JPH053382B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a chemically embossed decorative material that has a foam layer but is resistant to abrasion, heat, stains, etc.

(Prior Art) Decorative materials having a foam layer are well known per se and are used in a wide range of applications such as walls, floors, automobile interiors, and book cloths. Decorative materials with a foam layer are soft to the touch and have cushioning properties, so of course they are used in applications that take advantage of these characteristics. Furthermore, the texture of the surface can be improved by various methods of providing unevenness.

A method called chemical embossing (Japanese Patent Publication No. 43-28636, etc.) is well-known as a method of providing a printed pattern on a foam layer as well as unevenness corresponding to the printed pattern.
To give an example of the chemical embossing method, it consists of the following steps.

The company manufactures plastisol whose main ingredients include PVC powder, liquid plasticizer, stabilizer, foaming agent, and filler.

Plastisol is coated to a specified thickness on a base material such as paper or asbestos.

The coated base material is heated to a temperature at which the mixed foaming material does not foam and the vinyl chloride powder, liquid plasticizer, etc. melt and plasticize to form a film on the plastisol on the surface of the base material.

Images are printed directly or by transfer onto the film. At this time, a foaming suppressing portion is provided in the printed pattern.

If necessary, a plastisol containing no foaming agent is coated on the film provided with the printed pattern.

The foaming agent is heated to a foaming temperature to foam the film.

According to the method described above, the foaming suppressing portion does not foam or hardly foams, and there is a difference in level from the foamed portion, and the foaming suppressing portion can be provided at a desired portion in the printed pattern. Therefore, it is possible to obtain unevenness that is in sync with the printed pattern.

Decorative materials produced by chemical embossing are used as wall covering materials, floor materials, etc., depending on the type of base material, overall thickness, type of plastisol, etc. Decorative materials having a foam layer, such as decorative materials manufactured by chemical embossing, are applied to places where a soft feel is required. However, because it is soft, when it is applied to a floor that is placed outdoors and is directly stepped on by shoes, etc., the durability of the foam layer is not sufficient, so there are problems such as unevenness becoming unclear. The reality is that flooring materials having a foam layer are only used in homes, offices, etc. where foot traffic is relatively infrequent.

On the other hand, on the floors of public buildings where there is a high frequency of walking, or on the floors of places that are directly connected to the outdoors,
Flooring materials called for heavy walking are used. A typical flooring material for heavy walking is made by arranging pellet pieces containing polyvinyl chloride resin as a main component in a mosaic pattern on a base material and forming them into a sheet shape by hot pressing or the like. The pattern in this case is created by changing the color of each pellet piece in a pattern. If necessary, the surface may be coated with a coating agent to improve wear resistance.

Although the heavy walking flooring material manufactured in this way has improved strength as a flooring material, it requires a complicated process of arranging pellet pieces colored in various colors in a pattern on the base material. Therefore, only a simple mosaic-like pattern can be formed, and in order to form irregularities, pressing is performed in a later process or the size of the pellet pieces is adjusted, which is a complicated manufacturing method. It is necessary to take

The drawbacks of conventional decorative materials have been described above, mainly using flooring as an example, but these also apply to the walls of rooms and buildings that are frequently used. Also, again,
This also applies to various base materials, such as those based on iron plates and products using the same.

(Object of the Invention) Therefore, the object of the present invention is to provide a method for producing decorative materials that eliminates the drawbacks of conventional decorative materials typified by chemically embossed decorative materials such as chemically embossed flooring materials, and that takes advantage of the advantages of each individual product. Our goal is to provide the following. Specifically, an object of the present invention is to provide a method for producing a decorative material that is provided with an elaborate pattern and has excellent surface physical strength.

According to research conducted by the present inventors, when using the chemical embossing method, the effect of chemical embossing is not lost at all even if all or part of the plasticizer used in producing plastisol is replaced with a polyfunctional vinyl monomer. Moreover, it has been found that by irradiating the foamed layer with ionizing radiation after forming the unevenness, the foamed layer is crosslinked and its durability is improved.

The present invention was made as a result of further research based on these facts. By applying at least a foamable composition containing on a substrate, and heating to a temperature at which the foaming agent does not foam after application and the polyvinyl chloride resin powder and the polyfunctional vinyl monomer melt and plasticize. The coating layer of the foamable composition is melt-plasticized to form a film with a flat surface, and then a pattern is formed on the surface of the film by printing or transfer using a composition containing a foaming inhibitor. The foaming agent in the foamable composition is heated to a temperature at which it foams to foam the film, and the patterned portions of the composition mixed with the foaming inhibitor are formed into recesses, and the resulting foam is then exposed to ionization and radiation. curing the foam by irradiating with In addition, by heating the polyvinyl chloride resin powder and the polyfunctional vinyl monomer to a temperature at which they melt and plasticize, the coating layer of the foamable composition is melt-plasticized to form a film with a flat surface; Next, a pattern is formed on the surface of the film by printing or transfer using a composition containing a foaming inhibitor, and then a composition containing a polyvinyl chloride resin powder and a polyfunctional vinyl monomer and no foaming agent or ethylene is applied onto the pattern. A composition containing a monomer or oligomer having a sexually unsaturated bond and no foaming agent is applied, and the entire composition is heated to a temperature at which the foaming agent in the foaming composition foams. The film is foamed and the patterned portions of the composition mixed with the foaming inhibitor are formed into recesses, and the resulting foam is then irradiated with ionizing radiation to form a film of the composition that does not contain the foam or the foaming agent. It is characterized by being cured.

Hereinafter, the manufacturing method of the present invention will be explained in order.

(a) Polyvinyl chloride resin powder on the surface of the base material,
A foamable composition containing a polyfunctional vinyl monomer and a blowing agent is applied. Coating is performed by, for example, roll coating or knife coating, and the coating thickness varies depending on the composition of the foaming composition and the expansion ratio, but as an example, when the thickness of the foam layer after foaming is 1200 μm, it is around 400 μm.

(b) The obtained coated body is heated to a temperature at which the foaming agent in the foamable composition does not foam and the polyvinyl chloride resin powder and polyfunctional vinyl monomer melt and plasticize, thereby foaming the coated body. The composition is made into a film with a flat surface. Heating conditions vary depending on the composition of the foamable composition, but when the temperature in step (e) described below is 180 to 220°C, heating conditions are 90 to 220°C.
The temperature is around 170℃.

(c) A pattern is provided by directly printing on the formed film or by transferring it using a transfer sheet. At this time, part or all of the pattern is formed from a composition containing a foaming inhibitor. Known techniques can be used for the ink, printing, transfer sheet, and transfer used for direct printing. Further, the use of a composition containing a foaming inhibitor is described in the above-mentioned Japanese Patent Publication No. 43-286360, and the use of a foaming inhibitor by a transfer method using a transfer sheet is described in Japanese Patent Publication No. 57. The technology described in the -47018 publication can be used.

(d) After the pattern is provided, if necessary, a composition that is melted and plasticized by heating in the next step to form a transparent film is applied onto the pattern. The composition used is one of the above-mentioned foamable compositions without the foaming agent, filler, etc., or one containing a monomer or oligomer having an ethylenically unsaturated bond. This step can be omitted when the final product is not used very often, but it is better to add this step when the final product is used frequently. The thickness of the coating provided by this step is, for example, 300 μm.

(e) The whole is heated to a temperature at which the foaming agent in the foamable composition foams, and the patterned film is foamed. At this time, the portion corresponding to the pattern formed with the composition mixed with the foaming inhibitor does not foam and remains as a concave portion.

(F) Crosslink the foam layer by irradiating the entire area with ionizing radiation. The ionizing radiation used is electron beam,
It is suitable to use rays emitted from a high-energy ray source such as γ-rays because they penetrate from the surface layer into the foam layer. Accelerating voltage when using an electron beam
150keV~3000keV, irradiation dose 0.1~20Mrad
range is common.

The materials used, processing conditions, etc. in each of the above steps (a) to (f) will be explained next.

(Base material) The base material used in the present invention may be any material that has been conventionally used as a base material for decorative materials. Preferred examples include asbestos sheets, glass fiber woven fabrics, glass fiber non-woven fabrics, and flame-retardant paper for wallpaper lining, but other papers and plastic films can also be used, as well as wood substrates such as wood, plywood, particle board, and plaster. Board, gypsum base material such as gypsum slag board, fiber cement board such as pulp cement board, asbestos cement board, wood chip cement board, GRC, and metal foil or sheet of concrete, iron, aluminum, copper, etc.
Composites of the above base materials can also be used depending on the purpose.

(Polyvinyl chloride resin powder) The polyvinyl chloride resin powder used in the present invention is obtained by polymerizing vinyl chloride alone or a mixture of 80% by weight or more of vinyl chloride and a vinyl monomer copolymerizable with vinyl chloride. It is manufactured by. Further, these are composed of a collection of fine particles having a suitable particle size distribution (for example, 0.1 to 10 μm), and it is particularly preferable that particles having a particle size of 0.2 to 5 μm account for 60% by weight or more of the total. The molecular weight is preferably about 30,000 to 150,000.

(Polyfunctional vinyl monomer) Polyfunctional vinyl monomer refers to a compound containing two or more vinyl groups in the same molecule, including ethylene glycol dimethacrylate, ethylene glycol diacrylate, and polyethylene glycol dimethacrylate with a degree of polymerization of 2 or more. Methacrylate/polyethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, vinyl acrylate, acrylic anhydride, divinylbenzene, diallyl phthalate , diacrylic succinate, diallyl maleate,
Examples include diallyl adipate. These polyfunctional vinyl monomers can be used in an amount of 50 to 300 parts by weight based on 100 parts by weight of the polyvinyl chloride powder.

(Blowing agent) As the blowing agent, any foaming agent that is used in ordinary polyvinyl chloride resin plastisols may be used, such as diazoaminobenzene,
1,3-diphenyltriazene, azodicarbonamide, 1,1'-azobisformamide, 2,2'-
Azo compounds such as azobutyronitrile and azohexahydrobenzonitrile, hydrazide compounds such as benzenesulfonyl hydrazide, p,p'-oxobisbenzenesulfonylhydrazide, N,N'-
Examples include nitroso compounds such as dinitrosopentamethylenetetramine.

(Surface layer forming composition) Basically, it may be the foamable composition from which fillers such as calcium carbonate and titanium oxide and foaming agents involved in foaming are removed, and if necessary, foaming compositions may be used. As with the composition, organic diluents, stabilizers, conventional plasticizers, polymerization inhibitors, antioxidants, etc. can be added. Furthermore, as a composition for forming a surface layer, in addition to the above-mentioned polyvinyl chloride powder, which is melted and plasticized to form a film by heating, and a composition whose main component is a polyfunctional monomer, there are also compositions that are hardened by irradiation with ionizing radiation in the final step. It is also possible to use a composition whose main component is a monomer or oligomer having an ethylenically unsaturated bond.

Examples of prepolymers or oligomers having ethylenically unsaturated bonds that are cured by ionizing radiation include unsaturated polyesters, polyester acrylates, epoxy acrylates, urethane acrylates, polyether acrylates, polyol acrylates, various acrylates such as melamine acrylate, and polyesters. One or more types of methacrylates such as methacrylate, epoxy methacrylate, urethane methacrylate, polyether methacrylate, polyol methacrylate, and melamine methacrylate, and a monomer having an ethylenically unsaturated bond in the molecule, such as styrene and α-methyl. Styrenic monomers such as styrene; Acrylic acid esters such as methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, and phenyl acrylate; Methyl methacrylate , ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate,
Methacrylic acid esters such as ethoxytityl methacrylate, phenyl methacrylate, and lauryl methacrylate; unsaturated carboxylic acid amides such as acrylamide and methacrylamide; acrylic acid 2-(N,
N-dimethylamino)ethyl, methacrylic acid 2-
(N,N-dimethylamino)ethyl, 2-(N,N-dibenzylamino)ethyl acrylate, (N,N-dimethylamino)methyl methacrylate, 2-(N,N-diethylamino)propyl acrylate, etc. Substituted amino alcohol esters of unsaturated acids of acrylate,
Polyfunctional compounds such as ethylene glycol dimethacrylate, propylene glycol methacrylate, diethylene glycol dimethacrylate, and/or polythiol compounds having two or more thiol groups in the molecule, such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropane Pionate, pentaerythritol tetrathioglycol, etc. can be mixed and used.

(Foamable Composition) Polyvinyl chloride resin powder, polyfunctional vinyl monomer, and foaming agent are mixed in predetermined amounts and dispersed using a high-speed rotating disperser, roll kneader, or the like. Note that, if necessary, common plasticizers such as phthalate esters, organic diluents, stabilizers, fillers such as calcium carbonate or titanium oxide, polymerization inhibitors, and antioxidants may be added. Examples of polymerization inhibitors include hydroquinone, benzoquinone, phenothiazine, hydroquinone monomethyl ether, t-butylhydroquinone, methylhydroquinone, etc., and examples of antioxidants include phenols and bisphenols.

(Effects) According to the above method of the present invention, a foam is formed by heating and foaming, and then the foam is cured with ionizing radiation, so the surface is uneven and a lightweight thick foam layer is formed. It is possible to further impart durability against abrasion, heating, staining, etc., which has not been previously available, to a foamed decorative material having an elaborate printed pattern. In addition, even when used in areas that are frequently used and have harsh environments, such as flooring, it does not cause wear and tear due to walking, scorching due to cigarette burns, contamination due to mud, etc.

Examples are given below to further specifically illustrate the present invention.

Example 100 parts of vinyl chloride powder (Zeon 121, manufactured by Nippon Zeon), trimethylolpropane trimethacrylate (Light Ester TMP, manufactured by Kyoeisha Yushi)
100 parts, zinc stabilizer (Kyodo Yakuhin KF-80A-
8) A mixture obtained by roll kneading 4 parts of azodicarbonamide, 5 parts of calcium carbonate, and 5 parts of titanium white was coated on 0.5 mm thick asbestos paper to a thickness of 0.3 mm, continue,
This was heated with hot air for 1 minute to a maximum temperature of 150°C to dissolve the applied polyvinyl chloride resin plastisol and form a uniform film.

On the obtained film, print the area to be recessed using an ink containing trimellitic anhydride as a foaming inhibitor, and after drying, apply a composition for forming a surface layer with the following composition to a thickness of 0.2 mm. It is applied onto the printed pattern and heated for 2 minutes at a temperature of 200°C at which the foaming agent in the foaming agent layer foams, creating irregularities in the foaming agent layer and at the same time melting and plasticizing the composition in the surface layer, making it transparent. It was made into a film.

Composition vinyl chloride powder for surface layer formation (Zeon 121, manufactured by Nippon Zeon)
...100 parts trimethylolpropane trimethacrylate
...60 parts zinc stabilizer ...4 parts Next, using a Van de Graff electron beam accelerator,
Electron beam irradiation was performed under the conditions of 1MeV and 5Merad.
The obtained decorative material has an extremely strong surface layer, and as a heavy-traffic flooring material, it has been tested in a commonly used taper abrasion tester, i.e.
CS-17 exhibited extremely good properties in practice, with abrasion loss of less than 10 mg under the condition of 1000 rotations.

In addition, the effect of electron beam irradiation extends to the internal foam layer, and the graft reaction between vinyl chloride and the polyfunctional monomer is completed, making the foam layer stronger and at the same time improving its heat resistance. Using a method known as the cigarette resistance test, we placed a lit cigarette on the surface and observed the condition until it burnt, and found that there was no phenomenon such as melting or blackening of the surface layer. There was no phenomenon of melting or caving in, and as a heavy-duty flooring material, it had more beautiful printing than ever before, and was outstanding in both design and performance.

Example 2 100 parts of vinyl chloride powder (Zeon 121 manufactured by Nippon Zeon), trimethylolpropane triacrylate (light ester TMPA manufactured by Kyoeisha Yushi)
70 parts, di2-ethylhexyl phthalate (Kyowa Hakko Acid DOP) 30 parts, zinc stabilizer (Kyodo Yakuhin Co., Ltd.)
KF-85A-5) 5 parts, azodicarbonamide 5
A mixture obtained by roll kneading 30 parts of calcium carbonate, 30 parts of calcium carbonate, and 5 parts of titanium white was coated on a 0.3 mm thick zinc phosphate treated steel plate to a thickness of 0.05 mm, and then coated for 1 minute. The coated polychloride resin plastisol was heated with hot air to a maximum temperature of 140°C and dissolved to form a uniform film.

On the obtained film, thermal transfer was performed using a transfer paper on which the areas to be recessed were printed using an ink containing trimellitic anhydride as a foaming inhibitor, and then a surface layer forming composition having the following composition was applied. 0.03mm
It is applied uniformly to a thickness of It was made into a transparent film.

Composition vinyl chloride powder for surface layer formation (Zeon 121, manufactured by Nippon Zeon)
...100 parts trimethylolpropane triacrylate (manufactured by Kyoeisha Yushi, Light Ester TMPA) ...40 parts di2-ethylhexyl phthalate (manufactured by Kyowa Hakko,
DOP)...20 parts Zinc stabilizer...5 parts Next, using a Van de Graff type electron beam accelerator
Electron beam irradiation was performed under the conditions of 0.5 MeV and 5 Mrad. The obtained decorative material has an extremely strong surface layer with a pencil hardness of 2H or higher, and the effect of electron beam irradiation extends to the internal foam layer, indicating that the graft reaction between the vinyl chloride and the polyfunctional monomer has been completed. As a result, the foam layer became stronger and its heat resistance also improved.
In addition, since the surface layer also underwent a graft reaction, the stain resistance was also good. Furthermore, since a conventional plasticizer could be added to the composition, it was also possible to bend the material into a decorative steel material.

Claims (1)

[Claims] 1. A foamable composition containing at least a polyvinyl chloride resin powder, a polyfunctional vinyl monomer, and a foaming agent is applied onto a substrate, and the foaming agent does not foam after application, and the polychloride resin powder does not foam. By heating the vinyl resin powder and the polyfunctional vinyl monomer to a temperature at which they melt and plasticize, the coating layer of the foamable composition is melt-plasticized to form a film with a flat surface, and then the surface of the film is printed or A composition in which a pattern is created by a composition mixed with a foaming inhibitor by transfer, and then the whole is heated to a temperature at which the foaming agent in the foaming composition foams to foam the film, and the foaming inhibitor is mixed therein. 1. A method for producing a decorative material, which comprises forming a concave portion in a patterned portion of an object, and then irradiating the obtained foam with ionizing radiation to harden the foam. 2. A foamable composition containing at least a polyvinyl chloride resin powder, a polyfunctional vinyl monomer, and a foaming agent is applied onto a substrate, and the foaming agent does not foam after application, and the polyvinyl chloride resin powder and the polyfunctional vinyl monomer are not foamed. The coating layer of the foamable composition is melt-plasticized by heating to a temperature at which the functional vinyl monomer melts and plasticizes to form a film with a flat surface, and then a foaming inhibitor is applied to the surface of the film by printing or transfer. After a pattern is formed by the mixed composition, a composition containing polyvinyl chloride resin powder and a polyfunctional vinyl monomer and no blowing agent or a composition containing a monomer or oligomer having an ethylenically unsaturated bond and a blowing agent is formed on the pattern. The film of the foamable composition is foamed by applying a composition containing the foaming agent and heating the entire composition to a temperature at which the foaming agent in the foaming composition foams. A method for producing a decorative material, which comprises forming a patterned portion into a recess, and then irradiating the resulting foam with ionizing radiation to harden a film of a composition that does not contain the foam or a foaming agent.