JP2007246700A - Resin composition for decorative sheet and thermosetting resin coating paper and decorative sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain non-tacky thermosetting resin coating paper without a drying process, and to prevent the diffusion of VOC and the clouding and puncture of a molded article on thermal press-molding. <P>SOLUTION: This resin composition for the decorative sheets comprises a mixture resin comprising diallyl phthalate monomer and/or prepolymer and an unsaturated polyester resin, and a (meth)acrylate. The (meth)acrylate is used in an amount of 20 to 100 pts.wt. per 100 pts.wt. of the mixed resin, and has a boiling point of ≥150°C. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin composition for decorative board, a thermosetting resin-coated paper, and a decorative board.

A diallyl phthalate resin-based decorative board has been known so far, and since it is flexible and can be molded at low pressure and in a short time, it is hot-pressed by continuous molding. The decorative board is composed of a decorative layer and a core layer, and the decorative layer is made of resin-impregnated decorative paper impregnated with a resin liquid obtained by diluting diallyl phthalate resin with an organic solvent such as acetone or toluene and then dried. Yes.
JP 11-140777 A JP 62-149714 A

  In recent years, environmental considerations for manufacturing have been demanded. Conventional diallyl phthalate resin-based decorative boards have been exposed to concerns about the negative impact on the environment, as VOC (volatile organic chemicals) are diffused in the impregnation and drying process. Heat energy consumption has been an issue. As a technique for solving this problem, a solventless resin has been studied, but since it is difficult to reduce the viscosity, there is a problem that the coating method hardly penetrates the decorative paper, resulting in insufficient paper strength. Further, without the drying process, it is difficult to make the coated paper tack-free, and it is impossible to handle the coated paper as an intermediate product.

  The present invention has been studied in view of such circumstances, and a resin composition for a decorative board comprising a diallyl phthalate monomer and / or a prepolymer, an unsaturated polyester resin, and a (meth) acrylic acid ester, The decorative board is characterized in that the decorative paper is coated with the resin composition for decorative board and is prepared without drying, and further, the coated paper is hot-pressed together with the core material.

  The coated paper of the present invention can be dried by using a non-volatile (boiling point 150 ° C. or higher) (meth) acrylic acid ester as a reactive diluent as an alternative to the solvent that has been used so far. There is no tack even without a process, and in addition, it is possible to prevent a decrease in strength between papers due to insufficient penetration into decorative paper. Further, by using a solid diallyl phthalate resin and powdered silica, the tackiness is further reduced and the product can be handled as an intermediate product. Further, since the decorative board composition does not contain a volatile material, there is no volatile material during hot-press molding, and it is possible to prevent VOC emission and clouding and puncture of molded products.

  Examples of the diallyl phthalate prepolymer according to the present invention include diallyl orthophthalate prepolymer, diallyl isophthalate prepolymer, diallyl terephthalate prepolymer alone or a copolymer thereof, or a mixture thereof. Examples include orthophthalate, diallyl isophthalate or diallyl terephthalate, or a mixture thereof.

  The unsaturated polyester resin is composed of an unsaturated polyester and a polymerizable monomer, and the unsaturated polyester is an unsaturated dibasic acid and / or acid anhydride thereof and other saturated acid and / or acid anhydride used as necessary. And an acid component containing a polyhydric alcohol and a polyhydric alcohol subjected to a dehydration condensation reaction at about 160 to 230 ° C., preferably 210 to 230 ° C. in an inert gas atmosphere such as nitrogen or argon.

  Examples of the unsaturated dibasic acid and its acid anhydride include maleic acid, fumaric acid, itaconic acid, maleic anhydride and the like, and these may be used alone or in combination of two or more. The unsaturated dibasic acid and its acid anhydride are preferably used in an amount of 50 to 100 mol%, particularly preferably 60 to 100 mol%, in the acid component.

  Other saturated acids and / or acid anhydrides used as necessary include phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexahydrophthalic acid, tetrahydroanhydride Examples thereof include saturated dibasic acids such as phthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. These may be used alone or in combination of two or more. The blending amount of the saturated acid is 0 to 50 mol%, preferably 0 to 40 mol% in the acid component.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentadiol, 1,6- Examples thereof include dihydric alcohols such as hexanediol, triethylene glycol and neopentyl glycol, trihydric alcohols such as glycerin and trimethylolpropane, and tetrahydric alcohols such as pentaerythritol. These may be used alone or in combination of two or more. The blending amount is preferably in the range of 100 to 110 mol with respect to the total acid component 100.

  Examples of the polymerizable monomer include aromatic polymerizable monomers such as styrene, α-methylstyrene, vinyltoluene and paramethylstyrene, (meth) acrylic monomers such as methyl (meth) acrylate [(meth) acrylate Methacrylate and acrylate are shown. same as below. ], Ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl ( (Meth) acrylates, (meth) acrylic acid alkyl esters such as cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone-modified hydroxy Examples thereof include hydroxyl group-containing polymerizable monomers such as (meth) acrylate.

  Other dialkyl esters of unsaturated dibasic salts such as dimethyl maleate, dimethyl fumarate, dibutyl maleate, dibutyl fumarate, dimethyl itaconate, dibutyl itaconate, (meth) acrylamide, N-methylol (meth) acrylamide N-butoxymethylacrylamide, 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole, 2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl- Examples also include nitrogen-containing polymerizable monomers such as 2,2,6,6-tetramethylpiperidinyl methacrylate, acetate esters such as vinyl acetate, and polymerizable cyano compounds such as (meth) acrylonitrile.

  As (meth) acrylic acid ester, 2-hydroxyethyl (meth) acrylate [acrylate and methacrylate are represented as (meth) acrylate], 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyalkylene Glycol (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, and the like having a boiling point of 150 ° C. or higher are suitable. This may cause the emission of fog and clouding and puncture of molded products, and also volatilize during storage, leading to a decrease in storage stability of the coated paper.

  Examples of the polyalkylene glycol (meth) acrylate include polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate, which are obtained by reaction of polyalkylene glycol and (meth) acrylic acid.

  Epoxy (meth) acrylate is obtained by reacting an epoxy resin with an unsaturated monobasic acid. Examples of the epoxy resin include bisphenol A epoxy resin, halogenated bisphenol A epoxy resin, bisphenol A and ethylene oxide or propylene oxide. And diglycidyl ether of adducts with alkylene oxide, bisphenol F epoxy resin, novolac epoxy resin, cresol novolac epoxy resin and the like.

  Examples of monobasic acids include acrylic acid, methacrylic acid, crotonic acid, monomethyl malate, monopropyl malate, sorbic acid or mono (2-ethylhexyl) malate, and are polybasic used in combination with unsaturated monobasic acids. Examples of the acid include succinic acid, maleic acid, fumaric acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, adipic acid, azelaic acid, 1,12-dodecanedioic acid and other dimer acids. Examples of the dibasic acid anhydride include maleic anhydride and phthalic anhydride. A modified product using trimellitic anhydride as a tribasic acid anhydride can also be used.

  Epoxy (meth) acrylate usually contains a polymerizable unsaturated monomer for viscosity adjustment, and this polymerizable unsaturated monomer forms a skeleton of a cured product by polymerization. Examples thereof include aromatic monomers such as acid esters, methacrylic acid esters, styrene and vinyl toluene, and monomers such as acrylonitrile.

  In addition to these monomers, monomers that contribute to the formation of a cross-linked structure such as divinylbenzene, diallyl phthalate, and ethylene glycol dimethacrylate, or copolymerizable resins such as unsaturated polyester resins can be used as necessary. .

  Urethane (meth) acrylate can be obtained by mixing and reacting a diisocyanate compound, a polyol compound, a hydroxyl group-containing (meth) acrylate, and the like.

As the diisocyanate compound, known compounds can be used. For example, 1,2-diisocyanatoethane, 1,2-diisocyanatopropane, 1,3-diisocyanatopropane, hexamethylene diisocyanate, triresin diisocyanate , Trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, dimer acid diisocyanate, bis (4-isocyanatocyclohexyl) methane, methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,6-diisocyanate, 1,3-bis (isocyanatomethyl) Cyclohexane, 1,3-bis (isocyanatoethyl) cyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-bis (isocyanato) Chill) benzene, 1,3-bis (isocyanato-1-methylethyl) benzene and oligomers is these adducts can be mentioned.
Specific examples of the polyol compound include alkyl diol, polyether diol, and polyester diol.

  Examples of the alkyl diol include ethylene glycol, 1,3-propanediol, propylene glycol, 2,3-butanediol, 1,4-butanediol, 2-ethylbutane-1,4-diol, and 1,5-pentadiol. 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-diethyl Butane-1,3-diol, 4,5-nonanediol, 2-butene-1,4-diol, etc. That.

  As the polyether diol, those synthesized by polymerization of aldehyde, alkylene oxide, or glycol by a generally known method can be used. For example, formaldehyde, ethylene oxide, propylene oxide, tetramethylene oxide, epichlorohydrin, etc. are appropriately used. A polyether diol obtained by addition polymerization to an alkyl diol under certain conditions can be mentioned.

  Polyester diols include esterification reaction products obtained by reacting saturated or unsaturated dicarboxylic acids and / or their anhydrides with excess alkyl diols, and alkyl diols with hydroxycarboxylic acids and / or their internals. An esterification reaction product obtained by polymerizing a lactone that is an ester and / or a lactide that is an intermolecular ester can be used.

  Polyester (meth) acrylate is obtained by reaction of polyester polyol and (meth) acrylic acid. The polyester polyol is obtained by a reaction between a polyhydric alcohol and a polybasic acid. Examples of the polyhydric alcohol include neopentyl glycol, ethylene glycol, propylene glycol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, tricyclodecane dimethylol and bis- [hydroxymethyl] -cyclohexane. Examples of the polybasic acid include succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, and tetrahydrophthalic anhydride.

  The (meth) acrylic acid ester is preferably in the range of 20 to 100 parts by weight, preferably 30 to 80 parts by weight with respect to 100 parts by weight of the mixed resin of unsaturated polyester resin and diallyl phthalate resin. If the amount is less than 20 parts by weight, the permeability to the decorative paper cannot be obtained. After application, the coated paper remains tacky and cannot be handled as an intermediate product. If the amount exceeds 100 parts by weight, sufficient physical properties as a cosmetic material are obtained. I can't. The blending ratio of the unsaturated polyester resin and diallyl phthalate resin is preferably 10:80 to 90:20, more preferably 25:75 to 75:25, and more preferably 25 to 75 to 75:25 in terms of solid content. Is too sticky, and if it is small, the coating amount cannot be controlled.

  Organic peroxides used as radical polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide, acetylacetone peroxide, acetoacetate peroxide, cumene hydroperoxide, t-butyl hydroperoxide, diisopyrubenzene Hydroperoxides such as peroxide, diacyl peroxides such as acetyl peroxide, isobutyl peroxide, lauroyl peroxide, benzoyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide Dialkyl peroxides, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexa Peroxydicarbonates such as diesters, alkyl peresters such as t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate , Organic peroxides such as peroxyesters such as t-butylperoxyacetate and t-butylperoxyisobutyrate, 2,2-azobis (2,4-dimethylvaleronitrile), 2,2- Examples include azo compounds such as azobisisobutyronitrile and 1,1-azobis (cyclohexane-1-carbonitrile). These may be used alone or in combination of two or more. Preferably, an organic peroxide used in combination with a curing accelerator and having a low decomposition temperature is convenient in terms of curability. Specifically, methyl ethyl ketone peroxide, acetoacetate peroxide, and acetylacetone peroxide are used. Is preferred.

  It is preferable to blend powder silica having an average particle size of 1 to 150 μm in order to reduce tack when applied to decorative paper. The powder silica is preferably in the range of 1 to 10 parts by weight, preferably 3 to 7 parts by weight, based on 100 parts by weight of the mixed resin of unsaturated polyester resin, diallyl phthalate resin and (meth) acrylic acid ester. If the amount is less than 1 part by weight, tack remains on the coated paper after application, and the product cannot be handled as an intermediate product. If the amount exceeds 10 parts by weight, the appearance of the molded product becomes cloudy and the design is impaired.

  As the core material, generally known materials such as thermosetting resin-impregnated paper and thermoplastic resin-impregnated paper can be used.

Mixed resin (A)
37 parts by weight of diallyl orthophthalate prepolymer (Daiso Dup A Daiso Corporation)
Diallyl orthophthalate monomer 9 parts by weight unsaturated polyester resin (trade name: Aqualite XO-KC-108-7 manufactured by DH Material Co., Ltd.)
37 parts by weight of polypropylene glycol dimethacrylate (trade name: BLEMMER XO-KC-108-7, manufactured by NOF Corporation, boiling point 150 ° C. or higher, average molecular weight 560, viscosity 42.3 mPa · s)
17 parts by weight resin composition for decorative board (B)
Mixed resin (A) 100 parts by weight BPO (benzoyl peroxide) 0.5 parts by weight release agent (trade name Separ 326 manufactured by Chukyo Yushi Co., Ltd.) 0.5 parts by weight leveling agent 0.3 parts by weight silica particles (trade name) Fine seal X70 Average particle size 2.0μm Made by Tokuyama Corporation)
4 parts by weight The above decorative board resin composition (B) was applied to 100 g / m ² of printing paper with a comma coater so that the amount of the resin adhered after application was 100 g / m ² . No coated paper was obtained. Next, it was inserted into a double belt machine together with 200 g / m ² of latex resin-impregnated core paper, and subjected to hot pressing under conditions of a temperature of 140 ° C. and a pressure of 10 kg / cm ² to obtain a decorative board of Example 1.

Mixed resin (C)
Diallyl orthophthalate prepolymer 23 parts by weight (Daiso Dup A Daiso Corporation)
Diallyl orthophthalate monomer 4 parts by weight unsaturated polyester resin (trade name Aqualite XO-KC-108-7 manufactured by DH Material Co., Ltd.)
23 parts by weight of polypropylene glycol dimethacrylate (trade name: BLEMMER XO-KC-108-7, manufactured by NOF Corporation, boiling point 150 ° C. or higher, average molecular weight 560, viscosity 42.3 mPa · s)
A decorative board was obtained in the same manner as in Example 1 except that (C) was used for 50 parts by weight of the mixed resin.

In Example 2, neopentyl glycol dimethacrylate (trade name NK ester NPG, manufactured by Shin-Nakamura Chemical Co., Ltd., boiling point 150 ° C., molecular weight 240, viscosity 34.5 mPa · s) was used instead of polypropylene glycol dimethacrylate. It carried out similarly.

The same procedure as in Example 2 was performed except that 2-hydroxyethyl methacrylate (Mitsubishi Gas Chemical Co., Ltd., boiling point 205 ° C., molecular weight 130, viscosity 24.5 mPa · s) was used instead of polypropylene glycol dimethacrylate.

Comparative Example 1
Mixed resin (D)
Diallyl orthophthalate prepolymer 18 parts by weight (Daiso Dup A Daiso Corporation)
Diallyl orthophthalate monomer 4 parts by weight unsaturated polyester resin (trade name Aqualite XO-KC-108-7 manufactured by DH Material Co., Ltd.)
18 parts by weight of polypropylene glycol dimethacrylate (trade name: BLEMMER XO-KC-108-7, manufactured by NOF Corporation, boiling point 150 ° C. or higher, average molecular weight 560, viscosity 42.3 mPa · s)
It implemented like Example 1 except having used (D) for 60 weight part mixed resin.

Comparative Example 2
Mixed resin (F)
40 parts by weight of diallyl orthophthalate prepolymer (Daiso Dup A Daiso Corporation)
Diallyl orthophthalate monomer 10 parts by weight unsaturated polyester resin (trade name: Aqualite XO-KC-108-7 manufactured by DH Material Co., Ltd.)
40 parts by weight of polypropylene glycol dimethacrylate (trade name: BLEMMER XO-KC-108-7, manufactured by NOF Corporation, boiling point 150 ° C. or higher, average molecular weight 560, viscosity 42.3 mPa · s)
The same operation as in Example 1 was carried out except that (F) was used for 10 parts by weight of the mixed resin.

Comparative Example 3
A decorative board was obtained in the same manner as in Example 1 except that methyl methacrylate (boiling point: 101 ° C., molecular weight: 100, viscosity: 0.57 mPa · s) was used as the (meth) acrylic ester.
The evaluation results are shown in Table 1.

Note 1 Poor permeability to decorative paper, stickiness on coated paper, difficult to separate from polyester film, making operation difficult.
Note 2: The resin penetrated the decorative paper too well, and the coated paper was sticky, and the coated paper was sticky, making it difficult to separate from the polyester film, making the operation difficult.
Note 3 Peel between the boiling test cores, and also peeled between the cores in the cross-cut tape peel test, leaving only 2 out of 100.
Note 4: Resin did not penetrate the decorative paper, and blisters were generated in the boiling test.
Note 5: Uneven coating occurred due to high viscosity of the resin, resulting in poor appearance after molding.
Note 6: Methyl methacrylate volatilized during hot-press molding, causing puncture and gloss unevenness.
Note 7 The coated paper was sticky and difficult to separate from the polyester film, making it difficult to work.
Note 8: Methyl methacrylate volatilized during storage, the flowability of the resin decreased, and pinholes were generated on the surface.
The evaluation method was as follows.
Tack of coated paper: The stickiness of the coated paper was observed when the coated paper was produced or when the core was stacked and pressed.
Surface hardness: Pencil hardness was measured as a determination of curability.
Adhesiveness with the core: It was confirmed whether or not delamination occurred by a cross-cut tape peeling test and a boiling resistance test (based on JIS K6902).
Appearance: After press molding, the surface on which the coated paper was laminated was observed for appearance abnormalities such as missing portions of resin and glazed portions.
Preservability of coated paper: The coated paper was stored in a thermostat at 40 ° C. for 2 weeks, and then press-molded to confirm the surface appearance.

Claims (5)

A resin composition for a decorative board comprising a diallyl phthalate monomer and / or a prepolymer, an unsaturated polyester resin, and a (meth) acrylic acid ester. The (meth) acrylic acid ester is 20 to 100 parts by weight with respect to 100 parts by weight of the mixed resin of the diallyl phthalate monomer and / or the prepolymer and the unsaturated polyester resin. Resin composition for decorative board. The resin composition for decorative plates according to claim 1 or 2, wherein the (meth) acrylic acid ester has a boiling point of 150 ° C or higher. A thermosetting resin-coated paper obtained by applying the resin composition for a decorative board to decorative paper. A decorative board obtained by hot-pressing the coated paper together with a core material.