JP2002059433A - Method for forming decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for obtaining a decorative sheet comprising a good coating film short in curing time, generating no pinhole, having luster and free from haze, when forming the decorative sheet using an unsaturated polyester resin. SOLUTION: A surface coated with a composition, which contains 100 pts.wt. of (A) the unsaturated polyester resin and/or the vinyl ester resin and 0.1-10 pts.wt. of (B) a photopolymerization initiator having photosensitivity within a range from a visible region to a near infrared region, or the surface of the shaped film for forming the decorative sheet further applied to the coated surface is irradiated with light to cure the coated composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of forming a decorative board having various patterns such as a grain pattern of a natural tree, and more particularly to a flow coater method, a film method, a roll coater method, a brush coating method, and a spray method. The present invention relates to a method for forming a decorative board which is applied with a thermosetting resin and cured.

[0002]

2. Description of the Related Art A decorative board using an unsaturated polyester resin or a vinyl ester resin is inexpensive, can be easily molded at normal temperature, and can be molded at normal pressure or contact pressure.
In general, it is formed by attaching decorative paper on a paper-bonded plywood, applying the thermosetting resin by a flow coater method, a film method, a roll coater method, a brush coating method, and the like, and curing the resin.

Among these methods, in the method of applying and curing in an open system, such as a flow coater method, a roll coater method, and a brush coating method, it takes a long time to cure because of room temperature curing. In some cases, the commercial value of the decorative board, which is a molded article whose appearance is emphasized, is significantly reduced. In the case of application and curing in an open system, paraffin wax or the like is added because the curing of the resin is inhibited by oxygen in the air. Is inevitable. On the other hand, in the closed system by the film method, it is possible to prevent the invasion of foreign matter and the inhibition of hardening of the air contact surface, which are problems in the open system. Since the degree of curing is not constant due to the difference in time, the gloss and gloss of the surface are different, and it is difficult to obtain a uniform product. Further, in the conventional room-temperature curing method regardless of whether the system is open or closed, it takes a long time to cure, so that bubbles may be generated from the inside of the plywood after the application to the plywood and before the curing is completed, resulting in pinholes. As a method for solving the drawbacks of the room temperature curing method, a method of adding an ultraviolet polymerization initiator to a resin and curing the resin in a short time by irradiating ultraviolet rays is also known, but when a filler such as a pigment is filled. In addition, there is a disadvantage that the inside cannot be sufficiently cured by light irradiation with ultraviolet rays having low transmittance.

[0004]

SUMMARY OF THE INVENTION In view of these circumstances, it is an object of the present invention that when an decorative polyester is formed using an unsaturated polyester resin or a vinyl ester resin, it takes a long time to cure in an open system. It is an object of the present invention to provide a method of forming a decorative board that solves problems such as occurrence of uneven floating of wax, and that can obtain a stable gloss and gloss of the surface by the film method and that can be hardened to the inside in a short time. .

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have found that the above object can be achieved by using a specific photopolymerizing agent. The present invention has been completed based on such findings. That is, the present invention provides a photopolymerization initiator (A) having 100 parts by weight of an unsaturated polyester resin and / or a vinyl ester resin and (B) a photopolymerization initiator having photosensitivity in any range from a visible light region to a near infrared light region. A surface coated with a composition containing 1 to 10 parts by weight, or a surface coated with a molding film for forming a decorative plate, which is irradiated with light to cure the surface. It is a molding method. In the present invention, visible light refers to light in a wavelength range of 380 to 780 nm, and near-infrared light refers to light in a wavelength range of 780 to 1200 nm.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the method for molding a decorative sheet of the present invention, at least one of the unsaturated polyester resin and the vinyl ester resin (hereinafter, both resins may be collectively referred to as resin, etc.) as component (A). Use one of them. The unsaturated polyester resin converts an unsaturated polyester, which is a condensation product of an esterification reaction between a polyhydric alcohol and an unsaturated polybasic acid (and, if necessary, a saturated polybasic acid), into a polymerizable monomer such as styrene. Is dissolved,
The vinyl ester resin is also called an epoxy acrylate resin, and is generally formed by a ring-opening reaction between a compound having a glycidyl group (epoxy group) and a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid. A compound obtained by dissolving a vinyl ester, which is a compound having an unsaturated bond, in a polymerizable monomer such as styrene. Each of them is described in "Polyester Resin Handbook" (published by Nikkan Kogyo Shimbun, 1988) Dictionaries "(edited by the Society of Color Materials, published in 1993).

[0007] As the unsaturated polyester used as a raw material of the unsaturated polyester resin, those produced by a known method are used. Specifically, a polybasic acid having no polymerizable unsaturated bond such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid or an anhydride thereof and fumaric acid, maleic acid, itaconic acid And the like, and a polymerizable unsaturated polybasic acid or an anhydride thereof as an acid component, and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5- Pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2
Manufactured by reacting a polyhydric alcohol such as -dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, an ethylene oxide adduct of bisphenol A, or a propylene oxide adduct of bisphenol A as an alcohol component. It is.

[0008] As the vinyl ester used as a raw material of the vinyl ester resin (epoxy acrylate resin), those produced by a known method can be used, and an unsaturated monobasic acid such as acrylic acid or methacrylic acid is added to the epoxy resin. Α, β having an epoxy group in an epoxy (meth) acrylate obtained by reacting the above, or a saturated polyester having a terminal carboxyl group or an unsaturated polyester obtained from a saturated dicarboxylic acid and / or an unsaturated dicarboxylic acid and a polyhydric alcohol. A polyester (meth) acrylate of a saturated polyester or an unsaturated polyester obtained by reacting an unsaturated carboxylic acid ester.

Examples of the epoxy resin as a raw material of the vinyl ester resin include bisphenol A diglycidyl ether, its high molecular weight homologues, and novolak type polyglycidyl ethers. As the saturated dicarboxylic acid used for the polyester (vinyl ester raw material) having a terminal carboxyl group used for the production of the polyester (meth) acrylate, a dicarboxylic acid having no active unsaturated group, for example, phthalic acid, isophthalic acid, terephthalic acid , Tetrahydrophthalic acid, adipic acid, sebacic acid and the like. Examples of the unsaturated dicarboxylic acid include dicarboxylic acids having an active unsaturated group, such as fumaric acid, maleic acid, maleic anhydride, and itaconic acid. As the polyhydric alcohol component, for example, ethylene glycol,
Propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-
Butanediol, 1,5-pentanediol, 1,6-
Hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol,
Polyhydric alcohols such as cyclohexane-1,4-dimethanol, ethylene oxide adduct of bisphenol A, and propylene oxide adduct of bisphenol A are exemplified. Glycidyl methacrylate is a typical example of the α, β-unsaturated carboxylic acid ester having an epoxy group used in the production of polyester (meth) acrylate.

In the unsaturated polyester resin or vinyl ester resin used in the present invention, a monomer (reactive diluent) having an unsaturated group represented by a styrene monomer is usually added to the unsaturated polyester or vinyl ester. The monomer having an unsaturated group blended in the resin of the present invention is important for adjusting the resin viscosity or improving the hardness, strength, appearance, etc. of the molded product. Styrene monomer is effective in terms of ease and cost. The amount of the monomer having an unsaturated group is 10 to 250 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of the unsaturated polyester or vinyl ester. If the amount is less than 10 parts by weight, the workability is deteriorated due to the high viscosity. If the amount exceeds 250 parts by weight, sufficient strength cannot be obtained, which is not preferable as a resin for decorative board. When a styrene monomer is used as the monomer having an unsaturated group, a part or all of the styrene monomer is converted into a styrene-based monomer such as chlorostyrene, vinyltoluene, divinylbenzene, methyl (meth) acrylate, ethyl (meth) acrylate, Other polymerizable monomers such as ethylene glycol di (meth) acrylate can be substituted for and used without impairing the gist of the present invention.

In the present invention, a pigment can be used. There is no particular limitation on the type, and organic pigments or inorganic pigments can be used. At that time, an amount of at most 20 parts by weight, preferably up to 10 parts by weight, per 100 parts by weight of the resin or the like can be used.

The photopolymerization initiator used as the component (B) in the present invention and having photosensitivity in a range from the visible light region to the near infrared light region includes known visible light polymerization initiators and near infrared light initiators. A polymerization initiator can be used. As a photopolymerization initiator having photosensitivity in the visible light region, for example, Yamaoka et al.
"Surface", 27 (7), p. 548 (1989), Sato et al., "Abstracts of the 3rd Polymer Material Forum", 1
B, page 18 (1994), in addition to a single visible light polymerization initiator such as camphorquinone, benzyl, trimethylbenzoyldiphenylphosphine oxide, methylthioxanthone, bispentadienyltitanium-di (pentafluorophenyl), Organic peroxide catalyst / dye system,
Diphenyl iodonium salt / dye, biimidazole / keto compound, hexaarylbimidazole compound / hydrogen donating compound, mercaptobenzothiazole / thiopyrylium salt, metal arene / cyanine dye,
Known hybrid photopolymerization initiator systems such as hexaarylbiimidazole / radical generator described in JP-A-37377.

Similarly, a (bis) acyl phosphine oxide compound is suitably used as a photopolymerization initiator having photosensitivity in the visible light region. This (bis) acyl phosphine oxide compound has the general formula (4)

[0014]

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(Wherein R ⁵ , R ⁶ and R ⁷ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, or an alkynyl group); 5)

[0016]

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(Wherein R ⁸ , R ⁹ and R ¹⁰ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, or a heterocyclic group). .

The photopolymerization initiator comprising these (bis) acyl phosphine oxide compounds has photosensitivity even in the visible light region, is excellent in light transmittance, and is cleaved by light irradiation to produce an acyl radical and a phosphinoyl radical. It is said that polymerization initiation efficiency is higher than that of a conventionally used UV initiator.

Specific examples of the bisacylphosphine oxide compound of the general formula (4) include bis (2,6-dichlorobenzoyl) -phenylphosphine oxide and bis (2,6-dichlorobenzoyl) -2,5- Dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-biphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dichloro) Benzoyl) -4-chlorophenylphosphine oxa , Bis (2,6-dichlorobenzoyl) -2,2-dimethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -dodecylphosphine oxide, bis (2,6-dichlorobenzoyl) -4- Octylphenylphosphine oxide,
Bis (2,4,6-trimethylbenzoyl) -2,5-
Dimethylphenylphosphine oxide, bis (2,6
-Dichloro-3,4,5-trimethoxybenzoyl)-
2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide,
Bis (2-methyl-1-naphthoyl) -2,5-phenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-biphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-ethoxy Biphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2-naphthylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-propylphenylphosphine oxide, bis (2-methyl-1-naphthoyl)- 2,5-dimethylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-methoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, and the like. be able to.

Specific examples of the acylphosphine oxide compound of the general formula (5) include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,6-
Diphenylbenzoyl-diphenylphosphine oxide, 2,6-dimethoxybenzoyl-diphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyl-diphenylphosphine oxide, 2,6-dichlorobenzoyl-diphenylphosphine oxide,
2,3,6-trimethylbenzoyl-diphenylphosphine oxide, 2-phenyl-6-methylbenzoyl-diphenylphosphine oxide, 2,6-dibromobenzoyl-diphenylphosphine oxide, 2,8
-Dimethylnaphthalene-1-carbonyl-diphenylphosphine oxide, 1,3-dimethoxynaphthalene-
2-carbonyl-diphenylphosphine oxide,
2,4,6-trimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-dimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-dichlorobenzoyl-phenylphosphinic acid methyl ester, and the like.

Commercially available photopolymerization initiators containing these (bis) acylphosphine oxide compounds include, for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 1173, Ciba Specialty Co., Ltd.). Chemicals Co., Ltd.) and screws (2,6-
Irgacure-1700 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) mixed with dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd.) at a ratio of 75% / 25% ); 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure-18)
4, a ratio of 75% / 25% of bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (manufactured by Ciba Specialty Chemicals) and Ciba Specialty Chemicals (manufactured by Ciba Specialty Chemicals). 1800 (manufactured by Ciba Specialty Chemicals Co., Ltd.); trade names Irgacure 1850 (manufactured by Ciba Specialty Chemicals Co., Ltd.), bis (2) , 4,
6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819, manufactured by Ciba Specialty Chemicals Co., Ltd.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Lucirin TPO, manufactured by BASF Corporation) ); 2-
Hydroxy-2-methyl-1-phenylpropane-1-
ON (trade name: Darocur 1173, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Lucirin TPO, manufactured by BASF)
Trade name Darocur mixed at a ratio of 0% / 50%
4265 and the like. The above-mentioned photopolymerization initiator containing a (bis) acylphosphine oxide compound may be used alone or in combination.

As the photopolymerization initiator of the component (A),
General formula (1) D ⁺ · A ⁻ (1) (wherein, D ⁺ is a methine, polymethine, cyanine, xanthene, oxazine, thiazine, arylmethane, pyrylium-based compound having photosensitivity in the visible or near infrared light region) A ⁻ represents various anions.) A cationic dye represented by the general formula (2):

[0023]

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(Wherein, Z ⁺ represents an arbitrary cation;
¹ , R ² , R ³ and R ⁴ are each independently an alkyl group, aryl group, acyl group, aralkyl group, alkenyl group, alkynyl group, silyl group, heterocyclic group, halogen atom, substituted alkyl group, substituted aryl group , A substituted acyl group,
It represents a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group, a substituted silyl group or a substituted heterocyclic group. ) Can also be preferably used.

Examples of the cation represented by “Z ⁺ ” in the general formula (2) include a quaternary ammonium cation, a quaternary pyridinium cation, a quaternary quinolinium cation, a diazonium cation, a tetrazolium cation, and a sulfonium. Cations, oxosulfonium cations, metal cations such as sodium, potassium, lithium, magnesium, calcium, etc., (organic) compounds having a cation charge on oxygen atoms such as flavylium, pyranium salts, tropylium, cyclopropylium, etc. Examples include carbon cations, halogenium cations such as iodonium, and cations of metal compounds such as arsenic, cobalt, palladium, chromium, titanium, tin, and antimony.

By combining the organic boron compound with a cationic dye having a photosensitive wavelength in the visible or near-infrared light region, the dye irradiated with light having a wavelength in the photosensitive region is excited, and By exchanging electrons with electrons, the dye is decolorized and radicals are generated, thereby causing a polymerization reaction of the coexisting polymerizable unsaturated compound. In this polymerization reaction, unlike a conventional ultraviolet polymerization reaction or the like, generated radicals can be easily controlled, and a part of unsaturated groups in the resin can be easily stopped at the time of radical polymerization.
In addition, since long wavelengths in the visible light or near-infrared light region are used, the reaction can be easily performed even in a system in which a filler, a pigment, or the like is added.

Examples of the combinations of the above-mentioned cationic dyes and boron compounds are described in JP-A-3-111402, JP-A-3-179003, and JP-A-4-146905.
JP, JP-A-4-261405, JP-A-4-4-2
There are detailed descriptions in JP-A-61406, JP-A-5-194619 and the like. Tables 1 and 2 show specific examples of the cationic dye “D +”. Among these cationic dyes, cyanine-based, styryl-based cationic dyes and triarylmethane-based dyes are preferably used. Cyanine-based and styryl-based cationic dyes are preferred in that the electron transfer with an organic boron-based compound generally occurs easily, and the photocuring reaction of the present invention easily occurs.

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

[Table 3]

[0031]

[Table 4]

A ⁻ , which is a counter anion of the cationic dye represented by the general formula (1), is any anion such as p-toluenesulfonate ion, organic carboxylate ion, perchlorate ion and halide ion. And the following general formula (6)

[0033]

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(Wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent an alkyl group, an aryl group, an acyl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group, a heterocyclic group, a halogen atom And a substituted alkyl group, a substituted aryl group, a substituted acyl group, a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group, a substituted silyl group, or a substituted heterocyclic group.) .

The composition ratio of the organic boron compound represented by the general formula (2) to the cationic dye represented by the general formula (1) is 1/5 to 1 / 0.05, preferably 1/1 to 1 by weight.
1 / 0.1. From the viewpoint of the decolorization reaction of the dye and the radical generation efficiency, it is generally preferable to use more organic boron compounds than the cationic dye.

The amount of the photopolymerization initiator (B) added is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the resin. Can be used in combination. If the amount of the photopolymerization initiator is smaller than this, the surface cannot be dried sufficiently. If the amount is larger than this, it is economically disadvantageous and the physical properties of the cured product are deteriorated.

In the present invention, in addition to the photopolymerization initiator of the component (C), a polymerization initiator comprising the organic boron compound represented by the above general formula (2) and an acidic compound, or the organic boron compound, the acidic compound and General formula (3)

[0038]

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(Wherein L ¹ , L ² and L ³ each independently represent an aryl group or a substituted aryl group). It is preferable to combine a polymerization initiator comprising a hexaarylbiimidazole compound represented by the following formula:

Examples of the acidic compound used in combination in this manner include inorganic acids generally known as Bronsted acids, for example, hydrochloric acid, sulfuric acid, nitric acid and the like, or organic acids such as acetic acid, propionic acid, maleic acid and the like.
Examples include carboxylic acids such as adipic acid, (meth) acrylic acid, benzoic acid, and phthalic acids, and sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. Compounds having a hydroxyl group such as phenols and alcohols, compounds having a mercapto group such as various thiols, and substances capable of forming a covalent bond by receiving an electron pair known as a Lewis acid, such as aluminum chloride, stannic chloride, Boron chloride, boron tribromide, or the like can be used. These acids are described, for example, in "Organic Chemistry", Third Edition, 43, by Morrison Boyd.
See page for details. In addition, a substance having an acidic active site on a solid surface such as an acidic ion exchange resin, carbon black, and alumina, or an acidic gas compound such as hydrogen chloride and sulfurous acid gas can also be used. Among these acidic compounds, acidic compounds having a polymerizable unsaturated group such as (anhydride) maleic acid, fumaric acid, or their half esters, (meth) acrylic acid, and itaconic acid, or oligomers having their functional groups Alternatively, polymers and the like are preferably used.

Further, the substance itself is not an acidic substance,
A compound which decomposes or reacts by the action of heating, moisture in the air, oxygen or the like to generate an acidic compound also falls under the acidic compound of the present invention as a latent acidic compound. In addition, a substance that is decomposed by light irradiation to generate an acidic compound is also known. For example, a compound called a photocationic polymerization initiator also corresponds to the acidic compound of the present invention as a latent acidic compound. Various compounds such as diazonium compounds, sulfonium compounds, and iodonium compound metal complex compounds are known as photocationic polymerization initiators.
The details are described in, for example, "Applications and Markets of UV / EB Curing Technology", October 2005, paragraph 5, p. 78, published by CMC 1989.

Among these compounds which should be called latent acidic compounds, compounds which generate an acid by light or heat are desirable in consideration of availability, economy, stability in the composition, operability, and the like. More preferred are thermal acid-generating compounds, and particularly preferred are organic sulfonium compounds that generate an acid by being decomposed by heating. Organic sulfonium compounds are generally composed of an ion pair consisting of a sulfonium cation moiety having three substituents (such as an alkyl group and an aryl group) and an anion serving as a counter ion. It is preferable that at least one of the substituents of the sulfonium salt is an aryl group such as a (substituted) phenyl group and a (substituted) naphthyl group from the viewpoints of the function and the acid strength of the generated acidic compound. For example, sulfonium compounds having a cation moiety such as triphenylsulfonium and diphenylmethylsulfonium can be mentioned.
For example, when the pot life of the resin composition containing the photopolymerization initiator is sufficiently required, it is not preferable that the organic boron compound and the acidic compound come into contact at the time of blending the initiator. It is desirable to use a compound that generates an acidic compound when stimulated by heat or light.

Further, when light is irradiated by combining an organic boron compound and an acidic compound with a hexaarylbiimidazole compound, curing is further accelerated and a remarkable effect is observed. Therefore, it is preferable to use these in combination. Specifically, as a hexaarylbiimidazole compound,
Bis (2,4,5-triphenyl) imidazole, bis (2-o-chlorophenyl-4,5-diphenyl) imidazole, bis (2-o, p-dichlorophenyl-4,
5-diphenyl) imidazole, bis (2-o-bromophenyl-4,5-diphenyl) imidazole and the like. The hexaarylbiimidazole compound is described in detail in JP-B-41-3545.

An organic boron compound and a (latent) acidic compound when combined with the photopolymerization initiator of the component (B);
Alternatively, the optimal amount of the organic boron compound, the (latent) acidic compound and the hexaarylbiimidazole varies depending on the type of the resin and the like, the thickness to be applied, and the like. ~ 20 parts by weight,
Preferably it is 0.05 to 15 parts by weight. If the amount is less than 0.01 part by weight, the polymerization tends to be insufficient. If the amount exceeds 20 parts by weight, it is economically disadvantageous and the physical properties of the cured product are deteriorated. When the resin or the like contains an acidic compound in advance, maleic acid, fumaric acid, or their half esters, (meth) acrylic acid, itaconic acid, An oligomer or a polymer having a carboxyl group of the carboxylic acid may be used, or a resin or the like added with an arbitrary acidic compound may be used. In this case, the acid value of the unsaturated polyester resin or vinyl ester resin is 0.1 to 100 mgKOH / g, preferably 5 to 50 mKOH / g.
gKOH / g.

The composition ratio of the organic boron compound to the (latent) acidic compound is 0.1 / 5 to 5 / 0.1, preferably 0.5 / 5 to 5 / 0.5 by weight. When the use ratio of the organic boron compound is larger than the range (therefore, the use ratio of the (latent) acidic compound is smaller than the range), the pot life is short and the physical properties are deteriorated. When the ratio is smaller (therefore, the use ratio of the (latent) acidic compound is larger than the range), the pot life is short and the physical properties are reduced. Further, when hexaarylbiimidazole is combined with the organic boron compound and the (latent) acidic compound for further rapid curing, the weight ratio of the organic boron compound / hexaarylbiimidazole is 0.1 / 5.
５5 / 0.1, preferably 0.5 / 5 to 5 / 0.5. When the amount of hexaarylbiimidazole is less than this ratio, the effect does not appear. When the amount is too large, it is economically disadvantageous and the usable time under visible light (working time) is shortened, and the physical properties of the cured product are reduced. And so on.

In the present invention, it is preferable to combine an organic peroxide catalyst or a polymerization initiator comprising an organic peroxide catalyst and a reducing agent with the photopolymerization initiator of the component (C).
As the organic peroxide catalyst used at this time, known ketone peroxide, peroxyketal, hydroperoxide, diallyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate is classified. Yes, and azo compounds are also effective. Specific examples include, for example, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, 1,1-bis (t-butylperoxy) -3,3. , 5-Trimethylcyclohexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, 3-isopropylhydroperoxide, t-butylhydroperoxide, dicumyl peroxide, dicumylhydro Peroxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide,
3,3,5-trimethylhexanoyl peroxide,
Examples thereof include lauryl peroxide, and a polymerization initiator of an azo compound such as azobisisobutyronitrile and azobiscarbonamide can also be used.

Examples of the combination comprising an organic peroxide catalyst and a reducing agent include a known combination of a ketone peroxide and a reducing agent, a combination of a hydroperoxide and a reducing agent, and a combination of a diacyl peroxide and a reducing agent. Specific examples of the reducing agent include cobalt salts such as cobalt naphthenate and cobalt octylate;
Vanadium compounds such as vanadium pentoxide; amines such as dimethylaniline; Among them, a combination of a peroxyester and a cobalt salt is particularly effective in terms of pot life and the like.

The amount of the organic peroxide catalyst or the polymerization initiator obtained by combining the organic peroxide and the reducing agent varies depending on the setting of the pot life, but is generally based on 100 parts by weight of a resin or the like. 0.01 to 20 parts by weight, preferably 0.05
１５15 parts by weight. If the amount is less than 0.01 part by weight, the polymerization tends to be insufficient. If the amount exceeds 20 parts by weight, it is economically disadvantageous and the physical properties of the cured product are deteriorated.

In the present invention, the surface coated with the composition containing the resin (A) and the photopolymerization initiator (B), or a composition obtained by combining the above photopolymerization initiator with the composition is used. A decorative board is formed by irradiating light on the surface applied to a vinylon film or the like or the surface coated with a molding film for forming a decorative plate, and then curing. As a lamp that can be used as a light source for irradiating and curing light, any light source that indicates light in a wavelength range of 380 to 1200 nm may be used, such as a metal halide lamp, a xenon lamp, a mercury lamp, a sunlight lamp, a near-infrared lamp, a sodium lamp, and a solar lamp. Light or the like can be used, and a visible light lamp is preferably used. The light irradiation time for curing is appropriately selected depending on the effective wavelength range of the light source, the output, the irradiation distance, the thickness of the composition, and the like, and cannot be specified unconditionally, but 0.01 hour or more, preferably 0.05 More than an hour. By applying a composition containing a resin or the like and a photopolymerization initiator by the method of the present invention, or a composition in which a polymerization initiator is further combined, and photocuring, the composition is cured in a short time, and there is no unevenness of wax. Thus, a decorative plate with excellent gloss can be obtained.

[0050]

Next, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited by the following examples. Note that “parts” in each example is based on weight.

Example 1 1-hydroxy-cyclohexyl-phenyl-ketone: 25%, bis (2,6-dimethoxybenzoyl) in 100 parts of an unsaturated polyester resin (trade name: Rigolac 2260, manufactured by Showa Polymer Co., Ltd.) ) 2,2,4,4-trimethylpentylphosphine oxide: 75% bisacylphosphine oxide-based photopolymerization initiator (Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 1800, hereinafter abbreviated as I-1800) 2 .5 parts was added to obtain a photocurable resin composition. Next, a photo-curable resin was placed on a paper-laminated plywood, covered with a glossy vinylon film and spread evenly with a rubber roller. A 250 W metal halide lamp (Mitsubishi Electric Corporation) as a visible light source was used. ), The film was irradiated to light at a distance of 10 cm, and was cured to a level at which the film could be peeled in 30 seconds.
The state of the decorative plate from which the film was peeled after one minute of light irradiation was good without gloss and fogging. The results are shown in Table 3.

Comparative Example 1 Rigolac 2260: 100 parts by weight of permec N / Co naphthenate (Co: 6%) as a room temperature curing catalyst =
A room temperature curable resin composition to which 1.0 part / 0.5 part was added was obtained. Next, place the room temperature curable resin on the paper-laminated plywood,
After covering with a glossy vinylon film, it was spread uniformly with a rubber roller and allowed to stand at room temperature. After 30 minutes, the film was cured to a level at which the film could be peeled off. The state of the decorative plate from which the film was peeled after one hour of standing was a state with much fogging. The results are shown in Table 3.

Example 2 100 parts of a vinyl ester resin (manufactured by Showa Polymer Co., Ltd., trade name: Lipoxy H-630) was added to 100 parts of Table 1
1,5,5-tetrakis (p-diethylaminophenyl) -2,4-pentadienyl triphenyl-n-butyl borate (Near-infrared light-absorbing cationic dye manufactured by Showa Denko KK: hereinafter abbreviated as IRB) 0.1 part and tetra-n-
A photocurable resin composition obtained by adding a near-infrared photopolymerization initiator combined with 0.5 part of butylammonium triphenyl-n-butylborate (organic boron compound manufactured by Showa Denko KK, hereinafter abbreviated as P3B) I got Using this photocurable resin, a glossy vinylon film is covered by the same operation as in Example 1 and spread evenly with a rubber roller, and AL-spotlight (ALF- 1
0) Using 1KW (made by RDS), 2
Irradiation at a distance of 0 cm cured in 3 minutes to a level at which the film could be peeled off. The state of the decorative board from which the film was peeled after 5 minutes of light irradiation was good without gloss and fogging. The results are shown in Table 3.

Comparative Example 2 Room-temperature curable resin composition containing 1.0 part / 0.5 part of Permec N / Co-naphthenate (Co: 6%) as a room-temperature curing catalyst added to 100 parts of Lipoxy H-630 Use
When the same operation as in Comparative Example 1 was performed, the film was cured to a level at which the film could be peeled off at room temperature for 30 minutes similarly to Comparative Example 1. The state of the decorative plate from which the film was peeled after one hour of standing was a state with much fogging. The results are shown in Table 3.

Example 3 Vinyl ester resin (manufactured by Showa Polymer Co., Ltd., trade name:
Lipoxy R-806) 100 parts with black pigment (manufactured by Showa Polymer Co., Ltd., trade name: Rigolac Color RC-81) 8
Parts, 1.5 parts of phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide (trade name: Irgacure 819, manufactured by Ciba Specialty Chemicals Co., Ltd .; hereinafter abbreviated as I-819), P3B: 0.5 And 1.0 part of a light / heat latent acid generator (sulfonium compound) (trade name: CI-2624, manufactured by Nippon Soda Co., Ltd.), 2,
2'-bis (o-chlorophenyl) -4,5,4 ',
0.5 part of 5′-tetraphenyl-1,2′-bisimidazole was mixed to obtain a photocurable resin composition. next,
The same operation as in Example 1 was performed, and light irradiation was performed under the same conditions.
In minutes, the film was cured to a level where the film could be peeled off. The state of the decorative plate from which the film was peeled after 2 minutes of light irradiation was good without gloss and fogging. The results are shown in Table 3.

COMPARATIVE EXAMPLE 3 100 parts of Lipoxy R-806 were added with 1.0 part / 0.5 part of Permec N / Co naphthenate (Co: 6%) as a room temperature curing catalyst. When the same operation as in Comparative Example 1 was performed using the composition, Comparative Example 1
In the same manner as in the above, the film was cured to a level at which the film could be peeled off at room temperature for 30 minutes. The state of the decorative plate from which the film was peeled after one hour of standing was a state with much fogging. The results are shown in Table 3.

Example 4 Rigolac 2260: 100 parts of white pigment (trade name: Rigolac Color RC-10, manufactured by Showa Polymer Co., Ltd.) 1
5 parts, I-819: 1.5 parts, Permec N / Co naphthenate (Co: 6%) = 1.0 part / 0.5 part,
A photocurable / room temperature curable combined resin composition was obtained. Next, the same operation as in Example 1 was performed and light irradiation was performed under the same conditions, and the film was cured to a level at which the film could be peeled in one minute. The state of the decorative plate from which the film was peeled after 2 minutes of light irradiation was good without gloss and fogging. The results are shown in Table 3.

Comparative Example 4 Rigolac 2260: A cold curing resin composition containing 100 parts of a cold curing catalyst, Permec N / Co naphthenate (Co: 6%) = 1.0 part / 0.5 part, was used. And
The same operation as in Comparative Example 1 was performed. As in Comparative Example 1, the film was cured to a level at which the film could be peeled off at room temperature for 30 minutes. The state of the decorative plate from which the film was peeled after one hour of standing was a state with much fogging. The results are shown in Table 3.

Comparative Example 5 Rigolac 2260: A cold-curable resin composition was obtained by adding 1.0 part / 0.5 part of Permec N / Co naphthenate (Co: 6%) as a cold-curing catalyst to 100 parts. Was. Next, place the room-temperature curable resin on the paper-laminated plywood, cover it with a glossy vinylon film, spread it evenly with a rubber roller, and remove the film after 2 hours of standing. there were. The results are shown in Table 3.

Comparative Example 6 Rigolac 2260: A cold curing resin composition was obtained by adding permec N / Co naphthenate (Co: 6%) = 1.0 part / 0.5 part as a cold curing catalyst to 100 parts. Was. Next, place the room-temperature curable resin on the paper-laminated plywood, cover it with a glossy vinylon film, spread it evenly with rubber rollers,
Four hours after leaving the film, the state of the decorative plate from which the film was peeled was reduced, but the fogging was still not completely removed. The results are shown in Table 3.

Example 5 Rigo rack 2260: 100 parts of Rigo rack color R
C-10: 15 parts and I-819: 1.5 parts were mixed to obtain a photocurable resin composition. Next, a photocurable resin is applied onto the paper-bonded plywood by a brush coating method, and a 250 W metal halide lamp (manufactured by Mitsubishi Electric Corporation), which is a visible light source with an open surface, is used at a distance of 10 cm. Upon irradiation with light, the inside was cured in 1 minute. It was confirmed that it could be cured in an open system for a short period of time and that the surface of the decorative panel coating was good.

Comparative Example 7 Rigo rack 2260: 100 parts of Rigo rack color R
C-10: 15 parts, I-819: 1.5 parts, UV polymerization initiator 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) : Irgacure 651) 1.5 parts were mixed to obtain a photocurable resin composition. Next, a photo-curing resin is applied on the paper-bonded plywood by a brush coating method, and a 10-cm high-pressure mercury lamp, which is a surface open system and uses a 1 KW high-pressure mercury lamp, which is a light source of ultraviolet light, is used.
When irradiated with light at a distance of 30 seconds, the surface hardened,
No matter how much irradiation was continued thereafter, the inside could not be cured.

[0063]

[Table 5]

[0064]

As is clear from the above examples, according to the molding method of the present invention, a decorative plate having a good coating film having a short curing time, no generation of pinholes, and having no gloss and no fogging. Can be obtained. The industrial significance of the present invention is significant because such a high-quality decorative board can be stably obtained by the method of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C08F 2/50 C08F 2/50 4J027 299/02 299/02 299/04 299/04 // B29K 67:00 B29K 67:00 B29L 7:00 B29L 7:00 31:00 31:00 F term (reference) 2B002 AA04 AA10 BB07 BB08 2B250 AA01 AA11 BA02 FA28 FA33 GA03 HA01 4D075 AE03 BB46Z CB12 DA06 DB22 DC02 EA21 EB35 EB45 4F203 A24A DB01 DC01 DC07 DF01 4J011 QB12 QB19 QB20 QB22 SA76 SA78 SA84 SA87 UA06 VA01 WA02 4J027 AB02 AB06 AB07 AB08 AB15 AB16 AB17 AB18 AB23 AB24 AB25 AE02 AE03 BA05 CB10 CC04 CD00

Claims (6)

[Claims] 1. A photopolymerization initiator (A) having 100 parts by weight of an unsaturated polyester resin and / or a vinyl ester resin and (B) a photopolymerization initiator having photosensitivity in any range from a visible light region to a near infrared light region. A surface coated with a composition containing 1 to 10 parts by weight, or a surface coated with a molding film for forming a decorative plate, which is irradiated with light to cure the surface. Molding method. 2. The photopolymerization initiator of the component (B) is (bis)
The method for forming a decorative sheet according to claim 1, wherein the method is an acylphosphine oxide compound. Wherein component (B) photopolymerization initiator, the general formula ^{(1) D + · A -} (1) ( wherein, D ⁺ has photosensitivity in a visible light region or infrared light region At least methine, polymethine, cyanine,
One of xanthene, oxazine, thiazine, arylmethane or pyrylium dye cations, and A ⁻ represents various anions. And a cationic dye represented by the general formula (2): (In the formula, Z ⁺ represents an arbitrary cation, and R ¹ , R ² , R
³ and R ⁴ each independently represent an alkyl group, an aryl group, an acyl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group, a heterocyclic group or a halogen atom. The decorative board forming method according to claim 1, wherein the organic boron compound represented by the following formula is combined. 4. A polymerization initiator comprising an organic boron compound represented by the general formula (2) and an acidic compound, or the organic boron compound, the acidic compound and the general formula (3) ) (Wherein L ¹ , L ² and L ³ each independently represent an aryl group or a substituted aryl group.) A polymerization initiator comprising a hexaarylbiimidazole compound represented by the following formula: A method for forming a decorative plate according to any of the claims. 5. The photopolymerization initiator of the component (B) may be one or more organic peroxides selected from the group consisting of ketone peroxides, hydroperoxides, peroxyesters and diacyl peroxides. The method for forming a decorative plate according to any one of claims 1 to 3, wherein a polymerization initiator comprising a product catalyst or a polymerization initiator comprising said organic peroxide catalyst and a reducing agent is combined. 6. The method according to claim 1, wherein the light source for irradiating and curing the light is a visible light lamp.