JPH0598600A - Production of decorative material - Google Patents

Abstract

PURPOSE:To efficiently obtain a decorative material permitting to readily control its production line, having excellent quality and excellent gradation and useful for furnitures, etc., by disposing a printing layer on specific base paper for the decorative material and subsequently perfectly curing the paper CONSTITUTION:A thermosetting resin such as a melamine resin or a diallyl phthalate resin is impregnated into base paper such as thin paper having a base weight of 20-70g/m<2> and used for decorative materials and subsequently cured into a semi-cured state not reaching a perfectly cured state. Subsequently, a printing layer is formed on the decorative material base paper impregnated with the semi-cured thermosetting resin, and the impregnated resin is perfectly cured to obtain the objective decorative material. A top coat layer comprising a 0.1-10mum thick transparent resin layer is preferably formed on the surface of the decorative material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is applicable to, for example, furniture, wall surfaces,
The present invention relates to a decorative material that is attached to a surface such as a floor surface for the purpose of decoration or surface protection.

[0002]

2. Description of the Related Art A decorative material applied to the surface of a base material such as a building material or furniture for the purpose of decoration or surface protection, which uses a thermosetting resin as a material having excellent surface properties. Is commonly used. Decorative materials that use this thermosetting resin are (1) a method of impregnating a thermosetting resin on a base paper for decorative material with a printing layer and then curing the resin, and (2) applying heat to the base paper for decorative material. Impregnate with curable resin,
It is manufactured by a method such as applying a printing layer before curing this, and then curing the impregnating resin.

[0003]

[Problems to be Solved by the Invention] However, the conventional (1)
In the method of manufacturing a decorative material according to, since the semi-finished product impregnated with the thermosetting resin is already provided with the printing layer, the use of this semi-finished product is limited by the printing layer already provided. As a result, the semi-finished product has no versatility and cannot control the production line. Also,
The decorative material obtained by this method cannot show gradation in the glossy state of the surface. Furthermore, in the method for manufacturing a decorative material of (2), since the printing layer is formed on the base paper for a decorative material impregnated with the uncured thermosetting resin, paper breakage occurs in the step of forming the printing layer. It has the drawback of being easy.

On the other hand, according to the method of the present invention, since the printing layer is not yet applied in the semi-finished product state, the semi-finished product has general versatility, so that the production line can be easily adjusted.
Also, a method of manufacturing a cosmetic material characterized in that the printed layer can impart gradation to the gloss of the surface of the cosmetic material and that no paper breakage occurs during the manufacturing process of the cosmetic material To do.

[0005]

Means for Solving the Problems The method for producing a decorative material according to the present invention is a method in which a thermosetting resin impregnated in a base paper for a decorative material is brought into a semi-cured state before being highly polymerized and highly crosslinked, and The above-mentioned problems are solved by adding a printing layer to the above and then completely curing the thermosetting resin of the impregnating resin. That is, the first aspect of the present invention comprises a state in which after the base paper for a decorative material is impregnated with a thermosetting resin, the impregnating resin is not completely cured but the surface tackiness of the impregnating resin is lost. By the steps of curing to a semi-cured state, applying a printing layer to the base paper for decorative material impregnated with the thermosetting resin in the semi-cured state, and completely curing the impregnated resin, the desired cosmetic material is obtained. Consists of getting. Book second
In the invention of 1, after the base paper for decorative material is impregnated with the thermosetting resin, the impregnated resin is not completely cured, but is cured to a semi-cured state in which the surface tackiness of the impregnated resin is lost. By the step of, a step of applying a printing layer to the base paper for decorative material impregnated with the thermosetting resin in the semi-cured state, and a step of completely curing the impregnated resin and simultaneously performing embossing on the printing layer surface, It consists of obtaining the desired cosmetic material. The third aspect of the present invention is a semi-curing method in which after the base paper for a decorative material is impregnated with a thermosetting resin, the impregnating resin is not completely cured but the surface of the impregnating resin loses its tackiness. A step of curing into a state, and a step of attaching a printing layer to the base paper for decorative material impregnated with the thermosetting resin in the semi-cured state,
The desired cosmetic material is obtained by the steps of completely curing the impregnated resin and simultaneously embossing the surface of the printing layer, and filling the colored ink into the recesses formed by the embossing by wiping. The fourth aspect of the present invention is to provide a post-treatment step of forming a top coat layer of a transparent resin layer on the surface of the decorative material obtained by the method of the first, second or third aspect of the invention. It consists of obtaining cosmetic materials.

In the method for manufacturing a decorative material of the present invention having the above-mentioned constitution, a material having a good impregnation performance of a thermosetting resin is used as a base material for a decorative material. For example, thin paper, bleached kraft paper, linter paper, Rice basis weight of titanium paper etc. 20 to 2
Paper having a weight of about 00 g / m ² , and further laminated paper in which two or more kinds of these are laminated are used. In particular, from the viewpoint of the impregnation property of the thermosetting resin and the printability when applying the printing layer, the thin paper having a rice basis weight of about ²⁰ to 70 g / m ² is preferable.

The thermosetting resin to be impregnated into the base paper for decorative material is, for example, melamine resin, diallyl phthalate resin,
Phenol resin, urea resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin,
Thermosetting acrylic resins, aminoalkyd resins, melamine / urea copolymer resins, silicone resins, polysiloxane resins, and other thermosetting resins. These resins and additives added as necessary, for example, crosslinking An impregnating agent composed of a mixture of an agent, a curing agent such as a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, and an extender pigment is applied. As the curing agent added to the impregnating agent, an isocyanate compound is usually used for unsaturated polyester resin or polyurethane resin, an amine is used for epoxy resin, and methyl ethyl ketone peroxide is used for unsaturated polyester resin. Radical initiators such as peroxides and azobisisobutyronitrile are often used. As the isocyanate compound, a divalent or higher valent aliphatic or aromatic isocyanate compound can be used, and an aliphatic isocyanate compound is preferable from the viewpoint of thermal discoloration prevention and weather resistance, for example, tolylene diisocyanate and xylene diisocyanate. , 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate and the like are preferable.

The solvent used as necessary when adjusting the impregnating agent when the base paper for decorative material is impregnated with the thermosetting resin is appropriately selected according to the type of the thermosetting resin used. Examples thereof include esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone, pentane, hexane, heptane, and a mixture thereof such as gasoline, mineral spirits, Aliphatic hydrocarbons such as petroleum benzine, aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, halogenated hydrocarbons such as trichloroethylene, perchlorethylene, carbon tetrachloride, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol Monohydric alcohols such as ethi Glycol, polyhydric alcohols such as glycerin, ethyl ether, etc. ethers such as methyl ether, more mixtures of two or more of these, or the like.

After the base paper for decorative material is impregnated with the thermosetting resin, the impregnating resin is not completely cured, but the surface of the impregnating resin loses its tackiness, resulting in a semi-cured state. The step to be performed consists of impregnating the thermosetting resin and then touch-drying it, and forming the impregnated resin located on the surface of the base paper for decorative material into a semi-cured non-adhesive solid layer. In this semi-curing step, when a solvent is used in the impregnated resin, part or all of the solvent is volatilized, and the impregnated resin exposed on the surface of the base paper for decorative material is dried by touch. It is to make it a state. Therefore, in this drying process, it is necessary to prevent the thermosetting resin impregnated in the base paper for decorative material from reaching the complete curing, and the fluidity of the impregnated resin and the adhesiveness of the surface are required. Therefore, the impregnated resin itself needs to be left standing or heated and dried so that the impregnated resin itself does not reach full cure and retains thermoplasticity. That is, in the step of applying the printing layer, the impregnating resin exposed on the surface of the base paper for decorative material does not have fluidity or adhesiveness, and at least does not reach full curing and is in a semi-cured state. Must be maintained.

After the thermosetting resin impregnated in the base paper for decorative material is made into a semi-cured state, the printing layer attached to the base paper for decorative material impregnated with the thermosetting resin is a printing pattern layer using a printing ink or It consists of a solid printing layer on the entire surface, for example,
It is composed of a print picture pattern layer expressing wood grain, stone pattern, polka dot, lattice pattern, characters, figures, etc., and further, a combination of this with a solid print layer. To form the print layer, a means such as direct printing by gravure printing, silk screen printing or transfer printing is used. When a melamine resin is used as the impregnating resin, it is possible to form a printing layer with a printing ink using a mixed resin of butyral resin and melamine resin or a cellulosic resin as a vehicle, and as the impregnating resin, diallyl phthalate resin. In the case of using, it is possible to form a printing layer with a printing ink using a nitrocellulose / alkyd resin as a vehicle, because the impregnation performance of the impregnating resin is good, and the good performance between the impregnating resin and the printing layer. It is preferable in that adhesion can be obtained.

The complete curing step of the impregnated resin after applying the printing layer to the base paper for decorative material is the same as the complete curing step in the case of the usual thermosetting resin, and is 1 to 5 days at 40 to 60 ° C. A curing condition of about 300 minutes at 80 to 150 ° C. is used for polysiloxane resin.

In the second aspect of the present invention, the step of completely curing the impregnated thermosetting resin and at the same time embossing the surface of the printing layer is a cosmetic in which the impregnated thermosetting resin is in a semi-cured state. It is to form a concave portion having a shape corresponding to the printing layer attached to the raw material paper ~ distribution, for example, when the printing layer is made of a wood pattern, the concave portion expressing the conduit groove or hairline of the plate material, Further, when the printed pattern expresses leather, a concave portion which expresses a leather diaphragm, and when the printed pattern expresses stones, a concave portion which expresses a grain or stucco is further printed. When the pattern expresses a texture, a recess or the like having a shape expressing a stitch of the cloth is usually formed. In the embossing step according to the second aspect of the present invention, for example, an embossed plate having an embossed pattern of a conduit, which is obtained by electroforming the unevenness of the wood surface, or a photolithography method of the unevenness of the wood surface. An embossed plate or the like in which an embossed pattern of a conduit is formed by a photoetching method using the original plate prepared by the above method is used.

The wiping treatment in the third invention is, for example, after applying the wiping ink to the embossed surface by roll coating, knife coating, etc., scraping off with a doctor blade or wiping paper, and coloring only in the concave portion due to embossing. Paint-Ink wiping ink is filled.In this wiping process, the paint-ink viscosity, roll It is necessary to adjust the rotation speed, doctor angle, thickness, sheet speed, wiping paper speed, rubber roll hardness, etc. The color tone of the colored resin layer filled in the recesses by the wiping process is, for example, in the case of a decorative material in which the printing layer expresses a wood grain pattern, the color tone of the wood grain conduit groove is
In addition, in the case of a decorative material that expresses a stone pattern, one that exhibits a color tone that expresses grain or stucco is used, and a wiping ink with a hue that matches the printing layer depending on the application of the decorative material is used. used.

Examples of the ink for wiping include natural resins such as shellac, cobal, dammar, rosin and rosin ester or modified resins thereof, cellulose derivatives such as nitrocellulose, acetyl cellulose, ethyl cellulose and benzyl cellulose, phenolic resins and urea. Resins, phthalic acid resins, maleic acid resins, melamine resins, polyvinyl acetate resins, polyvinyl chloride resins,
Acrylic resin, polyvinyl alcohol, polyvinyl butyral, epoxy resin, silicon resin, polyester resin, polyamide resin, polyurethane resin, other synthetic resin, rubber derivatives such as chlorinated rubber, cyclized rubber, synthetic rubber, or Dyes, pigments, etc. using, as a vehicle, one or a mixture of two or more well-known ionizing radiation curable resins made of prepolymers and / or monomers having acrylates, polyesters, epoxies, etc., having a polymerizable unsaturated bond in the molecule. The coloring inks, coating materials, and the like, which are mixed with the above-mentioned coloring agents, extender pigments such as precipitated barium sulfate, and plasticizers are used. When a thermosetting resin, an electron beam or an ultraviolet ray curable resin is used as a vehicle for the wiping ink, a predetermined thermosetting treatment or an electron beam or ultraviolet ray irradiation treatment may be performed following the wiping step. Of course. In particular, when using a coloring ink having an ionizing radiation curable resin as a vehicle to a wiping ink using a paint, the quality of the cosmetic material can be stabilized and the production efficiency can be improved.

The top coat layer in the fourth invention is
It is preferable that the transparent resin layer having a thickness of about 0.1 to 10 μm is formed of a thermosetting resin or an ionizing radiation curable resin as described below. Thermosetting resin As thermosetting resin, melamine resin, diallyl phthalate resin, phenol resin, urea resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine / urea copolymer resin, silicon Resin, polysiloxane resin, etc. are used. The thermosetting resin may include a cross-linking agent,
Polymerization initiator, curing agent, polymerization accelerator, solvent, viscosity modifier,
An extender pigment or the like is added.

Ionizing Radiation Curable Resin As the ionizing radiation curable resin, a mixed resin composition of a prepolymer, an oligomer, and / or a monomer having a polymerizable unsaturated bond or an epoxy group in the molecule is used. .. Specific examples of the prepolymers and oligomers include unsaturated polyesters such as condensation products of unsaturated dicarboxylic acids and polyhydric alcohols, and methacrylates such as polyester methacrylate, polyether methacrylate, polyol methacrylate, and melamine methacrylate, Examples include acrylates such as polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate. Further, specific examples of the monomer include styrene-based monomers such as styrene and α-methylstyrene, methyl acrylate, and acrylic acid-2.
-Acrylic esters such as ethylhexyl, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, phenyl acrylate, etc., methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, methacryl Methacrylic acid esters with ethoxymethyl acrylate, phenyl methacrylate, acrylic acid-2-
(N, N-diethylamino) ethyl, methacrylic acid-2-
(N, N-Dimethylamino) ethyl, acrylic acid-2-
(N, N-dibenzylamino) ethyl, methacrylic acid-2
-(N, N-Dimethylamino) methyl, acrylic acid-2-
Substituted amino alcohol esters of unsaturated acids with (N, N-diethylamino) propyl, unsaturated carboxylic acid amides with acrylamide, methacrylamide, etc., ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1, Diacrylate compounds such as 6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol acrylate, propylene glycol dimethacrylate,
Polyfunctional compounds such as diethylene glycol dimethacrylate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, pentaerythritol tetrathioglycol, and other polythiol compounds having two or more thiol groups in the molecule. ..

The ionizing radiation curable resin is usually
5 to 95% by weight of the above prepolymer or oligomer
And a mixed composition of 95 to 5% by weight of the monomer and / or polythiol compound is utilized. Furthermore, when forming the top coat layer with ionizing radiation curable resin,
When the top coat layer is cured by irradiation with ultraviolet rays, for example, acetophenones, benzophenones,
A photopolymerization initiator such as Michler's benzoyl benzoate, α-amyloxime ester, tetramethylmeuram monosulfide, and thioxanthone, and a photosensitizer optionally added, for example, n-butylamine, triethylamine, tri- It goes without saying that a coating agent containing a photosensitizer such as n-butylphosphine is used.

[0018]

The method for producing a decorative material of the present invention is a semi-cured state in which the thermosetting resin impregnated in the base paper for a decorative material does not completely cure but the surface of the impregnated resin loses its tackiness. After that, a printing layer is attached to the base paper for decorative material impregnated with the thermosetting resin in the semi-cured state, and then the impregnated resin is completely cured. Since the use of the semi-finished product before it is determined by the printing layer formation process in the next process, it is versatile for the use of the semi-finished product impregnated with the thermosetting resin. Can be changed as appropriate. Therefore, management in mass production can be easily performed. Further, in the method for producing a decorative material of the present invention, by using a matte ink as a printing ink for forming a printing layer, gradation can be exhibited in the glossy state of the surface of the decorative material. It is possible to obtain a decorative material having an excellent design property. Further, the method for producing a decorative material of the present invention forms a printing layer when the thermosetting resin impregnated in the base paper for a decorative material impregnated with the uncured thermosetting resin is in a semi-cured state. Since it does so, no paper breakage occurs in the process of forming the printing layer, and a high-quality decorative material can be obtained. In the method for manufacturing a decorative material according to the second aspect of the present invention, the impregnating resin of the thermosetting resin is completely cured and at the same time, the printing layer surface is embossed. It is possible to obtain a decorative material. The method for manufacturing a decorative material according to the third aspect of the present invention comprises filling colored ink into the recesses formed by embossing by a wiping process. For example, a conduit groove for a wood grain printed pattern or a grain pattern for a stone printed pattern. Since stucco and stucco are expressed, it is possible to obtain a material similar to a decorative material made of natural products. Further, in the method for producing a decorative material of the fourth invention, a decorative material having a topcoat layer on the surface is obtained,
It is possible to obtain a decorative material having an excellent effect on weather resistance and the like. When the topcoat layer is formed on the surface of the decorative material obtained by the method according to the second or third aspect of the present invention, due to the effect of the embossed recesses, the recesses that are in synchronization with the embossed recesses form the topcoat layer. It may be formed on the surface.

[0019]

EXAMPLES The specific constitution of the method for producing a decorative material of the present invention will be described below with reference to examples. Example 1 decorative material base paper: impregnating resin mixtures according to the following composition to "Co. Kohjin Ltd. KW-1001P, a basis weight of 100 g / m ^2" and [A], at a rate of 100 g (dry) / m ² After impregnation, by drying at 80 ° C for 5 minutes by a belt press method, the impregnated resin is not completely cured but the surface of the impregnated resin has lost its tackiness and is cured to a semi-cured state. Let Impregnation resin mixture [A] diallyl orthophthalate prepolymer: 93 parts by weight diallyl orthophthalate monomer: 7 parts by weight Polymerization initiator (BPO): 5 parts by weight solvent (acetone) 100 parts by weight

After forming a wood grain pattern printing layer by gravure printing with a cellulosic mixed color ink on the surface of the base paper for decorative material impregnated with the thermosetting resin in a semi-cured state obtained in the above step, 200 1 in a heating atmosphere at ℃
0 m / min. While performing the roll embossing while allowing the impregnating resin to completely cure,
The intended cosmetic material was obtained.

[0021]

[Effect] According to the method for manufacturing a decorative material of the present invention, the semi-finished product has versatility, and therefore the production line can be easily adjusted. In addition, the gloss of the surface of the decorative material can be provided with gradation by the printing layer, and furthermore, the paper is not broken during the manufacturing process of the decorative material, and the decorative material of good quality can be efficiently obtained.

Claims (4)

[Claims] 1. A base paper for a decorative material is impregnated with a thermosetting resin, and then the impregnated resin is cured to a semi-cured state that does not reach complete curing, and then impregnated with the semi-cured thermosetting resin. A method for producing a decorative material, which comprises applying a printing layer to the existing base paper for decorative material, and then, completely curing the impregnated resin. 2. A base paper for a decorative material is impregnated with a thermosetting resin, and then the impregnated resin is cured to a semi-cured state that does not result in complete curing, and then impregnated with the thermosetting resin in the semi-cured state. A method for producing a decorative material, comprising applying a printing layer to the existing base paper for decorative material, and thereafter, completely curing the impregnated resin and simultaneously embossing the surface of the printing layer. 3. A base paper for a decorative material is impregnated with a thermosetting resin, and then the impregnated resin is cured to a semi-cured state that does not reach complete curing, and then impregnated with the semi-cured thermosetting resin. A printing layer is attached to the existing base paper for decorative material, after which the impregnating resin is completely cured and at the same time embossing is performed on the surface of the printing layer, and further, a wiping treatment is performed to fill the concave ink by embossing with colored ink. A method for manufacturing a decorative material, which is characterized by the above. 4. A makeup characterized by forming a top coat layer made of a transparent resin layer on the surface of a decorative material obtained by the method for producing a decorative material according to claim 1, claim 2 or claim 3. Method of manufacturing wood.