JP2002371232A - Unsaturated polyester resin composition for coating material for decorative laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an unsaturated polyester resin composition which, when used as a coating material for producing a decorative laminate, gives a laminate emitting no styrene odor. SOLUTION: This resin composition comprises an unsaturated polyester, styrene, and an unsaturated (meth)acrylate monomer. The ratio [B/(A+C)] of the molar number (B) of unsaturated groups of styrene to the sum (A+B) of the molar number (A) of unsaturated groups of the unsaturated polyester resin and the molar number (C) of unsaturated groups of the unsaturated (meth) acrylate monomer is 1.1 or lower.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an unsaturated polyester resin composition which is used for a decorative board paint having various patterns such as a grain pattern of a natural tree on its surface, and more particularly to a decorative board which does not generate styrene odor. The present invention relates to an unsaturated polyester resin composition for paint.

[0002]

2. Description of the Related Art Conventionally, a decorative board is obtained by applying an unsaturated polyester resin to a veneer plywood, a slate board, or the like by a flow coater method, a film method, a roll coater method, a brush coating method, a spray method, etc., and curing the resin. Manufactured. A decorative board molded using an unsaturated polyester resin in this manner uses a resin using styrene because the viscosity of the resin is easily adjusted, the curability of the resin, and the properties of the coating film are good. Have been.

However, when a decorative board is formed at room temperature with a resin using styrene, styrene cannot be completely polymerized, and a small amount of styrene remains in the decorative board, and furniture and the like are used using the decorative board. When assembled, furniture emits a styrene odor. In recent years, the problems of sick houses have been highlighted, and it is desired to reduce indoor pollutants such as formaldehyde, benzene, toluene, styrene, paradichlorobenzene, ethylbenzene, trichloroethylene, carbon tetrachloride, and chloroform. Along with that, in order to reduce the amount of styrene remaining on the decorative board, a curing agent,
Although a curing accelerator, a polymerization inhibitor and the like have been studied, it is difficult to eliminate odor of styrene.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a resin composition which does not generate a styrene odor in a decorative board formed using an unsaturated polyester resin.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies on the unsaturated polyester resin composition for decorative panel paint having the above-mentioned problems and found that unsaturated polyester, styrene and (Meth) using an unsaturated polyester resin composition comprising an acrylate unsaturated monomer, by dividing the value of the number of moles of unsaturated group of styrene by the total number of other unsaturated moles to 1.1 or less,
The inventors have found that the amount of residual styrene after curing is reduced, and generation of styrene odor is eliminated, and the present invention has been achieved.

That is, the present invention comprises an unsaturated polyester, styrene and a (meth) acrylate-based unsaturated monomer. The number of moles of unsaturated group (B) of styrene is changed to the number of moles of unsaturated group of unsaturated polyester (A). Wherein the value [B / (A + C)] divided by the sum of the number of moles of unsaturated groups (C) of the (meth) acrylate unsaturated monomer is 1.1 or less. It is an unsaturated polyester resin composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The unsaturated polyester resin composition used in the present invention comprises an unsaturated polyester, styrene and a (meth) acrylate unsaturated monomer and comprises a polyhydric alcohol and an unsaturated polybasic acid. It is a product obtained by dissolving a condensation product (unsaturated polyester) by an esterification reaction in styrene and a (meth) acrylate unsaturated monomer. In the esterification reaction for obtaining the unsaturated polyester, a monohydric alcohol and a saturated polybasic acid or a monofunctional carboxylic acid can be used in combination, if necessary.

The polyhydric alcohol used as a raw material of the unsaturated polyester resin includes 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,
Cyclohexane-1,4-dimethanol, an ethylene oxide adduct of bisphenol A, a propylene oxide adduct of bisphenol A, and the like are used, and a monohydric alcohol such as benzyl alcohol is used as needed.

Examples of the polybasic acid used as a raw material of the unsaturated polyester resin include polybasic acids having no polymerizable unsaturated bonds such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid and sebacic acid. An acid or an anhydride thereof and a polymerizable unsaturated polybasic acid such as fumaric acid, maleic acid, itaconic acid or an anhydride thereof are used. If necessary, a monofunctional carboxylic acid such as benzoic acid or octylic acid can be used in combination. The esterification reaction between the polyhydric alcohol and the polybasic acid is carried out by a known method to produce an unsaturated polyester.

The (meth) acrylate unsaturated monomers used in the unsaturated polyester resin composition of the present invention include methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth). ) Acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate,
Decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethylene glycol di (meth) A) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol # 200 di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Polypropylene glycol # 400 di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylol methane tri There is meth) acrylate, may be used in combination respectively used alone, or two or more kinds.

The unsaturated polyester resin composition of the present invention is obtained by blending the above unsaturated polyester with styrene and a (meth) acrylate unsaturated monomer, and has a low residual styrene content after curing and a styrene odor. There is no occurrence of. The relationship between the amount of residual styrene and the odor of styrene differs depending on the area of the decorative panel occupying the room, the degree of sealing, the standing time, the temperature, etc., but under general use conditions, the amount of residual styrene is 0.2% or less. If it is, the styrene concentration in the room can be suppressed to 1 ppm or less where odor is hardly felt.

That is, in the unsaturated polyester resin composition of the present invention, in the composition having the above composition, the number of moles of unsaturated group (B) of styrene is changed by the number of moles of unsaturated group (A) and (meta) of unsaturated polyester. ) The value obtained by dividing by the total number of moles of unsaturated groups (C) of the acrylate unsaturated monomer [B / (A
+ C)] is 1.1 or less. As described above, when the value obtained by dividing the number of moles of unsaturated groups of styrene by the total number of moles of other unsaturated groups is 1.1 or less, the residual styrene in the cured product can be reduced to 0.2% or less. It is. If the value obtained by dividing the number of moles of unsaturated groups of styrene by the total number of moles of other unsaturated groups is 1.2 or more, the residual styrene amount is 0.2
%, Which may cause odor trouble. Further, if the post-curing is performed by heating even at 1.2 or more, the amount of residual styrene can be suppressed to 0.2% or less, but there is a problem that the decorative plate is deformed by heating and the commercial value is significantly reduced. . When styrene is not used, a styrene odor does not naturally occur, but it is difficult to adjust the viscosity of the resin, and it is difficult to obtain good curability and coating film characteristics.

The (meth) acrylate unsaturated monomer blended in the unsaturated polyester resin composition of the present invention is important for adjusting the resin viscosity and improving the hardness, strength, appearance and the like of a molded product. is there. Therefore, the number of moles of the unsaturated group (C) of the (meth) acrylate unsaturated monomer is divided by the total number of moles of the unsaturated group (A) of the unsaturated polyester and the number of moles of the unsaturated group (B) of styrene. Value [C / (A +
B)] is preferably 0.12 or more.

In producing the unsaturated polyester resin composition of the present invention, a polymerization inhibitor is used to adjust curability and prevent gelation. There is no particular limitation on the polymerization inhibitor, hydroquinone, toluhydroquinone, trimethylhydroquinone, tertiary butylhydroquinone,
Ditertiary butyl hydroquinone, tertiary butyl catechol, methoxy hydroquinone, benzoquinone, tertiary butyl quinone, phenothiazine and the like are used.

When the unsaturated polyester resin composition of the present invention is used in a paint, a pigment is used. There is no particular limitation on the type of pigment, and organic pigments and inorganic pigments can be used. At that time, at most 60 parts by weight or less based on 100 parts by weight of the unsaturated polyester resin composition,
Preferably amounts of up to 40 parts by weight can be used.

As the organic peroxide catalyst of the polymerization initiator used when using the unsaturated polyester resin composition of the present invention in a coating material, there are known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides. , Diacyl peroxide, peroxyester and peroxydicarbonate, 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, dicumylhydroperoxide, acetyl peroxide, bis (4
-T-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, and azobisisobutyronitrile, azobis Azo-based polymerization initiators such as carbonamide can also be used.

As the room temperature curing agent used when the unsaturated polyester resin composition of the present invention is used in a paint, a known combination of a ketone peroxide and a reducing agent, a combination of a hydroperoxide and a reducing agent,
Examples of the combination of 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 and the like, amines such as dimethylaniline and the like. Can be 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 (curing agent) obtained by combining the organic peroxide and the reducing agent varies depending on the setting of the pot life. 0.01 to 2 parts by weight per 100 parts by weight of the composition
0 parts by weight, preferably 0.05 to 15 parts by weight. If the amount of the polymerization initiator is less than 0.01 part by weight, the polymerization tends to be insufficient, and if the amount exceeds 20 parts by weight, it is economically disadvantageous and the physical properties of the cured product are likely to be deteriorated.

[0019]

EXAMPLES Hereinafter, the content of the present invention will be more specifically described with reference to Examples and Comparative Examples. In addition, "part" in each example shows a weight basis. The “residual styrene amount” was measured by the following method. 0.5 g of 8% cobalt octylate and 0.05 g of dimethylaniline are added to 100 g of the unsaturated polyester resin composition.
g, 55% methyl ethyl ketone peroxide 1.0 g
And mix well, and place 3 on a 30 cm square paper plywood.
After loading 0 g and covering the vinylon film from above, the resin was uniformly spread with a roller. 55% vinylon film
After 120 minutes had passed after the addition of methyl ethyl ketone peroxide, it was peeled off to obtain a decorative panel. After peeling off the vinylon film and leaving it at 20 ° C. for 24 hours, the resin on the decorative board surface was scraped off with a cutter knife, and the resin was added to dimethylformamide.
After immersion at 0 ° C. for 24 hours, the amount of styrene extracted into dimethylformamide was measured by gas chromatography to determine the amount of residual styrene remaining in the resin on the surface of the decorative board.

Example 1 10 mol of propylene glycol, 5 mol of maleic anhydride and 5 mol of phthalic anhydride were subjected to a condensation reaction at 200 to 215 ° C. to obtain an unsaturated polyester. To 100 parts of the unsaturated polyester, 10 parts of styrene and 50 parts of 2-hydroxyethyl methacrylate were added and dissolved by stirring to obtain an unsaturated polyester resin composition. Using the obtained resin composition, a decorative board was produced by the above method, and the amount of residual styrene after standing for 24 hours was determined.

Examples 2 to 6, Comparative Examples 1 to 3 Unsaturated polyesters were prepared from polyhydric alcohols and organic acids (polybasic acids and monofunctional carboxylic acids) shown in Table 1.
A resin composition comprising the obtained unsaturated polyester and styrene and a (meth) acrylate unsaturated monomer was obtained. Using the obtained unsaturated polyester resin composition, a decorative board was produced by the above method, and the amount of residual styrene after standing for 24 hours was determined.

Measurement of the amount of polyhydric alcohol, organic acid, styrene and (meth) acrylate unsaturated monomer, the number of moles of unsaturated groups and their ratio, and the amount of residual styrene used in each of Examples and Comparative Examples. The values are shown in Table 1. In Table 1, the indication in the unsaturated polyester column is the number of moles of the resin composition raw material, and the indication in the monomer column is the unsaturated polyester 1
The number of moles of the unsaturated group and the number of moles of the unsaturated group relative to 00 parts are the moles when the monomer is added in the number of parts in the table to 100 g of the unsaturated polyester.

[0023]

[Table 1]

[0024]

As described above, by using the unsaturated polyester resin composition of the present invention, a decorative plate having a small amount of residual styrene can be obtained, and odor of styrene generated from the decorative plate can be eliminated. Therefore, the unsaturated polyester resin composition of the present invention, furniture,
It is extremely useful in fields where low odor decorative panels are required in view of health and livability, such as interiors of houses and interiors of shops, and can be widely used.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J038 CH122 CJ032 CJ132 DD201 GA03 GA09 MA07 MA10 NA01 NA27 PA18 PB05 PC06 PC08

Claims (2)

[Claims] 1. An unsaturated polyester, styrene and (meth) acrylate unsaturated monomer, wherein the number of moles of unsaturated group (B) of styrene is changed to the number of moles of unsaturated group of unsaturated polyester (A) and ( The value obtained by dividing by the total number of moles of unsaturated groups (C) of the (meth) acrylate-based unsaturated monomer [B
/ (A + C)] is 1.1 or less. 2. The number of moles of unsaturated groups (C) of the (meth) acrylate-based unsaturated monomer is changed to the number of moles of unsaturated groups of the unsaturated polyester (A) and the number of moles of unsaturated groups of styrene (B). The unsaturated polyester resin composition for decorative board paint according to claim 1, wherein a value [C / (A + B)] divided by the total is 0.12 or more.