JPS6018538B2 - Decorative board manufacturing method, decorative board surface material and resin emulsion used therein - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a conventional resin Z resin for impregnating a surface layer base material of a face plate using an organic solvent solution type or monomer solution type resin solution, a decorative board surface layer material impregnated with this resin, Furthermore, decorative laminates using such decorative laminate surface materials have inherent manufacturing, handling, storage, transportation, usage environment, occupational hygiene, and hazard prevention issues due to their solvents or monomers. It advantageously avoids troubles that are difficult to avoid, and easily and easily imparts an aesthetic appearance to the sun shade board that has excellent physical properties and transparency, and maintains and promotes the characteristics of the material of the surface layer base material of the decorative board to be impregnated. 2. A method for producing a decorative laminate which has the following advantages and also has excellent adhesion between the surface material and the glazed plywood; 2. An improved decorative laminate surface material used in the production of the decorative laminate and a resin emulsion for impregnating the same. Regarding.

Conventionally, decorative laminates have been known that use a decorative laminate surface material in which a surface layer base material of an IQ shipboard is impregnated with an organic solvent type resin solution or a resin solution using a monomer as a solvent. These decorative laminates are derived from organic solvents or monomers and have inherent drawbacks in terms of their manufacture, handling, storage, transportation, use, environmental and occupational hygiene, as well as risks such as fire and explosive gas formation. have inconvenient troubles. 3.Furthermore,
The adhesion to decorative laminate plywood is insufficient, requiring the use of adhesives, or the use of a top coat on the surface layer of the decorative laminate, which requires complicated and disadvantageous operations in the production of decorative laminates. There were some difficulties. In particular, when a thermosetting resin-impregnated decorative board surface material is used, as in Proposal 3 of the type using a monomer as a solvent (for example, Tokkan Sho 50-24 Maku No. 0), the above-mentioned defects and disadvantages may occur. is even more serious. In this proposal, a monomer solution of an unsaturated polyester resin, a monomer solution of an allyl resin, and a monomer solution of a modified polybutadiene resin to which an unsaturated 4-dibasic acid has been added are applied to a natural precious wood veneer as a surface layer base material for a decorative board. It uses impregnated surface material. The present inventors have conducted research to overcome the above-mentioned deficiencies or disadvantages associated with conventional proposals that utilize organic solvent type or monomer soot type resin solutions. and acrylonitrile, a thermosetting melamine resin, and at least one crosslinking-reactive vinyl monomer, the average particle diameter of the emulsion resin is about 0. A thermosetting aqueous emulsion of a mixed resin type containing a vinyl resin aqueous emulsion having 2 peaks or less and a thermosetting melamine resin is used as a resin emulsion for dipping the surface layer of the base material, and this aqueous emulsion is impregnated. The finished decorative laminate surface material can be firmly bonded and cured to the plywood by simply heat-setting it onto the plywood without using an adhesive layer, and is compatible with, for example, diallyl phthalate resin or other resins. It exhibits excellent physical properties since there is no need to further provide a finishing coating layer of a thermosetting resin such as an unsaturated polyester resin, and furthermore, it is easy to manufacture, handle, and process when using the organic solvent or monomer solvent solution type resin solution. It has been found that deficiencies in the storage, transportation, use environment and work hygiene, as well as deficiencies in preventing hazards such as fire and explosion, can be completely overcome. Furthermore, as described above, a hardened surface layer with excellent mechanical properties and transparency can be formed without the need for an additional finishing coating layer of thermosetting resin. When used as a base material, it exhibits a unique aesthetic appearance that maintains and promotes the pattern of the material of the impregnated base material and other characteristics of natural wood boards, as well as excellent physical properties. It was found that it could be firmly adhered to the A8 broadside plywood by just using the adhesive.

Furthermore, in the decorative board cured by heat-pressure adhesive, the average particle diameter of the emulsion resin of the vinyl resin aqueous emulsion used for forming the thermosetting aqueous emulsion of the above-mentioned mixed resin type is about 0.2r or less. It has been found that this is useful for further improving the transparency of the surface-cured resin layer and is particularly preferable for avoiding the whitening phenomenon.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for manufacturing a decorative board that has excellent appearance and physical properties, and has a surface layer material of an equatorial board that is firmly bonded and cured to plywood.

Another object of the present invention is to provide a thermosetting and aqueous resin emulsion for impregnating the surface layer material of the sun shade board and the surface layer base material of the 8 bonito board, which are suitable for use in the production of such excellent decorative laminates. There is something to do.

The above objects and many other objects and advantages of the present invention include:
It will become clearer from the following description that the resin emulsion for impregnating the decorative board surface layer base material of the present invention is made of a vinyl monomer selected from the group consisting of acrylate esters, methacrylate esters, styrene, and acrylonitrile. a vinyl resin aqueous emulsion in which the average particle diameter of the emulsion resin derived from at least one type of z, a thermosetting melamine resin, and at least one crosslinking-reactive vinyl monomer is about 0.2 μm or less; It consists of thermosetting water-based emulsion Z containing melamine resin.

Examples of the above pinyl resin include methyl acrylate,
A polymer of vinyl monomers selected from: acrylic acid esters such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.; methacrylic acid esters such as methyl methacrylate, 2-ethyl methacrylate, butyl methacrylate; styrene; acrylonitrile; Alternatively, copolymers can be mentioned.

In the present invention, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, acrylamide, methacrylamide, N-methylol, acrylamide, N-butoxymethylacrylamide, hydroxyethyl acrylate and methacrylate, Copolymerizing one or more vinyl monomers that are crosslinking-reactive with melamine resins, such as hydroxypropyl acrylate, methacrylate, glycidyl acrylate, and methacrylate, with one or more of the pinyl monomers 3. Uses pinyl resin. These crosslinking-reactive vinyl monomers are preferably used in an amount of, for example, about 1 to about 15% by weight based on the total amount of monomers. As the above monomers, it is preferable to select acrylic and/or methacrylic monomers as the main four monomers. The aqueous vinyl resin emulsion can be easily obtained by emulsion polymerization of the vinyl monomers described above in the presence of an emulsifier and a polymerization initiator by means known per se.

As the emulsifier, any known nonionic or anionic emulsifier or surfactant can be used, and as the polymerization initiator, a Hashidox type initiator or other known initiators can be used. Specific examples of these emulsifiers or surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester, higher alcohol Examples include sulfate ester salts, alkylaryl sulfonates, sulfonates of dibasic fatty acid esters, sulfonates and sulfates of aliphatic amides. Specific examples of polymerization initiators include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, and tertiary butyl hydroperoxide. Examples of the reducing agent used include sodium sulfite, sodium bisulfite, sodium metabisulfite, zinc formaldehyde sulfoate, and ascorbic acid. In the present invention, the average particle diameter of the resin in the aqueous vinyl resin emulsion is preferably about 0.2 m or less, more preferably about 0.15 m or less.

If the particle size is too large, the surface hardened resin layer of the decorative laminate surface material bonded under heat and pressure will whiten or become cloudy, impairing the characteristics of the surface material. This is inconvenient if you want a product that is both active and nurturing. In order to adjust the emulsion resin average particle diameter of the vinyl resin aqueous emulsion to about 0.2r or less, for example, increase the amount of emulsifier, use an anionic emulsifier, polymerization in which the emulsifier is present in the polymerization system from the start of polymerization. This can be done by means etc.

The polymerization conditions are known per se, and can be carried out, for example, in the presence of an emulsifier and a polymerization initiator, at a reaction temperature of 30 to 80 qo, and part or all of the monomers are added sequentially over a period of 2 to 6 hours. As mentioned above, in the resin emulsion for immersion in the decorative board surface layer of the present invention, it is preferable that the above-mentioned vinyl resin aqueous emulsion component has an average particle diameter of about 0.2 or less. This average particle diameter is determined by electron microphotography as follows. The emulsion particles were deposited and fixed on a collodion membrane supported by a metal net, examined under a microscope in the usual manner, and then photographed.The diameters of more than 100 particles were actually measured from the prints obtained at a magnification of 10,000 times. Determine the average particle diameter using the following formula. Blood = Fortress iXm4:
Average particle diameter fi: fraction of the particle diameter where the particle diameter is di di: actual measured value of particle diameter The other resin component in the resin emulsion for impregnating the decorative laminate surface layer base material of the present invention is a thermosetting melamine resin, Typically, melamine or at least one amino component selected from the group consisting of melamine, urea, and guanamine, and a methylol compound derived from an aldehyde, an alkyl ether compound thereof, or a condensate thereof, such as methylol melamine; Toxymethylmelamine;
Examples include thermosetting melamine resins such as methyl and ethyl or butyl etherified methylolmelamine, methylolated products and methylated methylolated products of melamine-urea mixtures, and condensates thereof.

The resin emulsion for impregnating a decorative board surface layer base material of the present invention is a thermosetting aqueous emulsion, and the amount of the thermosetting melamine resin as described above is the resin solid content of the vinyl resin aqueous emulsion. About 2 to about 15
It is preferable that the amount is about % by weight.

More preferably, it is about 5 to about 10% by weight, and even more preferably about 20 to about 7% by weight. Although it varies depending on the type and combination of both resins, if the amount of melamine resin added is too small, the surface hardness and chemical resistance of the decorative laminate surface material of the resulting decorative laminate tend to decrease, while if it is too much. Since there is a double direction that deteriorates the flexibility, it is desirable to use it within the above-mentioned preferred amount range. The decorative laminate surface material used in the present invention can be easily provided by impregnating the decorative laminate surface layer base material with a thermosetting aqueous emulsion as described above, and drying as desired.

The thermosetting aqueous emulsion is prepared by using a solvent such as acetone, alcohol, butyl cellosolve; a plasticizer such as dibutyl phthalate, butyl carbitol acetate, dibutyl carbitol; titanium dioxide,
Colorants such as pigments or dyes such as phthalocyanine pigments, chrome yellow, direct brown, auramine, etc.:
For example, curing catalysts such as triethylamine salts such as para-toluenesulfonic acid and formic acid; also for example, ammonia,
It may contain additives or auxiliaries such as stabilizers such as triethylamine, dimethylaminoethanol, etc.

There are no particular restrictions on the method of impregnating the surface layer of the salmon board with the thermosetting aqueous emulsion of the present invention.
Coating, spraying, and other desired impregnation methods can be employed.

In order to shorten the time of the impregnation operation, an impregnation operation under reduced or pressurized conditions gives favorable results. Although the amount of impregnation can be changed as desired, it is generally preferred to be about 2% by weight or more (total resin amount...as solid content) based on the weight of the surface layer base material of the falling board. Any material that can be impregnated with the thermosetting aqueous emulsion of the present invention can be used as the surface layer base material for the decorative laminate, and the material may have any natural or printed or other processed pattern, design, etc. .

Such materials include paper, pulp sheet, pulp board,
Various materials such as cloth, wood, and others can be used. In particular, when using a sheet-like natural wood board, for example, a material with a thickness of about 0.1 to about 1 willow obtained by thinly cutting a natural precious wood, the surface of the decorative board obtained using this material will have the preferred wood grain pattern and grain pattern of the natural precious wood. It is possible to impart a unique aesthetic appearance that maintains and enhances the natural texture of the material. According to the method of the present invention, a decorative board surface layer is obtained by impregnating a board surface layer base material with a thermosetting aqueous emulsion containing a vinyl resin aqueous emulsion and a thermosetting melamine resin obtained as explained above. By hot-pressing the material onto IQ salmon board plywood and curing the adhesive, it is possible to easily produce a decorative board that has excellent mechanical properties and transparency and is firmly adhered to the plywood. The plywood need not be in the form of a flat plate, but can be in other shapes that can be heat pressed, such as curved plates or other shapes. As the plywood, for example, wood plywood, wood board, fiberboard, mineral fiberboard, and other materials that can produce an anchor effect such as partially permeation hardening of the emulsion during heat-pressing operation can be preferably used.

The use of such plywood improves the adhesive strength of the dry board surface material of the present invention, which can be firmly bonded and cured by simply applying heat to the decorative plywood without using an adhesive layer. This is preferable because it further promotes this. The hot press operation can be performed using any hot press equipment, for example, about 80 to about 200oo, about 5 to about 30k9/
Heat and pressure conditions comparable to those of enemies can be adopted.

Usually, desired adhesive curing can be achieved in a heat-pressing time of about 5 to about 30 minutes. 1. In order to improve the cosmetic properties of the decorative laminate obtained by the present invention, the surface of the veneer is polished before resin impregnation, and finishing processing such as painting is performed to protect the decorative laminate or impart cosmetic properties. That is optional.
Z As mentioned above, the present invention uses a water-based thermosetting resin, which is the most preferable from the standpoint of occupational safety and health, and furthermore, this resin alone has the functions of a top coating agent, an impregnating agent, and an adhesive. It is possible to provide excellent decorative laminates with significantly simplified operations. In addition, since a thermosetting resin film is formed on the surface of the decorative board, it has high hardness, weather resistance, chemical resistance, and abrasion resistance, and the same thermosetting resin also makes it strong to bond with plywood. It is integrated and shows excellent adhesion. The present invention will be explained below based on Examples, but the present invention is not limited thereto.

Example 1 ■ Methyl methacrylate 6 parts by weight Butyl acrylate 282 Hydroxylethyl methacrylate 1
0 Methacrylic acid 2 {B) Polyoxyethylenesononyl phenyl ether (40 moles of ethylene oxide) 4 Sodium dodecylbenzenesulfonate 2'C' Calime persulfate
0.5 Sodium metabisulfite
A solution of 0.5 feet of emulsifier dissolved in 1 part by weight of water was placed in a 4-volume flask equipped with a rope stirrer, and at an internal temperature of 50 pm, the monomer mixture and the catalyst aqueous solution of 'C' (2 % aqueous solution).

The monomer was added dropwise over 3 hours and the catalyst was added dropwise over 3 and a half hours. After the catalyst addition was completed, the mixture was maintained at 50 qo for another hour and then cooled to obtain an emulsion polymer. The solids content of this emulsion was 42% and the average particle size was 0.11 mm. To 10 parts by weight of this emulsion, 3 parts by weight of an aqueous solution of methylated melamine resin (for example, Sanwa Chemical ■ Nikalak MW-14F) with a solid content concentration of 70% is added, and in this resin liquid a layer of 0.6 skin thick is added. Natural wood sheet veneer is soaked and impregnated under reduced pressure, excess resin liquid remaining on the surface of the veneer is removed, and after drying at room temperature for 18 minutes, it is stacked on plywood at a temperature of 130 qo and a pressure of 10 k9/
A veneer of salmon plywood was created by heat-pressure bonding for 1 hour and pressing time. The surface of this veneer decorative plywood was completely transparent and smooth, and it had excellent physical properties such as hardness, crack resistance, hot water resistance, and immersion and peelability. Example 2 W Styrene 5 parts by weight Ethyl acrylate IJlate 382 Hydroxyethyl methacrylate 10
Methacrylic acid 2 Emulsion polymerization was carried out in the same manner as in Example 1 except that the monomer composition of Example 1 was changed as described above to obtain an emulsion with a solid content of 42% and an average particle size of 0.12 mm.

Using this emulsion, resin-immersed veneer decorative plywood was prepared in the same manner as in Example 1. The surface of this decorative board was completely transparent and smooth, and its physical properties were excellent. Example
3 ■ Methyl methacrylate Part by weight of 5 Ethyl acrylate 43N-methylolacrylamide 5 Methacrylic acid
2 Emulsion polymerization was carried out in the same manner as in Example 1 except that the monomer composition of Example 1 was changed as described above and N-methylol acrylamide was dissolved in water and added sequentially, resulting in a solid content of 42% and an average particle size. An emulsion of 0.009 μm was obtained.

Claims (1)

[Claims] 1. Acrylic esters, methacrylic esters,
The average particle diameter of the emulsion resin derived from at least one vinyl monomer selected from the group consisting of styrene and acrylonitrile, a thermosetting melamine resin, and at least one crosslinking-reactive vinyl monomer is about 0.
．． A decorative laminate surface material is obtained by impregnating a decorative laminate surface layer base material with a vinyl resin aqueous emulsion having a particle size of 2μ or less and a thermosetting aqueous emulsion containing a thermosetting melamine resin, without using an adhesive layer. , a method for producing a decorative board, which is characterized by adhesively curing the decorative board by heat-pressing it onto a base plate. 2. The manufacturing method according to claim 1, wherein the decorative laminate surface layer base material is a sheet-like natural wood board. 3. The method of claim 1, wherein the amount of thermosetting melamine resin is from about 2 to about 150% by weight, as solids, based on the resin solids of the aqueous vinyl resin emulsion. 4 Acrylic esters, methacrylic esters,
The average particle diameter of the emulsion resin derived from at least one vinyl monomer selected from the group consisting of styrene and acrylonitrile, a thermosetting melamine resin, and at least one crosslinking-reactive vinyl monomer is about 0.
．． A decorative laminate surface base material is impregnated with a vinyl resin aqueous emulsion having a particle diameter of 2μ or less and a thermosetting aqueous emulsion containing a thermosetting melamine resin, and a decorative laminate base plate can be produced without using an adhesive layer. A decorative laminate surface material used to heat-press and harden the adhesive. 5. The decorative laminate surface material according to claim 4, wherein the decorative laminate surface layer base material is a sheet-like natural wood board. 6. The decorative laminate surface material according to claim 4, wherein the amount of the thermosetting melamine resin is about 2 to about 150% by weight, as a solid content, based on the resin solid content of the vinyl resin aqueous emulsion. 7 Acrylic esters, methacrylic esters,
The average particle diameter of the emulsion resin derived from at least one vinyl monomer selected from the group consisting of styrene and acrylonitrile, a thermosetting melamine resin, and at least one crosslinking-reactive vinyl monomer is about 0.
．． A decorative material consisting of an aqueous vinyl resin emulsion having a particle size of 2μ or less and a thermosetting aqueous emulsion containing a thermosetting melamine resin, which is adhesively cured by hot pressing onto a decorative board base plate without an adhesive layer. Resin emulsion for impregnating board surface materials. 8. The emulsion according to claim 7, wherein the decorative laminate surface layer base material is a sheet-like natural wood board. 9. The emulsion according to claim 7, wherein the amount of the thermosetting melamine resin is from about 2 to about 150% by weight, as a solid content, based on the resin solid content of the aqueous vinyl resin emulsion.