WO1997034952A1

WO1997034952A1 - Novel melamine resin composition and use thereof

Info

Publication number: WO1997034952A1
Application number: PCT/JP1997/000886
Authority: WO
Inventors: Seiji Nakamura; Yasumi Shimizu; Koji Aoki; Takayuki Ohtsuka; Tetsuya Yanagimoto
Original assignee: Daiso Co., Ltd.
Priority date: 1996-03-21
Filing date: 1997-03-19
Publication date: 1997-09-25
Also published as: TW384301B; DE19781658T1; AU1943097A; AU715580B2

Abstract

A melamine resin composition comprising a melamine resin solution and 0.2 to 30 parts by weight on a solid basis, based on 100 parts by weight of the melamine resin of the solution, of a copolymer microgel emulsion of a vinyl compound comprising diallyl phthalate as an indispensable component, and providing decorative sheets having good gloss.

Description

Description New melamine resin composition and its use

The present invention relates to a melamine resin composition comprising a melamine resin solution and a copolymer microgel emulsion with a vinyl compound containing diaryl phthalate as an essential component, and a cosmetic composition comprising the melamine resin composition as an impregnation resin composition. Regarding the board. Related technology

The conventional method of manufacturing high-pressure melamine decorative boards is to impregnate melamine spores into decorative paper with a pattern or coloring, and then heat-press the kraft impregnated paper impregnated with other thermosetting resin. Thus, there has been a method in which a two-layer body is formed, and the two-layer body is bonded to the surface of the base material with an adhesive.

However, although this production method can produce high quality products, it requires long continuous molding in the cycle of cold breath, hot breath and corned breath to laminate impregnated paper and kraft paper. Further, there is a disadvantage that the number of steps is large, such as the need to sand the adhesive surface. In recent years, a method has been adopted in which decorative paper is impregnated with a specially fast-curing melamine resin and then directly adhered to a substrate and molded at the same time. In other words, it is a low-pressure short-cycle melamine decorative board, and mass production has become possible.

However, in this case, the design is inferior to that of the high-pressure melamine decorative board, and the quality is low. The reason for this is that, for example, the impregnated resin is hardened in a short time, and the impregnated paper and the base material are molded at a high temperature and taken out from the hot bracelet. Curable resin Desorption products generated by condensation reaction are glossy in the process of exiting the molding surface It is said that the surface properties such as reduction tend to be deteriorated.

As a means to solve the above-mentioned point S in the manufacture of short cycle melamine decorative board, the amount of volatile components in the base material-impregnated paper should be reduced as much as possible (control the volatile matter to about 6%. ) There is a method, a method of increasing the amount of the thermosetting resin Jt in the impregnated resin and the amount of the catalyst, but the effect is not sufficient. In particular, the latter causes deterioration in thermal stability during the molding stage, and tends to deteriorate the surface properties of the product.

Summary of the Invention

An object of the present invention is to solve the above-mentioned problems in the decorative board manufacturing method (short cycle) in which the impregnated paper is directly bonded to the base material and simultaneously molded, and has gloss comparable to that of a high-pressure melamine decorative board. It is still another object of the present invention to provide a melamine resin composition for impregnation, which is also improved in the chalk abrasion resistance in many cases, and to provide a decorative board obtained by using this composition.

In the present invention ^, a melamine resin solution was prepared by adding a copolymer microgel emulsion with a vinyl compound containing diaryl phthalate as an essential component to 100 parts by weight of the melamine resin in the solution in terms of solid content. Provided is a melamine resin composition containing 2 to 30 parts by weight.

The present invention further provides a decorative board obtained by using the composition as a resin composition for impregnation.

Detailed description of the invention

In the copolymer microgel of the present invention with a vinyl compound containing diaryl phthalate as an essential component, the amount of diaryl phthalate is 5 to 90% by weight based on the total amount of diaryl phthalate and the vinyl compound. L, which is preferred.

Diaryl phthalate in the present invention is a general term for diaryl orthophthalate, diaryl isophthalate and diaryl terephthalate, and may be used alone or in combination. Here, the copolymer microgel emulsion containing diaryl phthalate as an essential component may be blended with another emulsion. When blended with a melamine resin, the emulsion may be used, and the emulsion may be dried and powdered, or redispersed in an organic solvent or water. An organic auxiliary solvent may be added to the emulsion or powder to be blended in an amount of 1 to 50 parts by weight based on 100 parts by weight of the solid content.

The polymerization rate of this copolymer microgel is not limited, but the higher the polymerization rate is, the better the odor and harmfulness, mechanical and chemical properties, etc. You.

The vinyl compound used in the present invention may have a group selected from a silyl group, an epoxy group, a hydroxyl group, a carbonyl group, an N-methylol group, an N- (0-alkylmethylol) group, a vinyl group and a halogen group. Good. Acrylic esters, methacrylic esters, aryl ethers, metharyl ethers, aryl esters, metharyl esters, arylamino compounds, metharylamino compounds, vinyl compounds having a cyano group, and unsaturated bonds & Aliphatic hydrocarbons, α, / 8-unsaturated aldehydes, a.iQ-unsaturated ketones, vinyl carboxylic acids or their anhydrides or salts, acrylic acid amides, methacrylic acid Preferred are those selected from acid amides, styrenes, α-methylstyrenes, vinyl ethers, bier esters, maleic esters, fumanoleates, vinylsilanes, aryl alcohol and methallyl alcohol.

Examples of acrylates include methyl acrylate, ethyl acrylate, η-propyl acrylate, is 0-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, ethyl acrylate, Cyclopentyl acrylate, Hexyl acrylate, Silicon acrylate Esters consisting of saturated aliphatic alcohols, such as chlorohexyl, butyl acrylate, methylcyclohexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, ethylene glycol diacrylate, and ethylene glycol dia Acrylate, propylene glycol diacrylate, pyrene glycol diacrylate at jib mouth, butanediol diacrylate, hexanediol diacrylate, glycerin triacrylate, trimethylolpropane triacrylate, pentaerythritol tetra Acrylate, dipentaerythritol hexacrylate, triazine triacrylate, phosphazene triacrylate, etc., have multiple acryl groups in the molecule; polyatalylates, acrylic acid 2-hydride Esters having a hydroxyl group, such as xicetyl, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, acrylate monoester of glycerin, and acrylate monoester of pentaerythritol; Acrylic ester consisting of fluorinated alcohol components such as tyl acrylate, trifluoroethyl acrylate, perfluoroalkyl acrylate, and perfluoro alcohol acrylate in which only one position is hydrogen-substituted Esters having a halogen group, such as compounds, esters having an alkoxysilyl group, such as trimethoxysilylpropyl acrylate and triethoxysilyl acrylate, epoxides such as glycidyl acrylate and 2-methylglycidyl acrylate Esters having a carbonyl group, esters having a carbonyl group such as acetoacetoxethyl acrylate, esters having a vinyl group such as acryl acrylate and methacryl acrylate, and the like. Can be

Methacrylic acid esters include methyl methacrylate, methyl methacrylate, n-propyl methacrylate, is-propyl methacrylate, and methacrylic acid. N-butyl methacrylate, is-butyl methacrylate, 0-butyl methacrylate, t-butyl methacrylate, pentyl methacrylate, cyclopentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, heptyl methacrylate, methylhexyl methacrylate Esters of saturated aliphatic alcohols such as octyl methacrylate, 2-ethylhexyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, propylene glycol dimethacrylate, dipyrene pyrene Glycol dimethacrylate, butanediol dimethacrylate, hexanediol dimethatalylate, glycerin trimethacrylate, trimethylonole propane trimetaacrylate, pentaerythritol tetate Polymethacrylates having multiple methacrylic groups in the molecule, such as lamethacrylate, dipentaerythritolhexamethacrylate, triazine triacrylate, phosphazene trimethacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypromethacrylate, etc. Bil, 3-hydroxybutyrate methacrylate, 4-hydroxybutyl methacrylate, methacrylic acid or methacrylic acid monoester of glycerin, methacrylic acid monoester of pentaerythritol, and esters having a hydroxyl group such as chloroethyl methacrylate, trifluoromethane Fluorinated alcohols such as roethyl methacrylate, perfluoroalkyl methacrylate, and perfluoroalcohol methacrylate in which only one position is hydrogen substituted Esters having a halogen group such as methacrylic acid esters composed of coal components, esters having an alkoxysilyl group such as trimethoxypropyl methacrylate, triethoxybromyl methacrylate, epoxy groups such as glycidyl methacrylate and 2-methyl glycidyl methacrylate An ester having a carboxy group such as acetocetoxycetyl methacrylate; Examples include esters having a vinyl group, such as ril methacrylate and metharyl methacrylate.

Examples of aryl ethers include methyl aryl ether, ethyl aryl ether, bromoaryl ether, butyl aryl ether, hexyl aryl ether, cyclohexyl aryl ether, 2-ethylhexyl aryl ether, and phenylaryl. Ethers, cresylaryl ether, diarylether, arylglycidylether, 2-methylglycidylarylether, and other aryl ethers, ethylene glycol diaryl ether, propylene glycol diaryl ether, hexanediol diaryl Has multiple aryl ether groups in the molecule such as ether, trimethylolpropane diaryl ether, pentaerythritol triaryl ether, dimethylol cyclohexanediaryl ether, and triaryl isocyanurate. Ariru ethers and the like that.

Examples of methallyl ethers include methyl methallyl ether, ethyl methallyl ether, propyl methallyl ether, butyl methallyl ether, hexyl methallyl ether, cyclohexyl methallyl ether,

2-ethylhexyl methallyl ether, phenyl methallyl ether, cresyl methallyl ether, dimethallyl ether, arylmethyaryl ether, methallyl glycidyl ether, 2-methyl glycidyl methallyl ether, etc. Are methallyl ethers, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, hexanediol dimethyl ether, trimethylolpropane dimethyl ether, pentaerythritol trimethallyl ether, dimethylol cycle hexane Dimethallyl ether, trimetharyl isocyanurate, etc.Metharyl ethers having multiple methallyl ether groups in the molecule No.

The aryl esters include aryl esters such as aryl acetate, aryl propionate, aryl butyrate, aryl benzoate, and aryl lactate, diaryl carbonate, diaryl oxalate, diaryl succinate, diaryl fumarate, diaryl maleate, and adipic acid. Examples include diaryl and diaryl cyclohexanedicarboxylate, and aryl esters having a plurality of aryl ester groups in the molecule.

Examples of methacrylic esters include methacrylic acid esters, methacrylic acid propionate, methacrylic acid butyrate, methacrylic acid benzoate, methacrylic acid lactate, and the like, dimethylaryl carbonate, dimethyl oxalate, dimethyl succinate, dimethyl succinate, dimethylaryl fumarate, and maleic acid. Metharyl esters having a plurality of metharyl ester groups in the molecule, such as dimethylaryl methacrylate, dimethylaryl adipate, and dimethylaryl cyclohexanedicarboxylate.

Examples of the arylamino compound include arylamino compounds having an aryl group such as arylamine, diarylamine, triarylamine, dimethylarylamine, methyldiarylamine, dimethyldiarylammonium chloride, and the like.

Examples of the methallylamino compound include amino compounds having a methallyl group such as dimethallylamine, trimethallylamine, dimethylmethallylamine, methyldimetharylamine, and dimethyldimethallylammonium chloride.

Examples of the vinyl compound having a cyano group include acrylonitrile, methacrylonitrile, and the like.

Aliphatic hydrocarbons having an unsaturated bond include propylene, butene, Multiple unsaturated bonds such as aliphatic hydrocarbons having one unsaturated bond in the molecule, such as pentene, hexene, and cyclohexene, butadiene, isoprene, 1.5-hexadiene, and vinylcyclohexene Aliphatic hydrocarbons or butadiene monoepoxide, isoprene monoepoxide, 1,5-hexadiene monoepoxide, vinylcyclohexene monoepoxide, and at least one other unsaturated bond leaving at least one unsaturated bond. Epoxidized aliphatic hydrocarbons and the like are listed.

a,; 3-Unsaturated aldehydes include acrolein, methacrolein, crotonaldehyde and the like.

Examples of the a, j9 + unsaturated ketones include methyl vinyl ketone and ethyl vinyl ketone.

Vinyl carboxylic acids or acid anhydrides or salts thereof include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, phthalic acid monoallyl ester, phthalic acid monomethallyl ester, maleic acid monoate Examples thereof include allyl ester, monometharyl maleate, monoaryl fumarate, monometharyl fumarate, and acid anhydrides or salts thereof.

Examples of acrylamides and methacrylamides include amides such as acrylamide and methacrylamide, and N-methylol groups such as N-methylol acrylamide and N-methylol methacrylamide. N- (0-methylmethylol) acrylamide, N- (0-methylmethylol) methacrylamide, N- (0-butylmethylol) acrylamide, N- (0-butylmethylol) Amides having etherified or non-etherified methylol groups, such as methacrylamide, and saturated amines having 1 to 5 carbon atoms, such as isopropylamide acrylate and isopropylamide methacrylate. Amides having a carbonyl group, such as amides, diacetone acrylamide, diacetone methacrylamide, ethylenediamine diacrylamide, hexanediamine diacrylamide, phenylenediamide Amides having multiple acrylamide groups in the molecule, such as diacrylamide, ethylenediamine dimethacrylamide, hexanediamine dimethacrylamide, phenylenediamine dimethacrylamide, and more than one methacrylamide in the molecule Examples include amides having a group.

Styrenes such as styrene or ortho- or para-chlorostyrene, ortho- or para-methylstyrene, ortho- or para-chloromethylstyrene, divinyl benzene, trivinylbenzene, etc. in which the aromatic ring is a halogen or alkyl group, or a halogenated alkyl or vinyl group Exchanged styrenes.

a; -Methylstyrenes include α-methylstyrene or ortho- or para-methyl α-methylstyrene, ortho- or para-methyl α-methylstyrene, ortho- or para-chloromethyl at-methylstyrene, diisobrozenylbenzene, and other aromatic rings. And methyl styrenes substituted with a halogen or alkyl group or a hagenogenated alkyl group or a vinyl group.

Vinyl ethers include methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, isobutyl vinyl ether, n-amyl vinyl ether, isoamyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, aryl vinyl ether, and meta Examples thereof include vinyl ethers having 3 to 10 carbon atoms such as aryl vinyl ether.

Examples of vinyl esters include vinyl citrate, vinyl propionate, Beova 10 (trade name, manufactured by Shirle Japan Co., Ltd.) and Beoba 9 (trade name, Shionore Japan Co., Ltd.) And the like.

Examples of the maleic acid ester include a maleic acid ester of a saturated or unsaturated aliphatic alcohol having 1 to 8 carbon atoms, such as dimethylmaleic acid, getylmaleic acid, dibutylmaleic acid, diarylmaleic acid, and dimetharylmaleic acid. .

Examples of fumaric acid esters include fumaric acid esters of saturated or unsaturated aliphatic alcohols having 1 to 80 carbon atoms, such as dimethyl fumaric acid, getyl fumaric acid, dibutyl fumaric acid, diaryl fumaric acid, and dimetharyl fumaric acid.

Examples of vinylsilanes include alkoxysilanes such as trimethoxyvinylsilane, triethoxyquinvinylsilane, and trimethylaryloxysilane; alkylvinylsilanes such as vinyltrimethylsilane and vinylethylmethylsilane; divinyldimethylsilane, divinylgetylsilane, and acryloxyb. Toxisilane, methacryloxyb mouth bil trimethoxysilane and the like.

These vinyl compounds can be used alone or in combination of two or more.

In the present invention, the content of diaryl phthalate in the copolymer microgel with a vinyl compound containing diaryl phthalate as an essential component is 5 to 90% by weight based on the total amount of the vinyl compound and the vinyl compound. If the content is less than 5% by weight S, gloss is insufficient when a composition with a melamine resin is formed, and if it exceeds 90% by weight, the storage stability of the obtained copolymer microgel emulsion is insufficient.

In the present invention, the copolymer microgel comprises (1) diaryl phthalate, (2) a (meth) acrylate, and (3) a vinyl carboxylic acid and / or a (meth) acrylate having a hydroxyl group. It is preferred. The amount of diaryl phthalate in the copolymer is 5 to 90% S%, For example, 10 to 80% by weight, particularly 20 to 80% by weight, and the amount of the (meth) acrylic acid ester excluding the hydroxyl group-containing (meth) acrylic acid ester is 2 to 95% by weight. 0 to 89% by weight, especially 10 to 78% by weight, the amount of vinyl carboxylic acid and (meth) acrylate having a hydroxyl group or a hydroxyl group is 0 to 15% by weight, for example, 1 to 10% by weight, In particular, it may be 2 to 10 overlap%.

In the present invention, the emulsifier used at the time of polymerization of diaryl phthalate and a vinyl compound is a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, an anion-nonionic mixed system or a mixture thereof. Although a combined surfactant is used, usually, an anionic surfactant or an anionic nonionic mixed surfactant gives preferable results.

Examples of the cationic surfactant include primary amine hydrochloride, secondary amine hydrochloride, tertiary amine hydrochloride, and quaternary ammonium salt.

Examples of anionic surfactants include fatty acid salts, ester salts of higher alcohols, sulfates of liquid fatty oils, sulfates of aliphatic amines and aliphatic amides, phosphates of fatty alcohols, and dibasic fatty acid esters. Sulfonic acid salt, aliphatic amide sulfonate, alkylaryl sulfonate, formalin condensed naphthalene sulfonate and the like.

Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene polyoxypropylene aryl ether, polyoxyethylene alkyl aryl ether, and polyoxyalkylene. Ethylene polyoxypropylene alkylaryl ether, polyoxyethylenepolyoxybrovilene alkyl ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, sol

U Examples thereof include a bitane alkyl ester and a polyoxyethylene sorbitan alkyl ester.

Examples of the amphoteric surfactant include an amino acid type, a betaine type, a sulfate type, a sulfonate type and a phosphate type.

A reactive emulsifier having a polymerizable double bond in one molecule may be used as a surfactant. Specific examples are Sanyo Kasei Kogyo Co., Ltd., Elminol JS-2.RS-30, Daiichi Kogyo Seiyaku Co., Ltd., Aqualon RN-20, RN-30, RN-50, HS- 10. HS-20, HS-1025, New Frontiers, trade name of Nippon Emulsifier Co., Ltd. Antox—MS-60> i Antox—MS—2N, Antox—MS—NH4, RA—1000 series, RMA — 500 series, RMA— 1120—MA series, MPG-130—MA.

The use amount of these surfactants is suitably in the range of 0.1 to 10% by weight based on all monomers. When the amount is less than 0.1% by weight, agglomerates are liable to be generated during the polymerization, and when the amount exceeds 10% by weight, no improvement in the reaction stability due to a small addition amount is observed. Preferably, 0.5 to 7% by weight is used. Further, the surfactant may be added at once, or may be supplied separately according to the progress of the reaction.

Examples of the water-soluble radical initiator used to obtain the emulsion of the present invention include known to-solvents such as ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, a water-soluble azo catalyst or redox. System catalysts.

Examples of water-soluble azo catalysts include 2.2'-azobis (2-methyl-N-fluoropropionamidine) dihydrochloride, and 2,2'-azobis (N- (4-cyclophenyl) -12-methylpropiona). Dajin) Jihai Drokurorai 2,2'-azobis (2-methyl-N- (phenylmethyl) propionamidine) dihydrochloride, 2.2'-azobis (2-methyl-N- (2-propenyl) propionamidine) dihydrochloride Hydrochlorides of azo compounds containing amino and imino groups such as 2.2'-azobis [2- (5-methyl-2-imidazoline-2-inole) propane) dihydrochloride, 2.2'-azobis (2 — (2-imidazoline-2-yl) propane) dihydrochloride, 2,2'-azobis (2- (4,5,6,7-tetrahydraulot 1H—1,3—dazebine-2-yl) ) Propane) dihydrochloride, 2,2'-azobis (2- (5-hydroxy-3,4,5.6-tetrahydropyrimidin-1-yl) propane) dihydrochloride and other cyclic amino groups, Hydrochlorides of azo compounds containing a mino group may be mentioned.

Examples of redox catalysts include a combination of potassium persulfate or ammonium persulfate with sodium sulfite, sodium metabisulfite, sodium acid sulfite, or potassium sulphate (sodium formaldehyde sulfoquinate dihydrate). Examples thereof include a combination of an organic peroxide such as t-butyl hydride peroxide and cumene hydride, and sodium acid sulfite or Rongalite. In particular, a combination of a persulfate and a reducing agent is preferable in that the polymerization can be stably performed.

If necessary, lipophilic peroxides such as benzoyl peroxide and t-butyl hydroperoxide, 2.2-azobisisobutyronitrile, 1.1-azobis (cyclohexane-111 carbonyl) Lipophilic azo compounds such as tolyl) can also be used as initiators.

The amount of the catalyst used is usually 0.05 to 5% by weight based on the monomer, and may be added all at once or sequentially.

Melamine resin of the melamine resin solution used in the present invention is a melamine resin for low pressure molding. Preferably, it is a min resin. Above all, a rapidly curable melamine resin for short cycle molding is preferable. The melamine resin may be a melamine resin for high-pressure molding.

Examples of the solvent for the melamine resin solution include water and water-soluble organic solvents, such as methanol, ethanol, and isopropanol. A mixture of water and a water-soluble organic solvent may be used.

The resin concentration of the melamine resin solution is suitably 20 to 90% by weight, preferably 30 to 80% by weight.

As described above, the composition of the present invention can be obtained by blending a copolymer microgel emulsion with a vinyl compound containing diallyl phthalanolate as an essential component in a melamine resin solution. It can be produced by the following method using diaryl phthalate and a vinyl compound.

The monomer concentration of the total amount of diaryl phthalate and vinyl compound is usually 5 to 50% by weight, which is approximately the concentration of the emulsion from which they are obtained. In the method of supplying the monomers, they may be added all at once, or may be added sequentially as the reaction progresses. The form of the addition may be either the monomer liquid itself or an emulsion using an emulsifier.

In Emulsion, the copolymer microgel is dispersed in the medium. Examples of the emulsion medium include water and water-soluble organic solvents such as methanol, ethanol, and isopropanol. Mixtures of water and water-soluble organic solvents may be used.

The polymerization temperature should be determined depending on the type of the initiator used, but is usually from 40 to 100, preferably from 50 to 9 (TC. The obtained copolymer microgel has an average The particle size is 5 to 100 nm, preferably 10 to 100 nm. Those having a range of 50 0ηπ are preferable for achieving the object of the present invention.

The amount of the copolymer microgel emulsion to be added to the melamine resin solution is suitably from 0.2 to 30 parts by weight based on 100 parts by weight of the melamine resin in terms of solid content. When the amount is less than 0.2 part by weight, or when the amount exceeds 30 parts by weight, there is no improvement in gloss in the synthetic type. The amount of the copolymer microgel emulsion may be from 0.2 to 25 parts by weight on solids, for example from 0.2 to 20 parts by weight.

The above compounding liquid may be used as necessary, such as a curing accelerator, release agent, inorganic or organic filler, plasticizer, dispersant, thickener, viscosity modifier, defoamer, preservative, ultraviolet absorber, etc. It may contain the additives used. Known aqueous emulsions can be added within a range that does not impair the effects of the composition of the present invention. The decorative paper is prepared by impregnating the melamine resin composition into the impregnated paper cloth, drying, superimposing on the substrate, and hot-pressing with a press.

Molding is performed by the HOT-Η OT press method without cooling, similar to ordinary short cycle melamine. The molding pressure is 10 ~ 30 kgZcm ² , preferably 15 ~ 25 kg / cia ² , the molding & degree is 130 ~ 250, preferably 150 ~ 220, and the molding time is 10 Seconds to 30 minutes, preferably 30 seconds to 10 minutes. Examples of the paper-containing cloth include titanium paper, thin paper, reinforced paper, craft paper, cellulose paper, and non-woven cloths such as polyester, rayon, acrylic, and vinylon. Substrates include particle board, veneer plywood, MDF (medium density male board), slate board, calcium silicate board, aluminum board and stainless steel board.

Example

Hereinafter, the present invention will be described by way of examples. In the examples,% is based on heavy S.

(19 made of diaryl emulsion)

One diaryl based emulsion 1 The following materials were added to a 1 L separable flask equipped with a stirrer, thermometer, condenser, gas inlet, and sampling port, and the emulsifier aqueous solution was converted.

Sodium dodecylbenzenesulfonate (trade name “Neogen R” manufactured by Dai-ichi Shu Pharmaceutical Co., Ltd.) 7.2 g 430 g ion-exchanged water Separately, a monomer mixture having the following composition was prepared.

Diaryl phthalate (DAP) 90g (25% monomer)

Ethyl acrylate (EA) 261 g (72.5% monomer) Acrylic acid (AA) 9 g (2.5% monomer) Heat the internal temperature of the flask to 80, and use a half-moon type stirring »under 30 ΟΓ _{Ρ of} stirring. After sufficient nitrogen replacement, 10% of the prepared monomer mixture was charged, and an aqueous solution obtained by dissolving 0.54 g of ammonium persulfate in 10 g of ion-exchanged water was added. The remaining 90% of the monomer was added sequentially over about 3 hours (monomer addition method). Polymerization was carried out at 80 at the catalyst for 9 hours. The resulting emulsion had a solid content of 45%, a conversion of 97% for DAP, 100% for EA, and an average particle size of 127.3 nm.

Here, the polymerization rate was determined by measuring the residual DAP and EA by gas chromatography (column: CBP-1) and calculating as follows.

Polymerization rate (%)

= (Weight of charged monomer per weight of unreacted monomer) 100 / weight of charged monomer per weight The average particle size was measured using a laser particle size analysis system PHOT ON CORREL AT OR LPA-3000 (Otsuka Electronics Co., Ltd.).

One Diaryl Emulsion 21

a equipped with a stirrer, thermometer, condenser, gas inlet, and Samblingro The following emulsifier aqueous solution was prepared in a 1 L separable flask.

1.92 g of sodium dodecylbenzenesulfonate

Ion exchange water 160 g

Separately, the following emulsified monomers were prepared.

DAP 160 g (50% monomer)

EA 152g (47.5% monomer)

AA 8 g (2.5% monomer) Sodium dodecylbenzenesulfonate 4.48 g

310 g of ion exchange water

The internal temperature of the flask was heated to 70, and the mixture was sufficiently purged with nitrogen while stirring at 30 ° C with a half-moon stirring blade. 10% of the emulsifying monomer was charged, and 1.12 g of ammonium persulfate was added to ion-exchanged water 10 solution for 1 hour reaction added dissolved in g, it was added sequentially with 4 hours the remainder of the emulsified monomer only gun (Emarushi _s emissions addition method). The polymerization was carried out at 70 for 9 hours from the catalyst addition. The obtained emulsion had a solid content of 40%, a polymerization rate of DAP of 91.4%, an EA of 100%, and an average particle size of 98. Inn.

One diaryl emulsion 3—

The following emulsifier aqueous solution was converted into a 1-L separable flask equipped with a stirrer, thermometer, condenser, gas inlet, and Samblingro.

1.92 g of sodium dodecylbenzenesulfonate

160 g ion-exchanged water

Separately, the following emulsified monomers were prepared.

DAP 240 g (75% monomer) 2-Ethylhexyl sulfate (2-EtHA) 80 g (25% monomer) Sodium dodecylbenzenesulfonate 4.50 g 310 g of ion exchange water

Heat the inner temperature of the flask to 70 ° C, perform sufficient nitrogen replacement with a half moon stirring under 30 OrpiD stirring, charge 10% of the emulsifying monomer, and ionize 1.12 g of ammonium persulfate. A solution dissolved in 10 g of exchanged water was added, the reaction was performed for 1 hour, and the remaining emulsified monomer was successively added in 4 hours (emulsion addition method). The polymerization was carried out at 70 for 9 hours from the catalyst addition. The obtained emulsion had a solid concentration of 40%, a polymerization rate of DAP 87.3%, 2-EtH A1-00%, and an average particle diameter of 117.Οηπ.

One Diaryl Emulsion 4

The following emulsifier aqueous solution was prepared in a 1 L separable flask in which a stirrer, a thermometer, a condenser, a gas inlet, and a Sambulingro were designated.

1.40 g of sodium dodecylbenzenesulfonate

430 g ion-exchanged water

Separately, the following emulsion monomers A and B were produced.

Emulsifying monomer A

DAP 54 g (25% monomer)

EA 60g (22.5% monomer) Sodium dodecylbenzenesulfonate 1.6g

57 g of ion exchange water

Emulsifying monomer B

DAP 54g (25% monomer)

EA 60 g (22.5% monomer)

AA 12 g [5% monomer] Sodium dodecylbenzenesulfonate 1.8 g

Ion exchange water 63 g Therefore, the overall compounding ratio is DAP (50% monomer), EA (45% monomer), and AA (5% monomer).

Heat the internal temperature of the flask to 70, and sufficiently purge with nitrogen while stirring at 300 rpn with a half-moon type stirring blade.Add 20% of emulsifying monomer A, and add 0.84 g of ammonium persulfate to ion-exchanged water 10 The solution dissolved in g was added and the reaction was carried out for 1 hour, and the remaining emulsified monomer A was successively added in 1.5 hours. Subsequently, the emulsified monomer B was added sequentially over 1.5 hours (emulsion addition method). Polymerization was performed at 70 ° C for 9 hours from the addition of the to medium. The resulting emulsion had a solid content of 30%, a conversion of 94.7% for DAP, 100% EA, and an average particle size of 84. Onm.

(Preparation of impregnation liquid)

The above diaryl emulsions 1, 2, 3, and 4 are specially formulated into melamine resin for rapid curing and low pressure molding (average addition of formaldehyde to 1 mol of melamine, J6 is 2.8 mol). To obtain an impregnated resin solution (refer to Table 1 for E).

Examples 1 to 11, Comparative Examples 1 to 3

(Manufacture of decorative boards)

80 g / m ² of white titanium paper is impregnated with the impregnated resin solution of each formulation so that the resin adhesion amount is 60% (based on the weight of the impregnated paper), and then dried for 80 ^ x 15 minutes and dried according to the present invention. An indulgent paper was obtained. For comparison, an impregnated paper was prepared in the same manner as in the Examples, using an impregnated resin solution to which no diaryl emulsion was added, and an impregnated resin solution in which the formulation S of the emulsion was out of the range of the present invention. Next, decorative boards were manufactured using these impregnated papers. A particle board with a thickness of 18ππη was used as the base material, and a brass chrome plating mirror plate was used for the flat plate press. The molding was HOT-OTT molding. Table showing resin formulation, breath conditions, and surface characteristics of the resulting decorative board Put together in 1.

Here, the gloss was measured using a gloss meter (Horiba Seisakusho Co., Ltd. Gloss Ticker IG-320) with 60-degree incidence and 60-degree photometry. The pencil hardness was determined according to JIS 540, and the hardness of a pencil lead that did not scratch the surface was examined (the dents were excluded from the scratches). The hardness of the bow I was measured according to the Japanese Agricultural and Forestry Standard JAS-B test of special plywood, and the depth of the scratch was measured at a load of 200 g. The abrasion resistance was measured in accordance with the Japanese Agricultural and Forestry Standard JAS-A test (500 g load) of special plywood. Stain resistance was determined by marking the decorative plate surface with red and black magic inks respectively, leaving the plate at room temperature for 24 hours, and then observing traces of wiping with ethanol. Adhesion was performed by the X-force tape method according to JIS K- + 540. Alkali resistance was determined by dropping a 5% NaOH aqueous solution onto a decorative plate and observing the change after 3 hours. Regarding contamination resistance, adhesion and alkali resistance, the evaluation was evaluated as pass (no change) by 〇, and failed (changed) by X.

When the impregnated paper was made using the liquid-impregnated liquid of the present invention and the decorative sheet was molded under the same molding conditions as a normal short cycle melamine decorative panel, the gloss and abrasion resistance were higher than that of the ordinary short cycle melamine decorative panel. sex it was bought minute that very excellent ₀

When the surfaces of these decorative plates were observed with a scanning microscope, the surface of the decorative plate obtained by the present invention was smooth, while the surface of the decorative plate obtained by the present invention was conspicuous, while the surface of the normal product was noticeable.

It is considered that the good gloss of the present invention is due to the smoothness of the surface, and the good abrasion resistance is due to the thickness of the resin above the titanium paper pattern surface.

Normally, high-pressure melamine suppresses the generation of surface irregularities due to gas by increasing the pressure, but the product of the present invention dissolves by incorporating microgel emulsion. It is thought that the melt viscosity increased, the pressure was applied evenly, the generation of surface irregularities due to gas was suppressed, and the viscosity increased due to the increase in viscosity.

Table 1. Chemical manufacturing data Example] 2 3 4 5 6 7 8 9 10 11 Comparative example 1 2 3 Emma * shi ^. 1 1 1 1 1 2 2 3 4 4 4-1 1 Formulation DAP 25 25 25 25 25 50 50 75 50 50 50 25 25

£ A 72.572.572.572.572.547.547.5 45 45 45 72.572.5

2-EtHA 25

ΛΑ 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 5 5 5 2.5 2.5 Formulation with S-containing (solid weight

Melamine resin liquid 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Emboss, 0.6 5 10 20 10 2.5 5 5 5 10 5-0.1 40

'Less condition

Hot plate £ degree 0;) 160 160 160 160 180 160 160 180 160 160 180 160 160 160 Molding pressure (kg / en 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 Molding Ra (nin) 6 6 6 6 1 6 6 1 6 6 1 6 6 6 Surface

Gloss 6) 87 92 110 87 110 10 105 106 102 108 1 5 83 83 77 i & SX. 9H 8H 7H 7H 7H 8H 8H 8H 8H 8H gH 9H 9H 6H Friendly gft (2.2 2.6 3.2 6.8 3.4 2.5 2.7 2.9 2.6 2.8 2.6 2.2 2.211.5 Wear wear (times) 290 320 430 320 420 340 390 390 360 440 340 270 270 290 House wear (ng) 23 23 23 23 23 23 23 23 21 20 22 23 23 23 Stain resistance 耐〇〇 * 〇〇〇〇〇〇〇〇〇〇 * * 性 * 性性性〇〇 * 性〇アル〇〇アル性性性性性性性性性性性性性性性性性性性性性性性性 The invention's effect

By blending a diaryl phthalate emulsion with melamine resin, it is possible to obtain a decorative plate with good gloss while ensuring good workability. Even when a melamine resin for low pressure molding is used, good gloss can be obtained as obtained with a melamine resin for high pressure molding.

Claims

The scope of the claims

1. In a melamine resin solution, 100 to 100 parts by weight of the melamine resin in the solution, 0.2 to 30 parts by weight of a copolymer microgel emulsion with a biel compound containing diaryl phthalate as an essential component in terms of solid content Melamine resin composition blended.

2. The melamine resin composition according to claim 1, wherein the microgel of the copolymer microgel emulsion is a copolymer microgel containing 5 to 90% by weight of diaryl phthalate.

3. Acrylic ester, methacrylic acid, wherein the vinyl compound may have a group selected from silyl group, epoxy group, hydroxyl group, carbonyl group, N-methylol group, N-alkoxymethylol group, vinyl group and halogen group Acid esters, vinyl carboxylic acids, acrylic acid amides, methacrylic acid amides, styrenes, monomethylstyrenes, vinyl ethers, vinyl esters, maleic esters, fumaric esters, vinyl silanes, acrylonitrile 3. The scope of the subject matter selected from trill and medacrylonitrile. The melamine resin composition according to item 1 or 2.

4. · A decorative board obtained by impregnating paper cloth with the melamine resin composition according to any one of claims 1 to 3, drying, laminating on a substrate, and hot pressing.