JP2003183543A - Resin composition for odorless decorative laminate, method for producing decorative laminate using the same, and apparatus therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for decorative laminates which uses a (meth)acrylic monomer without using styrene, does not foam when mixed with a specific curing agent, and gives a cured product with a color comparable with that of a conventional polystyrene resin for decorative laminates. <P>SOLUTION: This resin composition contains (A-1) an unsaturated polyester or (A-2) a reaction product of an unsaturated polyester with a glycidyl (meth) acrylate compound, (B) a (meth)acrylate compound having a double bond, (C-1) an organic ketoneperoxide, (C-2) an organic peroxyester and (C-3 an organic hydroperoxide compound. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for odorless decorative boards and a method for producing decorative boards using the composition for odorless decorative boards. More specifically, the present invention relates to a resin composition for an odorless decorative board that does not use styrene in the resin composition for a decorative board, a method for manufacturing a decorative board using the composition for an odorless decorative board, and an apparatus for manufacturing the decorative board.

[0002]

BACKGROUND OF THE INVENTION So-called unsaturated polyester resins prepared by dissolving unsaturated polyester in styrene have been used as resins for decorative boards. However,
Recently, from the indoor air pollution problem (sick house syndrome),
There has been a social demand for the development of materials that do not use styrene, which is designated as a substance that pollutes indoor air.

In order to meet such a demand, a resin in which an epoxy acrylate is dissolved in a (meth) acrylate compound which is a monomer replacing styrene has been developed. However, this type of resin has a problem that if a curing agent used for a styrene resin is used, the resin foams and a uniform cured product cannot be obtained.
Further, when a dedicated curing agent for this type of resin that does not foam is used, there is a problem that the color tone of the cured product is not the same as that of the conventional styrene resin. Therefore, in order to obtain the same color tone as conventional styrenic resins so that they can be used as decorative boards, it is necessary to add individual pigments to each resin or use new pigments. Therefore, it took a lot of work. Further, when the same kind of pigment is used, it may be necessary to install equipment for supplying a plurality of resins. Further, there is a problem in that it is necessary to strictly control the raw material such as resin or pigment and the control is complicated.

That is, a resin composition which is an alternative to an unsaturated polyester resin in which an unsaturated polyester is dissolved in styrene and which is suitable for a decorative board has not been widely used. For this reason, it is a resin for decorative boards that uses a monomer of a (meth) acrylate compound that replaces styrene, and there is no foaming phenomenon when a curing agent is mixed, and the color of the cured product is the same as that of conventional styrenic cosmetics. The advent of a resin composition that can provide a resin equivalent to a plate resin is desired.

[0005]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and does not use styrene, but uses a (meth) acrylate compound monomer instead of styrene as a decorative board. An odorless decorative board resin composition which is a resin for use, which does not cause a foaming phenomenon when a curing agent is mixed, and which can provide a resin whose cured product has a color equivalent to that of a conventional styrene-based decorative board resin, An object of the present invention is to provide a method and an apparatus for manufacturing a decorative board using the resin composition.

[0006]

SUMMARY OF THE INVENTION The present inventors have conducted extensive studies to solve the above problems, and when a resin composition comprising an unsaturated polyester, a (meth) acrylate compound and a specific organic peroxide is used, odor The present invention has been completed by finding that the hue of the cured product is the same as that of the styrene type resin, and that the foaming phenomenon of the curing agent can be avoided.

Further, it has been found that when the same pigment is used, it is possible to provide a decorative board having a color tone equivalent to that of a conventional styrene-based decorative board resin, and the existing styrene-based decorative board production line can be used as it is. The inventors have found that it is possible to easily provide an odorless decorative board by switching the raw materials to be supplied, and have completed the present invention. That is, the present invention is as follows.

The resin composition for odorless decorative boards according to the present invention is
(A-1) Unsaturated polyester or (A-2) unsaturated polyester and a reaction product obtained by reacting a (meth) acrylate compound having a glycidyl group, and (B) a (meth) acrylate system having an unsaturated double bond Compound, (C-
1) Ketone peroxide-based organic peroxide, (C-2)
It is characterized by containing a peroxyester-based organic peroxide and a (C-3) hydroperoxide-based organic peroxide.

The method of manufacturing a decorative board according to the present invention is (A-
1) a reaction product obtained by reacting an unsaturated polyester or (A-2) unsaturated polyester with a (meth) acrylate compound having a glycidyl group, and (B) a (meth) acrylate compound having an unsaturated double bond, Odorless decorative board resin containing (C-1) ketone peroxide-based organic peroxide, (C-2) peroxyester-based organic peroxide, and (C-3) hydroperoxide-based organic peroxide A step (step I) of obtaining a composition (1) by mixing a raw material comprising the composition and a pigment (F), and applying the composition (1) to a predetermined surface of a substrate, and applying the composition. (1) is heat-cured to obtain a decorative board (step II).

The method of manufacturing a decorative board according to the present invention is
(A-1) Unsaturated polyester or (A-2) unsaturated polyester and a reaction product obtained by reacting a (meth) acrylate compound having a glycidyl group, and (B) a (meth) acrylate system having an unsaturated double bond A compound, (C-
1) Ketone peroxide-based organic peroxide, (C-2)
A decorative board resin composition supplying step (P1) for supplying a decorative board resin composition (1) containing a peroxyester organic peroxide and (C-3) hydroperoxide organic peroxide (P1), ( From D) a decorative plate resin composition supplying step (P2) for supplying a decorative board resin composition (2) containing an unsaturated polyester and (E) styrene, and a pigment supplying step (P3) for supplying a pigment The raw material supplying step (S1), the raw material mixing step (S2) in which the supplied raw materials are mixed to obtain a composition, and the composition is applied onto the surface of a substrate, and the applied composition is cured by heating. To obtain a decorative sheet (S3), in the raw material supplying step (S1), the pigment supplied in the pigment supplying step (P3) is substantially the same, and the decorative board resin is used. Composition supply step (P1) and the above Plate resin composition supplying step (P
It is characterized in that it can be switched to 2).

An apparatus for manufacturing a decorative board according to the present invention is (A-
1) a reaction product obtained by reacting an unsaturated polyester or (A-2) unsaturated polyester with a (meth) acrylate compound having a glycidyl group, and (B) a (meth) acrylate compound having an unsaturated double bond, Resin composition for decorative board containing (C-1) ketone peroxide-based organic peroxide, (C-2) peroxyester-based organic peroxide and (C-3) hydroperoxide-based organic peroxide A raw material supply means (M1) for supplying a raw material comprising the substance (1) and a pigment to a mixing tank, a raw material mixing means (M2) for mixing the raw materials supplied to the mixing tank to obtain a composition, and the composition A coating means (M3) for coating the surface of the substrate with a coating material, and a heating means (M) for curing the coated composition by heating to obtain a decorative sheet.
It is characterized by consisting of 4) and.

Further, the manufacturing apparatus of a decorative board according to the present invention is
(A-1) Unsaturated polyester or (A-2) unsaturated polyester and a reaction product obtained by reacting a (meth) acrylate compound having a glycidyl group, and (B) a (meth) acrylate system having an unsaturated double bond A compound, (C-
1) Ketone peroxide-based organic peroxide, (C-2)
A decorative plate resin composition supply means (Q1) for supplying a decorative plate resin composition (1) containing a peroxyester-based organic peroxide and a (C-3) hydroperoxide-based organic peroxide. D) A decorative board resin composition supplying means (Q2) for supplying a decorative board resin composition (2) containing an unsaturated polyester and (E) styrene, and a pigment supplying means (Q3) for supplying a pigment. Raw material supplying means (N1) and the resin composition for decorative board supplying means (Q1)
And the resin composition supply means for decorative plate (Q2), and a raw material mixing means (N3) for mixing the supplied raw materials to obtain a composition.
And a coating means (N4) for coating the composition on the surface of the substrate.
And a heating means (N5) for heat-curing the applied composition to obtain a decorative board.

[0013]

DETAILED DESCRIPTION OF THE INVENTION [Odorless Decorative Board Resin Composition] The odorless decorative board resin composition according to the present invention comprises (A-1) unsaturated polyester or (A-2) unsaturated polyester and glycidyl group. A (meth) acrylate compound having an unsaturated double bond, (C-1) a ketone peroxide organic peroxide, and (C- 2) It contains a peroxyester-based organic peroxide and (C-3) hydroperoxide-based organic peroxide. Further, if necessary, a curing accelerator and a curing retarder may be contained, and an air blocking agent and other additives may be added.

Examples of the unsaturated polyester (A-1) include α, β dibasic acids such as maleic acid, maleic anhydride and fumaric acid, and optionally phthalic acid, isophthalic acid, terephthalic acid, adipic acid, Saturated dibasic acid such as tetrahydrophthalic anhydride and diethylene glycol, ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, bisphenol A Examples thereof include those obtained by esterifying a glycol such as an ethylene oxide adduct of 1) by a conventional method.

The reaction product (A-2) obtained by reacting the unsaturated polyester with the (meth) acrylate compound having a glycidyl group is, for example, a carboxyl group at the terminal of the unsaturated polyester (A-1) molecule, An unsaturated double bond derived from a (meth) acrylic acid ester is introduced at the terminal of an unsaturated polyester molecule by reacting an unsaturated double bond with a glycidyl group of a compound having a glycidyl group in one molecule such as glycidyl methacrylate. The compound obtained by the above is mentioned. Specific examples thereof include glycidyl methacrylate.

A reaction product (A-) obtained by reacting the unsaturated polyester (A-1) or the unsaturated polyester with a (meth) acrylate compound having a glycidyl group.
2) may be used alone or in combination. Further, a reaction product (A-2) obtained by reacting the unsaturated polyester (A-1) or the unsaturated polyester with a (meth) acrylate compound having a glycidyl group.
And can be used together.

Examples of the (meth) acrylate compound (B) having an unsaturated double bond used in the present invention include methyl methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate and 2-hydroxy. Propyl methacrylate, 2-hydroxyethyl acrylate, 2
-Hydroxypropyl acrylate, methoxytriethylene glycol methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, glycerin dimethacrylate, 1,4-butanediol dimethacrylate, trimethylolpropane trimethacrylate , Dicyclopentenyloxyethyl methacrylate and the like. These are compounds having a reactive double bond which replaces styrene.

The odorless decorative board resin used in the present invention is a reaction product obtained by reacting the unsaturated polyester (A-1) or the unsaturated polyester obtained by the above-mentioned method with a (meth) acrylate compound having a glycidyl group. (A-2)
Is mixed with and dissolved in the (meth) acrylate compound (B) having an unsaturated double bond. The amount of the (meth) acrylate compound (B) having an unsaturated double bond used is the reaction product of the unsaturated polyester (A-1) or the unsaturated polyester and the (meth) acrylate compound having a glycidyl group ( A-2) It is preferably 40 to 150 parts by mass, more preferably 50 to 100 parts by mass, relative to 100 parts by mass.

The odorless resin for decorative plate thus obtained can be cured by adding a curing agent, a curing accelerator, a curing retarder, and a pigment (F) if necessary. It is preferable to use a curing accelerator in combination for early curing. The curing agent used in the present invention is (C-
1) Ketone peroxide-based organic peroxide, (C-2)
It is a mixture of three organic peroxides, a peroxyester organic peroxide and a (C-3) hydroperoxide organic peroxide. If at least one compound is used from each compound group, a plurality of compounds may be used in combination.

As the organic peroxide used in the present invention, examples of the ketone peroxide organic oxide (C-1) include methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide,
Methyl acetoacetate peroxide and the like can be mentioned.

Peroxyester-based organic oxide (C-
Examples of 2) include t-butylperoxybenzoate, t-butylperoxylaurate, t-hexylperoxybenzoate and t-butylperoxyacetate. Examples of the hydroperoxide-based organic peroxide (C-3) include diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, 1,1,3,3.
-Tetramethylbutyl hydroperoxide and the like can be mentioned.

The use amount (total amount) of these curing agents is preferably 0.5 to 5 with respect to 100 parts by mass of the solution.
It is desirable that the amount is, and more preferably 0.7 to 3 parts by mass. Ketone peroxide-based organic peroxide (C
-1), peroxyester-based organic peroxide (C-
2), hydroperoxide-based organic peroxide (C-3)
The mixing ratio (weight) of the curing agent is preferably (C-
1) :( C-2) :( C-3) = 1: 0.2 to 0.6:
It is preferably 0.2 to 0.6. If the proportion of the ketone peroxide-based organic peroxide (C-1) is increased, decomposition products having a strong odor of the ketone peroxide-based organic oxide are accumulated in the cured resin, which is not desirable.

Examples of the curing accelerator that can be used as required include, for example, cobalt naphthenate, manganese naphthenate, copper naphthenate, potassium naphthenate,
Metal soaps such as calcium naphthenate and cobalt octylate, amines such as dimethylaniline, N, N-dimethyltoluidine, N, N-diethylaniline, N, N-di (hydroxy) -4-methylaniline, acetylacetone, Examples thereof include β-diketones such as ethyl acetoacetate and N, N-dimethylacetoacetamide, β-ketoesters, β-ketoamides, and oxides such as vanadium pentoxide.

The amount of the curing accelerator used is Solution 1
With respect to 00 parts by mass, preferably 0.05 to 5 parts by mass,
The amount is more preferably 0.1 to 1 part by mass, and particularly preferably 0.2 to 0.5 part by mass. As the curing retarder used as necessary in the present invention, for example, both quinone type and hydroquinone type can be used.

Examples of the quinone series include p-benzoquinone, naphthoquinone, toluquinone and methyl p-benzoquinone. Examples of the hydroquinone system include hydroquinone, 2,5 ditertiary butyl hydroquinone, hydroquinone monomethyl ether, and mono-t-butyl hydroquinone. The amount of these curing retardants used is preferably 0.00 based on 100 parts by mass of the resin liquid.
It is desirable that the amount is 1 to 0.1 parts by mass.

As the pigment (F) that can be used in the present invention, conventionally known pigments used when an unsaturated polyester resin composition obtained by dissolving an unsaturated polyester in styrene is used for a decorative plate. Can be used. As such a pigment (F), specifically, either an organic pigment or an inorganic pigment can be used.

For example, as organic pigments, pendicine yellow, hansa yellow, resole red, alizarin lake, pigment scarlet 3B, brilliant carmine 6B, permanent red F-5R, permanent red 4R, rhodamine lake B, rhodamine lake Y, lake red. C, para red, peacock blue rake, phthalocyanine blue, phthalocyanine green, aniline black, permanent yellow HR, PV
Examples include violet BL, quinacridone, perinone, anthraquinone, chromophthal yellow 6G, chromophthal yellow 3G, and chromophthal yellow GR.

As the inorganic pigment, titanium oxide, zinc white, lithobon, white lead, cadmium yellow, yellow lead, titanium yellow, zinc chromate, loess, chrome vermillion, red mouth pigment, amber, yellow iron oxide, red iron oxide, cadmium. Examples include red, red lead, dark blue, ultramarine, cobalt blue, oxidized chrome green, mineral violet, carbon black, iron black.

The decorative board resin composition described above can be applied to the surface of various substrates and cured to produce a decorative board. Such a decorative board is composed of a cured product of the resin composition for decorative board and a base material, and for example, the cured product of the resin composition for decorative board is laminated on the base material. As such a substrate, plywood is generally used, but it is also possible to use wood, particle board, fiber board, calcium silicate board, gypsum board, concrete, cement board, straight, paperboard, metal board, etc. it can.

[Method for Manufacturing Decorative Board] The method for manufacturing a decorative board according to the present invention is a reaction in which the unsaturated polyester (A-1) or the unsaturated polyester is reacted with a (meth) acrylate compound having a glycidyl group. Object (A-2)
A (meth) acrylate compound (B) having the unsaturated double bond, the ketone peroxide organic peroxide (C-1), the peroxyester organic peroxide (C-2), and A step of mixing the resin composition for an odorless decorative board containing a hydroperoxide organic peroxide (C-3) with the pigment (F) to obtain a composition (1) (step I), Applying the composition (1) to a predetermined substrate surface,
It is characterized by comprising a step (step II) of obtaining a decorative board by heating and curing the applied composition (1).

In the step (I) of obtaining the composition, the respective components are supplied to a predetermined place, for example, a mixing tank or the like and mixed. The supply method and the mixing method are not particularly limited, and
The order in which the components are mixed is not limited. The composition (1) obtained by mixing is supplied, for example, to the surface of a base material made of a plywood, a resin, or the like that constitutes a decorative board, to form a thin film of the composition. A thin film of the composition (1) formed on the surface of a base material is further heated and cured, and a desired decorative plate in which the cured product is laminated on a substrate as a resin composition thin film-like cured product for decorative plate Can be obtained.

The curing conditions are not particularly limited, and known conditions for producing a decorative plate can be used. It is also possible to form a uniform film by covering the surface of a thin film of the composition with, for example, a film such as PET and degassing bubbles in the resin film with a derolling roller. The heating temperature is preferably room temperature to about 80 ° C., and the heating time is preferably about 1 minute to 60 minutes.

In such a decorative board manufacturing method, when the same pigment is used, a decorative board having a color tone equivalent to that of a conventional styrene decorative board can be provided. It is possible to provide an odorless decorative board by simply switching and supplying a raw material (in particular, a resin composition for decorative board) to be supplied as needed without adding any special equipment.

For example, the following modes can be adopted. The method for producing a decorative board according to the present invention comprises: a reaction product obtained by reacting (A-1) unsaturated polyester or (A-2) unsaturated polyester with a (meth) acrylate compound having a glycidyl group; (Meth) acrylate compound having saturated double bond, (C-1) ketone peroxide organic peroxide, (C-2) peroxyester organic peroxide and (C-3) hydroperoxide A decorative board resin composition supplying step (P1) for supplying a decorative board resin composition (1) containing a system organic peroxide.
(D) a decorative plate resin composition supplying step (P2) for supplying a decorative board resin composition (2) containing an unsaturated polyester and (E) styrene; and a pigment supplying step (P3) for supplying a pigment. And a raw material mixing step (S1) of mixing the supplied raw materials to obtain a composition.
2) and a step (S3) of applying the composition onto the surface of a base material and heat-curing the applied composition to obtain a decorative plate. In the raw material supplying step (S1), It is possible to switch between the decorative plate resin composition supplying step (P1) and the decorative plate resin composition supplying step (P2) while the pigments supplied in the pigment supplying step (P3) remain substantially the same. Is.

Therefore, according to the method for manufacturing a decorative board of the present invention, an odorless decorative board having the same color tone can be easily prepared by using the same pigment as that of the conventional styrenic decorative board and by using the same production line. Obtainable. In addition, the above (D)
Examples of the unsaturated polyester include the same unsaturated polyesters as the unsaturated polyester (A-1).

[Vacuum Board Manufacturing Apparatus] As shown in FIGS. 1 and 3, the decorative board manufacturing apparatus of the present invention has an unsaturated polyester (A-1) or an unsaturated polyester and a glycidyl group (meta). ) A reaction product (A-2) obtained by reacting an acrylate compound, a (meth) acrylate compound (B) having an unsaturated double bond, a ketone peroxide organic peroxide (C-1), and a peroxy compound. Raw material 1 consisting of a resin composition for an odorless decorative board containing an ester organic peroxide (C-2) and a hydroperoxide organic peroxide (C-3), and a raw material 1 is mixed or mixed. 3 and the mixing tank 3
A raw material mixing means (M2) for obtaining a composition by mixing the raw materials supplied to the above with a stirring device 2 and the like, and a coating means (M3) for applying the composition onto the surface of the base material 5. And heating means (M4) for curing (6) the composition to obtain a cured product 7 of the resin composition for decorative board. In this way, the decorative plate 8 can be obtained. The application can be performed from the composition discharge part 4. As an alternative to coating, the substrate can be dipped in the mixed composition.

The method for manufacturing a decorative board according to the present invention is
As shown in FIGS. 2 and 4, the unsaturated polyester (A
-1) or an unsaturated polyester and a reaction product obtained by reacting a (meth) acrylate compound having a glycidyl group (A
-2), a (meth) acrylate compound (B) having an unsaturated double bond, a ketone peroxide organic peroxide (C-1), and a peroxyester organic peroxide (C-2). A decorative board resin composition supply means for supplying a decorative board resin composition 9 (that is, the odorless decorative board resin composition according to the present invention) containing a hydroperoxide-based organic peroxide (C-3). Q1), (D) unsaturated polyester and (E) styrene resin composition supplying means for supplying a resin composition 10 for decorative boards containing styrene (Q)
2), and pigment supply means (Q3) for supplying the pigment 11
A raw material supplying means (N1), and a decorative board resin composition switching means (N2) for switching between the decorative plate resin composition supplying means (Q1) and the decorative board resin composition supplying means (Q2). ) And the supplied raw materials are mixed by, for example, a stirrer 2 to obtain a raw material mixing means (N3).
And a coating means (N for coating the composition on the surface of the substrate 5).
4) and heating means (N5) for heating (6) the applied composition to cure to obtain a cured resin composition 7 for decorative board. In this way, the decorative plate 8 can be obtained.
Raw materials such as the cosmetic resin composition and the pigment are finally supplied to the mixing field or the mixing tank 3 for mixing.

In such a decorative board manufacturing apparatus, since the supply of the decorative board resin composition is switched by the switching means (N2), the decorative board resin composition 9 and the decorative board resin composition 10 are supplied. And will not be supplied at the same time. Further, any one of the above-mentioned decorative plate resin composition supplying means (Q1)
Also in (Q2), the raw material supply means can be configured by mixing with the same pigment.

As the switching means N2, for example, means for switching the kind of the composition supplied by the switching section 12 at a desired timing and using the same supply line 13, the odorless cosmetic resin composition and the cosmetic resin composition There is a means for switching the supply timings from different supply lines at desired timings. According to such a decorative board manufacturing apparatus of the present invention, an odorless decorative board having the same color tone can be easily prepared by using the same pigment as that of the conventional styrene-based decorative board and by using substantially the same production line. Can be obtained.

[0040]

The resin composition for odorless decorative boards according to the present invention has no odor, no foaming phenomenon, and is completely cured.
Moreover, it is possible to manufacture a decorative board having surface hardness and color tone which are not different from those of the conventional styrenic unsaturated polyester resin. In addition, when the pigment is common, it is possible to provide a decorative board with a color tone equivalent to that of the conventional styrene-based decorative board resin, so while using the existing styrene-based decorative board production line as it is, the raw material to be supplied is the desired raw material. (Odorless decorative board resin composition) can be easily switched to provide an odorless decorative board easily.

[0041]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

[0042]

[Synthesis Example 1] A 5-liter four-necked flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet tube was charged with 540 parts by mass of maleic anhydride, 815 parts by mass of phthalic anhydride, and 920 parts by mass of propylene glycol by a conventional method. Then, the temperature was gradually raised under a nitrogen stream, and finally the reaction was carried out at 200 ° C. for 8 hours to obtain an unsaturated polyester having an acid value of 50. This unsaturated polyester was cooled to 120 ° C., 0.4 parts by mass of hydroquinone monomethyl ether and 1720 parts by mass of triethylene glycol dimethacrylate were added and dissolved, and then cooled to room temperature to obtain a solution 1.

[0043]

[Synthesis Example 2] A 5 liter four-necked flask equipped with a stirrer, a condenser, a thermometer, and a gas inlet tube was charged with 540 parts by mass of maleic anhydride, 815 parts by mass of phthalic anhydride, and 920 parts by mass of propylene glycol by a conventional method. Then, the temperature was gradually raised under a nitrogen stream, and finally the reaction was carried out at 200 ° C. for 7 hours to obtain an unsaturated polyester having an acid value of 70. This unsaturated polyester is cooled to 115 ° C., 160 g of glycidyl methacrylate is added, and while blowing air, 1
The reaction is carried out at 15 to 120 ° C until the acid value reaches 50,
After completion of the reaction, 0.4 part by mass of hydroquinone monomethyl ether, 186 of triethylene glycol dimethacrylate
0 part by mass was added and dissolved, and cooled to room temperature to obtain a solution 2.

[0044]

[Synthesis Example 3] 1480 g of epoxy resin Epomic R140 (manufactured by Mitsui Chemicals) was charged into a 2-liter four-necked flask equipped with a stirrer, a condenser, a thermometer, and an air introduction tube, and 120 ° C. while blowing 10 L of dry air per minute. The temperature was raised to. After raising the temperature, 2,5-di-t which is a polymerization inhibitor
2 g of -butyl-4-methylphenol (polymerization inhibitor) was added, and 670 g of methacrylic acid was added dropwise over 2 hours. The acid value was measured every hour after 3 hours from the end of the dropping, and after confirming that the acid value was 15 mgKOH / g or less, the reaction was terminated. After completion of the reaction, 1 g of hydroquinone (polymerization inhibitor) was added to obtain a vinyl ester.

This vinyl ester was cooled to 100 ° C., 1760 g of dicyclopentenyloxyethyl (meth) acrylate and 0.33 g of hydroquinone were added and dissolved, and then cooled to room temperature to obtain a solution 3.

[0046]

[Synthesis Example 4] A 5-liter four-necked flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet tube was charged with 540 parts by mass of maleic anhydride, 815 parts by mass of phthalic anhydride, and 920 parts by mass of propylene glycol by a conventional method. Then, the temperature was gradually raised under a nitrogen stream, and finally the reaction was carried out at 200 ° C. for 8 hours to obtain an unsaturated polyester having an acid value of 35. This unsaturated polyester was cooled to 120 ° C., 0.4 parts by mass of hydroquinone and 1720 parts by mass of styrene were added and dissolved, and then cooled to room temperature to obtain a solution 4.

[0047]

Example 1 In 500 g of the solution 1 obtained in Synthesis Example 1,
1.0% of 8% cobalt octenoate solution, 50 g of gray toner for decorative board, 2.5 g of ketone peroxide-based acetylacetone peroxide as a curing agent, 0.8 of peroxyester-based t-butylperoxybenzoate
5 g and 1.0 g of hydroperoxide-based diisopropylbenzene hydroperoxide were added and mixed uniformly.

The state of the resin liquid during this mixing was observed. Next, this resin solution is placed on a 2.7 mm-thick paper-bonded plywood board, and is further polyethylene terephthalate (PET).
Then, the air bubbles in the resin film were degassed with a derolling roller to form a uniform resin film, and the resin film was allowed to stand in an 80 ° C. thermostat for 10 minutes to cure the resin.

The odor inside the thermostat during curing was observed. After the completion of curing, the decorative plate was taken out from the constant temperature bath, left to stand and cooled to room temperature. After cooling, the PET film was peeled off, the cured state, gloss and color tone were observed, and the pencil hardness was measured. table
1, the mixing ratio of resin, etc., the situation when mixing, the situation of odor,
Observation results and measurement results are shown.

[0050]

Example 2 A decorative board was produced in the same manner as in Example 1 except that Solution 2 obtained in Synthesis Example 2 was used in place of Solution 1, and the cured state, pencil hardness and gloss were measured. In Table 1,
The compounding ratios of resins, etc., odor conditions, mixing conditions, observation results, and measurement results are shown.

[0051]

Comparative Example 1 Solution 3 (500 g) obtained in Synthesis Example 3
To the above, 1.0 g of an 8% cobalt naphthenate solution, 50 g of a gray toner for a decorative plate, and 5 g of a ketone peroxide type methyl ethyl ketone peroxide, which is usually used as a curing agent for styrene resin, were added and mixed uniformly.

The state of the resin liquid during this mixing was observed. Then, a decorative board was produced in the same manner as in Example 1, and the cured state, pencil hardness, and gloss were measured. Table 1 shows the blending ratio of resins and the like, the odor situation, the situation at the time of mixing, observation results, and measurement results.

[0053]

Comparative Example 2 A decorative board was manufactured in the same manner as in Example 1 except that Solution 3 was used instead of Solution 1, and the cured state, pencil hardness and gloss were measured. In Table 1, the compounding ratio of the resin,
The mixing status, odor status, observation results, and measurement results are shown.

[0054]

Comparative Example 3 A decorative board was manufactured in the same manner as in Comparative Example 1 except that Solution 4 obtained in Synthesis Example 4 was used in place of Solution 3, and the cured state, pencil hardness and gloss were measured. In Table 1,
The compounding ratios of resins, mixing conditions, odor conditions, observation results, and measurement results are shown.

[0055]

Comparative Example 4 A decorative board was manufactured in the same manner as in Example 1 except that Solution 4 was used instead of Solution 1, and the cured state, pencil hardness, and gloss were measured. In Table 1, the compounding ratio of the resin,
The mixing status, odor status, observation results, and measurement results are shown.

[0056]

Comparative Example 5 3.11 g of a ketone peroxide-based acetylacetone peroxide and 1.24 g of a hydroperoxide-based diisopropylbenzene hydroperoxide were used as curing agents, except that a peroxyester-based curing agent was not used. In the same manner as in Example 1,
A decorative board was manufactured, and the cured state, pencil hardness, and gloss were measured.

Table 1 shows the blending ratio of the resin and the like, the state of mixing, the state of odor, the observation result, and the measurement result.

[0058]

Comparative Example 6 2.5 g of ketone peroxide-based acetylacetone peroxide and 1.10 g of peroxyester-based t-butylperoxybenzoate as a curing agent.
Was used, and a decorative board was manufactured in the same manner as in Example 1 except that the hydroperoxide type was not used.
The cured state, pencil hardness, and gloss were measured.

Table 1 shows the blending ratio of the resin and the like, the state of mixing, the state of odor, the observation result, and the measurement result.

[0060]

[Comparative Example 7] As a curing agent, 2.0 g of peroxyester-based t-butylperoxybenzoate and 1.35 g of hydroperoxide-based diisopropylbenzene hydroperoxide were used, and no ketone peroxide-based one was used. Except for the above, in the same manner as in Example 1,
A decorative board was manufactured, and the cured state, pencil hardness, and gloss were measured.

Table 1 shows the blending ratio of the resin and the like, the state of mixing, the state of odor, the observation result, and the measurement result.

[0062]

Comparative Example 8 Using 4.35 g of a ketone peroxide type acetylacetone peroxide as a curing agent,
A decorative board was manufactured in the same manner as in Example 1 except that the peroxyester type and hydroperoxide type were not used, and the cured state, pencil hardness, and gloss were measured.

Table 1 shows the blending ratio of the resin and the like, the state of mixing, the state of odor, the observation result, and the measurement result.

[0064]

[Comparative Example 9] The same as Example 1 except that 4.35 g of peroxyester-based t-butylperoxybenzoate was used as a curing agent and no ketone peroxide-based or hydroperoxide-based ones were used. Then, a decorative board was manufactured, and the cured state, pencil hardness, and gloss were measured.
Table 1 shows the compounding ratios of resins and the like, the state of mixing, the state of odor, observation results, and measurement results.

[0065]

Comparative Example 10 Hydroperoxide-based diisopropylbenzene hydroperoxide 4.3 as a curing agent
Example 1 except that 5 g were used and no ketone peroxide and peroxy ester based ones were used.
In the same manner as above, a decorative board is manufactured, and the cured state, pencil hardness,
The gloss was measured. Table 1 shows the compounding ratios of resins and the like, the state of mixing, the state of odor, observation results, and measurement results.

[0066]

[Table 1]

[Brief description of drawings]

FIG. 1 is a functional block diagram for explaining an operation procedure for realizing manufacturing of a decorative board according to the present invention.

FIG. 2 is a functional block diagram for explaining an operation procedure for realizing manufacturing of the decorative board according to the present invention.

FIG. 3 is a schematic diagram showing an outline of an apparatus for manufacturing a decorative board according to the present invention.

FIG. 4 is a schematic view showing an outline of a decorative board manufacturing apparatus according to the present invention.

[Explanation of symbols]

M1 raw material supply means M2 raw material mixing means M3 application means M4 heating means Q1 Odorless decorative board resin composition supply means Q2 Resin composition supply means for decorative boards Q3 Pigment supply means N1 raw material supply means N2 switching means N3 raw material mixing means N4 application means N5 heating means 1 Raw material containing resin composition for decorative board and pigment 2 stirrer 3 mixing tanks 4 composition discharge part 5 base materials 6 heat 7 Resin composition cured product for decorative board 8 Veneer 9 Resin composition for decorative boards 10 Resin composition for decorative board 11 pigments 12 Switching unit 13 supply lines

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08F 290/06 C08F 290/06 C09D 4/00 C09D 4/00 167/06 167/06 (72) Inventor Tatsuya Shibata 2-26-1, Muraokahigashi, Fujisawa-shi, Kanagawa Mitsui Chemicals Co., Ltd. (72) Inventor Masayoshi Fujiyoshi 2-26-1, Muraokahigashi, Fujisawa, Kanagawa Mitsui Chemicals Co., Ltd. Inner F-term (reference) 4D075 AC84 BB16X BB26Z CA02 CA31 CB04 DA06 DB01 DB12 DB18 DB22 DB25 DC31 EA07 EB14 EB22 EB33 EB35 EC11 EC37 4F042 AA02 AA16 CA01 CA06 CB02 CB02 AB17 AB17 AB17 AB17 AB17 AB17 AB10 AB07 AB02 AB03 AB03 AB02 AB03 AB10 AB07 AB02 AB03 AB10 AB07 AB02 AB03 AB03 AB02 AB03 AB17 AB02 AB03 AB10 AB02 AB03 AB02 AB03 AB02 AB03 AB02 AB03 AB03 AB02 AB03 AB17 AB17 AB02 AB03 AB10 BA08 BA17 BA19 BA20 BA26 CA14 CA24 CA25 CA29 CA34 CB04 CC02 CD08 4J038 CG141 CH171 DD181 FA04 FA11 JA66 KA03 NA27

Claims (5)

[Claims] 1. A reaction product obtained by reacting (A-1) unsaturated polyester or (A-2) unsaturated polyester with a (meth) acrylate compound having a glycidyl group, and (B) having an unsaturated double bond. (Meth) acrylate-based compound, (C-1) ketone peroxide-based organic peroxide, (C
-2) Peroxyester-based organic peroxide and (C-
3) A resin composition for an odorless decorative board, which contains a hydroperoxide-based organic peroxide. 2. A reaction product obtained by reacting (A-1) unsaturated polyester or (A-2) unsaturated polyester with a (meth) acrylate compound having a glycidyl group, and (B) having an unsaturated double bond. (Meth) acrylate-based compound, (C-1) ketone peroxide-based organic peroxide, (C
-2) Peroxyester-based organic peroxide and (C-
3) A step (step I) of mixing a resin composition for an odorless decorative board containing a hydroperoxide-based organic peroxide and a raw material comprising (F) a pigment to obtain a composition (1), and the composition. A method for producing a decorative board, which comprises a step (step II) of applying (1) to a surface of a predetermined base material and heat-curing the applied composition (1) to obtain a decorative board. 3. A reaction product obtained by reacting (A-1) unsaturated polyester or (A-2) unsaturated polyester with a (meth) acrylate compound having a glycidyl group, and (B) having an unsaturated double bond. (Meth) acrylate-based compound, (C-1) ketone peroxide-based organic peroxide, (C-1)
-2) Peroxyester-based organic peroxide and (C-
3) Veneer board resin composition supplying step (P1) of supplying a resin composition (1) for a decorative board containing a hydroperoxide type organic peroxide, containing (D) unsaturated polyester and (E) styrene And a raw material supply step (S1) comprising a decorative board resin composition supply step (P2) for supplying a decorative board resin composition (2) and a pigment supply step (P3) for supplying a pigment. From a raw material mixing step (S2) of mixing raw materials to obtain a composition, and a step (S3) of applying the composition onto the surface of a base material and heat-curing the applied composition to obtain a decorative sheet. In the raw material supply step (S1), the pigment supplied in the pigment supply step (P3) is kept substantially the same, and the resin composition supply step (P1) for the decorative board and the decorative board are used. Switching from the resin composition supply process (P2) A method for manufacturing a decorative board, which is possible. 4. A reaction product obtained by reacting (A-1) unsaturated polyester or (A-2) unsaturated polyester with a (meth) acrylate compound having a glycidyl group, and (B) having an unsaturated double bond. (Meth) acrylate-based compound, (C-1) ketone peroxide-based organic peroxide, (C-1)
-2) Peroxyester-based organic peroxide and (C-
3) Raw material supply means (M1) for supplying a raw material comprising a resin composition (1) for a decorative board containing a hydroperoxide-based organic peroxide and a pigment to a mixing tank, and the above-mentioned raw material supplied to the mixing tank. A raw material mixing means (M2) for mixing raw materials to obtain a composition, a coating means (M3) for coating the composition on the surface of a base material, and the coated composition is heat-cured to obtain a decorative sheet. An apparatus for manufacturing a decorative plate, which comprises a heating means (M4). 5. (A-1) unsaturated polyester or (A
-2) A reaction product obtained by reacting an unsaturated polyester with a (meth) acrylate compound having a glycidyl group, (B) a (meth) acrylate compound having an unsaturated double bond, and (C-1) a ketone peroxide -Based organic peroxide, (C
-2) Peroxyester-based organic peroxide and (C-
3) A decorative board resin composition supply means (Q1) for supplying a decorative board resin composition (1) containing a hydroperoxide type organic peroxide, (D) an unsaturated polyester and (E) styrene. Material supply means (N1) comprising a resin composition supply resin for decorative plate (Q2) for supplying the resin composition (2) for decorative plate and a pigment supply means (Q3) for supplying pigment, and the decorative plate Resin composition supply means (Q1) and decorative plate resin composition supply means (Q2) switching means (N2) for switching decorative resin composition, and the supplied raw materials are mixed to form a composition. It comprises a raw material mixing means (N3) for obtaining, a coating means (N4) for coating the surface of the substrate with the composition, and a heating means (N5) for heat-curing the coated composition to obtain a decorative sheet. An apparatus for manufacturing a decorative plate, which is characterized in that