JPH06279566A - Active energy ray curable composition for polyvinyl chloride - Google Patents

Abstract

(57) [Summary] [Structure] A reaction product of diglycidyl ether of bisphenol A added with 3 mol of ethylene oxide and acrylic acid, and an isobornyl acrylate having an aliphatic ring having a bridge bond in the molecule are essential. An energy ray-curable composition for a vinyl chloride flooring material, which is included as a component. [Effect] An energy ray-curable composition for vinyl chloride flooring material having excellent adhesion to the vinyl chloride flooring material is obtained, and the vinyl chloride flooring material coated with the composition of the present invention has a particularly remarkable effect that the warp is small. Play.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an active energy ray curable composition for vinyl chloride.

[0002]

2. Description of the Related Art Polyvinyl chloride flooring materials (hereinafter abbreviated as vinyl chloride flooring materials) are widely used on floors of houses, offices, and stores as polyvinyl chloride tiles and cushion flooring materials. In Japan, there are still few cases where UV coating is used for these PVC flooring materials, and they are only used in some of the shops and offices where people walk on the ground. Unsaturated polyester resins and epoxy acrylates are used as photosensitive resins for UV coating of PVC flooring. For example, as a vinyl chloride flooring coating composition using an epoxy acrylate, a bisphenol A type epoxy acrylate and a polyfunctional (meta) such as trimethylol propane triacrylate can be used.
An ultraviolet curable composition is known in which a photoinitiator is used in combination with an acrylate.

[0003]

However, when a coating composition using the above-mentioned unsaturated polyester resin or epoxy acrylate is coated on a vinyl chloride flooring material, the vinyl chloride flooring material may shrink due to curing shrinkage of the coated film. However, there is a problem that the coating film is peeled off due to the insufficient adhesion between the coating film and the vinyl chloride flooring material.

[0004]

The inventors of the present invention have made diligent studies in view of the above situation and found that a specific epoxy resin-adduct (A) with an unsaturated monobasic acid and a specific (meth) acrylic acid are used. A composition containing an ester (B) as an essential component is
The present invention has been completed by finding that the PVC flooring material has little warpage and excellent adhesion.

That is, the present invention relates to an adduct (A) of a polyalkylene oxide-added aromatic epoxy resin and an unsaturated monobasic acid, and a (meth) acrylic acid ester having an aliphatic ring having a bridge bond in the molecule. An active energy ray-curable composition for polyvinyl chloride containing (B) as an essential component.

Hereinafter, polyvinyl chloride is abbreviated as "vinyl chloride", and polyvinyl chloride base material is abbreviated as "vinyl chloride base material".

The epoxy resin-unsaturated monobasic acid adduct (A) used in the present invention has a structure in which a polyalkylene oxide-added aromatic epoxy resin and an unsaturated monobasic acid are added, It can be easily obtained by reacting the epoxy resin with an acid.

Examples of the polyalkylene oxide-added aromatic epoxy resin used here include diglycidyl ether of bisphenol A polyethylene oxide adduct, diglycidyl ether of bisphenol A polypropylene oxide adduct, and bisphenol F polyethylene oxide adduct. Diglycidyl ether, diglycidyl ether of polypropylene oxide adduct of bisphenol F, polyglycidyl ether of polyethylene oxide adduct of phenol novolac, polyglycidyl ether of polypropylene oxide adduct of phenol novolac, polyglycidyl of polyethylene oxide adduct of cresol novolac ether,
Examples thereof include polyglycidyl ether which is a polypropylene oxide adduct of cresol novolac. These resins may be used alone or in combination of two or more.

Examples of unsaturated monobasic acids include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, acrylic acid dimer, monomethylmalate, monopropylmalate, monobutylmalate, mono (2-ethylhexyl). ) Malate, or sorbic acid.
These acids may be used alone or in combination of two or more kinds.

The mixing ratio of the epoxy resin and the unsaturated monobasic acid is not particularly limited, but is usually 0.1 to 1.2 of the acid relative to 1.0 equivalent of the epoxy group of the resin. It is a molar range.

In carrying out the present invention, a resin and an acid are essential components, and if necessary, an esterification catalyst and a polymerization inhibitor can be used.

An esterification catalyst can be used in order to efficiently proceed the esterification reaction between the resin and the acid and suppress other side reactions.

Examples of the esterification catalyst include triethylamine, benzyldimethylamine, α-methylbenzyldimethylamine, dimethylaminomethylphenol,
Tertiary amines such as tridimethylaminomethylphenol; quaternary ammonium salts such as trimethylammonium chloride, trimethylammonium bromide, triethylbenzylammonium chloride; imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole An organic phosphine compound such as triphenylphosphine and the like.

When such an esterification catalyst is used, the amount used is usually 0.01 to 0.01 with respect to the total weight of the resin and the acid.
The range of 5.0% is preferably 0.05 to 2.0.
The range of% is appropriate.

During the esterification reaction, polymerization is carried out in order to prevent gelation during the production of the adduct (A) and to prevent gelation of the completed adduct (A) during storage. It is preferable to use inhibitors.

Examples of such a polymerization inhibitor include hydroquinone, pt-butylcatechol, and 2,5-di-t.
-Hydroquinones such as butyl hydroquinone and mono-t-butyl hydroquinone; p-benzoquinone, naphthoquinone, phenanthraquinone, 2,5-diphenyl-
Examples thereof include quinones such as p-benzoquinone; phenols such as hydroquinone monomethyl ether and di-t-butyl-p-cresol; copper salts such as copper naphthenate.

Typically, the adduct is preferably an epoxy (meth) acrylate obtained by adding the epoxy resin to acrylic acid or methacrylic acid using an unsaturated monobasic acid. In the present invention, acrylate and methacrylate are collectively referred to as “(meth) acrylate”.

The epoxy (meth) acrylate (A) is preferably epoxy acrylate (ester obtained by esterifying the epoxy resin with acrylic acid as an essential component).

The (meth) acrylic acid ester (B) having an aliphatic ring having a bridge-like bond in the molecule is
For example, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl polyoxyethyl (meth) acrylate, dicyclopentenyloxypropyl ( (Meth) acrylate, dicyclopentenyl polyoxypropyl (meth) acrylate,
Examples thereof include tricyclodecane dimethylol di (meth) acrylate and di (meth) acrylate of an adduct of tricyclodecane dimethylol with ε-caprolactone.

The (meth) acrylic acid ester (B) having an aliphatic ring having a bridge-like bond in the molecule may be used alone or as a mixture of two or more kinds. The amount used is 20 to 100 parts by weight of the adduct (A).
A proportion of 300 parts by weight, preferably 30 to 250 parts by weight is suitable.

Examples of the active energy rays referred to in the present invention include electron rays, α rays, β rays, γ rays, X rays, neutron rays and ultraviolet rays.

Furthermore, when the active energy ray-curable composition of the present invention is used for ultraviolet curing, it is necessary to add a photopolymerization initiator in order to initiate the polymerization reaction of the composition by ultraviolet rays.

Typical examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether,
Benzoin and its alkyl ethers such as benzoin isobutyl ether and benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 2, 2
-Diethoxy-2-phenylacetophenone, 1,1-
Acetophenones such as dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one; methylanthraquinone, 2
Anthraquinones such as ethylanthraquinone, 2-tacharybutylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; thioxanthone,
Thioxanthones such as 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone , Benzophenones such as 4,4-bismethylaminobenzophenone and azo compounds.

These can be used alone or as a mixture of two or more kinds, and further, tertiary amines such as triethanolamine and methyldiethanolamine; benzoic acids such as 2-dimethylaminoethylbenzoic acid and ethyl 4-dimethylaminobenzoate. It can be used in combination with a photoinitiating auxiliary agent such as a derivative.

The amount used is 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the total weight of the adduct (A) and ester (B).

Further, in the resin composition of the present invention, if necessary, an inorganic filler such as silica powder, an organic filler such as hydrogenated castor oil and an inorganic thixotropic agent such as Aerosil, and a coloring agent are used. The various properties of the coating film can be enhanced by the combined use of agents, leveling agents, defoaming agents, fillers, release agents, polymerization inhibitors and the like.

The composition of the present invention thus obtained is
After coating on a known and commonly used PVC substrate, the composition is irradiated with active energy rays to cure the composition, whereby a cured product film can be formed on the substrate, particularly for coating PVC flooring. It is valid.

The thickness of the composition to be applied is not particularly limited, but the thickness of the composition (as a cured film) is 1 of the substrate thickness.
It is generally set to / 20 to 1/500.
The thickness of the base material itself is not particularly limited, but is usually 0.
It is 5 to 5 mm. The effect of the present invention is particularly remarkable when the substrate has a thickness of 4 mm or less and the composition (as a cured film) has a thickness of 1/50 to 1/150 of the substrate thickness.

[0029]

EXAMPLES Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following, all parts and% are based on weight unless otherwise specified.

[Synthesis Example 1] A stirrer, a cooler, a thermometer,
In a 4-necked flask equipped with a gas inlet tube and a heating device, an epoxy equivalent of 309, a diglycidyl ether of bisphenol A with 3 moles of ethylenelenoxide, "Epiclon 715" [manufactured by Dainippon Ink and Chemicals, Inc.] 309
Parts (1 equivalent) and 72 parts of acrylic acid (1 equivalent) were charged,
0.27 parts of hydroquinone based on the total weight, 2
Add 1.6 parts of methyl imidazole and add 12
The reaction was allowed to proceed for a period of time, and when the acid value reached 1 mgKOH / g, the reaction was terminated to obtain epoxy acrylate (A-1).

[Synthesis Example 2] The acid value was 3 mgKO in exactly the same manner as in Synthesis Example 1 except that "Epiclone 715" was changed to bisphenol A type epoxy resin "Epiclone 850".
H / g epoxy acrylate (A'-1) was obtained.

Example 1 100 parts of an epoxy acrylate composition obtained by heating and dissolving 50 parts of the epoxy acrylate (A-1) obtained in Synthesis Example 1 above and 50 parts of isobornyl acrylate. In contrast, 2-hydroxy-2-methyl-1-phenylpropan-1-one “Darocure-1
173 "(manufactured by Merck Japan Ltd.) was added and mixed well to prepare an active energy ray curable composition for PVC flooring.

The prepared composition was rolled with a roll coater at 30 ×.
A 30 cm square and 3 mm thick polyvinyl chloride tile was applied with a thickness of about 30 μm, and then a quartz ultraviolet lamp (80 w / cm condensing type) manufactured by Iwasaki Denki Co., Ltd.
The coating film was cured by irradiating twice at 5 cm and a line speed of 10 m / min. The warpage of the obtained coated plate and the adhesion of the coating film were measured. The results are shown in Table-1.

The test methods and criteria for performance shown in Table 1 are as follows. Adhesion: Cross-cuts are made in a grid pattern according to JIS K5400 8.5 test method, and then cellophane
Peeling test was performed. Table 2 shows how to express the evaluation scores.

Amount of warp deformation of plate: A coated plate was placed with the coated surface upward on a smooth glass plate of 50 cm square, and the amount of floating of the outer peripheral portion of the coated plate was measured with a caliper.

[Examples 2 to 4] Using the epoxy acrylate (A-1) obtained in Synthesis Example 1, a predetermined amount of (meth) acrylic acid ester (B) was added as shown in Table 1, and
A resin composition was prepared and the same test as in Example 1 was performed. The results are shown in Table-1.

Comparative Examples 1 and 2 Using the epoxy acrylate (A'-1) obtained in Synthesis Example 2, the photopolymerizable vinyl monomer shown in Table 1 was added in a predetermined amount to prepare a resin composition. Then, the same test as in Example 1 was performed. The results are shown in Table-1.

[0038]

[Table 1]

[0039]

[Table 2]

From Table 1, it was confirmed that the resin compositions of the present invention of Examples 1 to 4 were excellent in adhesiveness as compared with the conventional resin compositions, and PVC flooring materials having a small warpage were obtained.

[0041]

As described above, the resin composition of the present invention is
An essential component is an epoxy acrylate (A) obtained by the reaction of a polyalkylene oxide-added aromatic epoxy resin and (meth) acrylic acid and a (meth) acrylic acid ester having an aliphatic ring having a bridge-like bond in the molecule. Therefore, as compared with the conventional epoxy acrylate resin composition, there is a particularly remarkable effect that a vinyl chloride flooring material having excellent adhesion to a vinyl chloride flooring material and excellent appearance with little warpage can be obtained.

Claims (2)

[Claims] 1. An adduct (A) of a polyalkylene oxide-added aromatic epoxy resin and an unsaturated monobasic acid, and a (meth) acrylic acid ester (B) having an aliphatic ring having a bridge bond in the molecule. An active energy ray-curable composition for polyvinyl chloride, which comprises and as an essential component. 2. The ester (B) is isobornyl (meth).
Acrylate, dicyclopentenyl (meth) acrylate
Dicyclopentenyloxyethyl (meth) acryle
The composition according to claim 1, which is at least one selected from the group consisting of G.