a photocurable resin composition composed of a C component comprising a photopolymerization initiator, wherein the total amount of the A component and the B component is
It is composed of 5 to 95 parts by weight of the component A and 95 to 5 parts by weight of the component B in 100 parts by weight, and the component C is a mixture of the components A and B 100
A photocurable resin composition having a composition ratio of 0.1 to 10 parts by weight based on parts by weight.