JPS5914345B2 - Decorative material manufacturing method - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for producing a decorative material having clear shading.

Conventionally, a wooden surface material is immersed in a resin liquid made by dissolving an unsaturated polyester resin and its curing catalyst, and then the wooden board is made.
Layer it on a base material such as veneer plywood, hardboard, plasterboard, etc. and bond it by heat, or dip it in and impregnate it and then harden it by heat press or the like, or heat it without hardening and heat it. It is known to produce decorative materials by.

However, when manufactured by this method, it is difficult to sharpen the shading in the spring and summer areas of the wooden surface material that is the surface of the decorative material, and furthermore, the unsaturated polyester resin itself is essentially hardened. Since it has the property of shrinking when it is heated, it has the disadvantage that cracks are likely to occur during the process of integrating it with the base material by thermocompression bonding.

Therefore, in order to solve the above problem, the present inventors have conducted intensive studies and found that by using specific 10 low-shrinkage unsaturated polyester resin compositions as the resin liquid, the surface layer of the decorative material can be The inventors have discovered that it is possible to obtain a decorative material in which the shading of the spring and summer parts of a wood surface material is clear and does not cause cracks, etc., and has thus arrived at the present invention.

15 That is, the present invention provides a method for preparing a wooden surface material using an unsaturated polyester resin, (B) a polymerizable monomer that is liquid at room temperature and can be copolymerized with the resin, (C) an alkyd-based low-shrinkage imparting agent, and a former polymerization agent. After soaking and impregnating in a low shrinkage unsaturated polyester resin composition containing a catalyst as an essential component, it is superimposed on a base material and bonded by thermocompression, or after soaking and impregnating, it is cured or bonded without curing. This is a method for producing a decorative material, which is characterized by superimposing it on a base material via an agent and bonding it under heat.

25 The unsaturated polyester resin that is the (support) component used in the present invention is one that has been conventionally used in the production of decorative materials, and is not particularly limited, but generally unsaturated polyester resins are used. It is in the form of a condensation product of a divalent carboxylic acid or its anhydride and a dihydric alcohol.

Of course, the method for producing this product is not limited to the condensation reaction, and can be easily produced by methods known in the art. Such unsaturated polyesters usually have an average molecular weight of 500 to 10
000, preferably 1,000 to 400,035, and an acid value of 5 to 100, preferably 10 to 60.

Various unsaturated divalent carboxylic acids can be used, and typical examples include maleic acid, fural acid, citraconic acid, and itaconic acid. Unless otherwise specified, a portion of the unsaturated divalent carboxylic acid or its anhydride may be replaced by a saturated divalent carboxylic acid or its anhydride. Examples of such saturated divalent carboxylic acids include succinic acid, adipic acid, sebacic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, heddic acid,
Examples include hexachlorocyclopendadiene-tetrahydrophthalic anhydride adduct. Examples of dihydric alcohols include ethylene glycol, diethylene glycol, polyethylene glycol, 1,3-propanediol, 1,2-propanediol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, and Pentyl glycol, 1,6-hexanediol, hydrogenated bisphenol, 3,3,3-trichloropropylene oxide, 2-methyl-3,3,3-trichloropropylene oxide, dibromoneopentyl glycol, 2,2-di( 4-hydroxypropoxy-2,
Examples thereof include 2',4,4'-tetrapromophenyl)propane and diphenylsulfone dichlorohydrin ether. Of course, each of the dihydric carboxylic acids and dihydric alcohols may be used alone or in a mixture of two or more thereof. Such unsaturated polyester resins can also be used in combination with unsaturated epoxy acrylate resins, diallyl phthalate resins, and the like.

The polymerizable monomer copolymerizable with the unsaturated polyester resin, component I3), is liquid at room temperature and has at least one ethylenic bond in one molecule.

This polymerizable monomer must be capable of crosslinking and thermosetting by reacting with the unsaturated polyester resin, and must also be capable of dissolving the unsaturated polyester resin. Specific examples of such polymerizable monomers include styrene, vinyltoluene, lower alkyl esters of acrylic acid or methacrylic acid (for example, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, acrylic propyl acid, butyl methacrylate, butyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate), methacrylic acid, acrylic acid, divinylbenzene, chlorostyrene,
α-methylstyrene, diaryl phthalate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, 2,5-dichlorostyrene, 2,
5-dibromostyrene, pentapromophenol allyl ether, tripromophenyl acrylate, dialkylphosphonic acid, antimony trioxide, diallylbenzene phosphonate, triacryl phosphate, triallyl phosphate, diallyl ethyl phosphate,
Examples include methyl β-(methylethynolyphosphonoacrylate, (diallylphosphonomethynolyether), but styrene is mainly used.

Of course, each of these monomers is not only one type, but also two types.
A mixture of more than one species can also be used. Hereinafter, a solution obtained by dissolving the unsaturated polyester resin as the component (4) in the copolymerizable monomer as the component (B) will be abbreviated as an unsaturated polyester resin liquid. (Examples of the alkyd-based low shrinkage imparting agent, which is the O component, include epoxy-modified alkyd resins and other alkyd resins described in Japanese Patent Publication No. 32272/1983.

Alkyd resins are obtained from polyhydric carboxylic acids and polyhydric alcohols, but are usually obtained from saturated dihydric carboxylic acids and saturated dihydric alcohols, and small amounts of trivalent or higher hydric carboxylic acids and alcohols may also be mixed. Examples of the saturated dihydric carboxylic acid and saturated dihydric alcohol include those exemplified in the section of component (4) above. Examples of trivalent or higher carboxylic acids and alcohols include trimellitic acid, pyromellitic acid, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and the like. These alkyd-based low shrinkage imparting agents can be dissolved in an unsaturated polyester resin liquid and used as a one-component solution.

The (auto) component polymerization catalyst may be a conventional one, such as cyclohexanone peroxide, methyl ethyl ketone peroxide, benzoyl peroxide, cumene hydroperoxide, di-1-butyl peroxide, dicumyl peroxide, t-butyl perbenzoate. , t-butyl peracetate and the like.

The low-shrinkage unsaturated polyester resin composition of the present invention has the above four components (4) to (self) as essential components, but if necessary, an impregnation improver such as a surfactant or melamine resin may be added. , antifoaming agents, curing accelerators, inhibitors, low-boiling polar solvents such as methanol, ethanol, dioxane, ethylene glycol, and acetone, and organic solvents such as toluene to reduce viscosity. be done.

Furthermore, plasticizers exemplified by dibutyl phthalate and dioctyl phthalate, coloring agents such as dyes and pigments, thickeners such as Erosil, etc. can also be added. In the present invention, a decorative material is manufactured by impregnating a wooden surface material in such a low-shrinkage unsaturated polyester resin composition and then integrating it with a base material. There is a way.

(1) A method in which a wooden surface material impregnated by immersion in a resin composition is directly stacked on a base material and bonded by thermocompression.

(2) A method in which a wooden surface material impregnated with a resin composition is superimposed on a base material via an adhesive and bonded by thermocompression. (3)
A method in which a wooden surface material impregnated with a resin composition is cured in advance using a heat press, etc., and then overlapped with a base material via an adhesive and bonded by heat.

In the case of method (2), the adhesive used should avoid those that inhibit the curing of the resin composition in the surface material, and preferred adhesives include, for example, polyol/isocyanate adhesives. , phenoxy resin adhesive, epoxy resin/acid anhydride adhesive, unsaturated polyester resin adhesive, epoxy acrylate adhesive, and the like.

Examples of water-based adhesives include rubber latex-based natural resin-based emulsions, polyvinyl acetate-based emulsions, ethylene monovinyl acetate-based emulsions, and epoxy resin-based emulsions. Furthermore, hot melt adhesives,
Examples include rosin/polyamide adhesives and ethylene monovinyl acetate sheet adhesives. In the case of method (3), there is no restriction as mentioned above, and epoxy resin/amine compound adhesives having active hydrogen, epoxy resin/thiol or phenol group-containing curing agent adhesives, or polyamine/isocyanate adhesives are used. It can be used in a wide range of ways, including

The base material and wood surface material used in the present invention are those conventionally used for this purpose. For example, the base material is veneer plywood, particle board, etc., and the wood surface material is Japanese pine veneer. , cedar straight-grained boards, rice toga straight-grained boards, or wood-grained boards.

In the present invention, the method for impregnating the surface material with the resin composition of the present invention is not particularly limited, and conventionally known methods such as normal pressure, reduced pressure, pressurization, or a combination thereof can be applied as is.

Moreover, conventionally known conditions are applied to the thermocompression bonding of the thus treated surface material and the base material, and there are no particular limitations.

The present invention will be explained below using examples.

In addition, in the middle part of the example, % indicates the weight unit.

Example 1 Smearp MG-1L (ortho-unsaturated polyester resin liquid + alkyd-based low shrinkage agent, Sumitomo Chemical company product) 1
A toga straight-grained board with a thickness of 0.6 ml is immersed in a resin solution made by blending 0.00 parts with 1 part of benzoyl peroxide.
! Impregnation was carried out under reduced pressure of H9.

On the other hand, SumiPly 1100 (plywood adhesive, manufactured by Sumitomo Chemical Industries, Ltd.) was evenly applied to the surface of the lauan plywood at a ratio of 1509/I, and after an open time of 5 minutes, the toga straight-grain board impregnated with the resin liquid was Overlapping, 120℃, 5kg/~
Thermocompression bonding was carried out for 8 minutes under the following conditions. The thus obtained decorative material had a milky opaque color in the summer part and had a clear appearance of light and shade. Comparative Example 1 A 0.611 thick straight-grained board was immersed in a resin solution prepared by blending 1 part of benzoyl peroxide with 100 parts of Smearp NG-3 (ortho-unsaturated polyester resin liquid, manufactured by Sumitomo Chemical Co., Ltd.). Impregnated under reduced pressure of 3 to 20 ml LH9,
A decorative material was made in the same manner as in Example 1, but not only was it not possible to obtain a deep decorative material, but also fine cracks were produced on the surface.

Example 2 Smearp MG-1L 70 parts, Smearp M
G-1201 (ortho-unsaturated polyester resin liquid, Sumitomo Chemical Co., Ltd. product) 10 parts, Smearp EVR-911 (
A 0.6 mm thick straight-grained board was immersed in a resin solution containing 20 parts of unsaturated epoxy acrylate resin (product of Sumitomo Chemical Co., Ltd.) and 1 part of benzoyl peroxide.
Impregnation was carried out under reduced pressure of m1H9.

The veneer was heated to 120℃ and 5kg/c! Heat pressing was carried out for 8 minutes under the conditions of 11. By adhering the veneer thus obtained to plywood using Sumikadyne 1500 (room-temperature curing epoxy adhesive), a decorative material with clear shades of summer with a milky-white tone in the summer areas can be created. I was able to get it. Comparative Example 2 A decorative material was produced in exactly the same manner as in Example 2, except that Smearup MG-3 was used instead of Smearup MG-1L.

However, it was not possible to obtain a decorative material with clear shading like that obtained in Example 2. Example 3 Smearp MG-
0.61 to a resin liquid containing 100 parts of 1L, 20 parts of dioctyl phthalate, and 1 part of benzoyl peroxide.
Lm of rice pine straight grain board was soaked and impregnated under reduced pressure of 3~201!1H9, then stacked on lauan plywood and heated at 120°C.
, 5 kg/Cd for 8 minutes.

The decorative material thus obtained had clear shading with a milky white color in the summer part.

Comparative Example 3 A decorative material was produced in the same manner as in Example 3 except that Smearp MG-3 was used instead of Smearp MG-1L.

However, not only were minute cracks formed on the surface of the decorative material obtained, but also the adhesion to the base material was poor, resulting in partial peeling.

Claims (1)

[Claims] 1 Wooden surface material, (A) unsaturated polyester resin, (
B) a polymerizable monomer that is liquid at room temperature and can be copolymerized with the resin;
(C) A low shrinkage type unsaturated polyester resin composition containing an alkyd-based low shrinkage imparting agent and (D) a polymerization catalyst as essential components. After immersion in a low shrinkage type unsaturated polyester resin composition, the composition is superimposed on a base material and bonded by thermocompression, or Alternatively, a method for producing a decorative material is characterized in that after being dipped and impregnated, it is superimposed on a base material via an adhesive and bonded under heat without curing or curing.