JP2023125577A - Manufacturing method of embossment transfer resin plate for hot-pressing mold - Google Patents

Abstract

To provide a manufacturing method of an embossment transfer resin plate for a decorative plate hot-pressing mold having an uneven pattern on its surface, wherein the uneven pattern of an embossment mother die is adversely transferred without a crush of the uneven pattern in preparation of the embossment transfer resin plate even when a thermoplastic resin-made embossment mother die is used.SOLUTION: In preparation of an embossment transfer resin plate, heat insulation means 21 having a specific thickness is disposed between a back side (unevenness-free face) 20B of an embossment mother die 20 and a heating platen 25B, or hot pressing hardening is conducted only by pressure application from the back side (unevenness-free face) 20B of the embossment mother die 20, then the embossment mother die 20 and a protective film 24 are removed.SELECTED DRAWING: Figure 1

Description

The present invention relates to an embossed transfer resin plate for hot-press molding.

It is generally known that embossing is applied to the surface of a synthetic resin laminated decorative board to improve the aesthetic appearance of the decorative board.
Embossing is usually carried out using an embossing matrix, and the embossing matrix must (1) not be deformed during hot-pressure molding, that is, have heat resistance and pressure resistance under heat, and (2) be made of the same matrix. (3) reproducibility when molded using the same mold, (4) ability to produce the same pattern as the sample (perfect transferability), (5) ability to withstand long-term use (durability). (6) low price, etc. are required.
Conventionally, metal embossing master molds were often used, but manufacturing the master mold was time-consuming, and since the base material itself was made of metal, it was heavy and difficult to handle. When manufacturing a decorative board, a large number of molds are required, which poses a cost problem (for example, see Patent Document 1).

In order to solve the above-mentioned problems with a metal embossing master mold, a method of producing a resin embossing master mold is known (see, for example, Patent Document 2).

JP2016-153167 Japanese Patent Application Publication No. 8-164559

However, if the embossing matrix is made of a material that is sensitive to heat and pressure, such as thermoplastic resin, the uneven pattern of the emboss will be crushed and cannot be transferred when hot-press molded. There was a problem in that it was necessary to use a synthetic resin, which took time and effort.

Therefore, an object of the present invention is to provide an embossed transfer resin plate for decorative laminate thermo-pressure molding having an uneven pattern on the surface, and to provide an embossed transfer resin plate for decorative laminate thermoforming, even when a thermoplastic resin embossing matrix is used. Provided is a method for manufacturing an embossed transfer resin plate for decorative laminate hot-pressure molding, in which the uneven pattern of an embossing matrix is reversely transferred without crushing the uneven pattern during production, and an embossed transfer resin plate obtained by the manufacturing method. An object of the present invention is to obtain an embossed decorative board with excellent reproducibility of the embossed uneven pattern when embossing is performed using the material as a pressing plate when producing a decorative board.

As a result of intensive studies to achieve the above object, the present inventors found that when producing an embossing transfer resin plate, a certain thickness was established between the back side of the embossing matrix (the surface without irregularities) and the heating plate. The above problem can be solved by taking heat insulation measures or by applying heat and pressure only to the back side of the embossing mold (the surface without irregularities) and then removing the embossing mold and the protective film. I found a solution. The present invention was completed through further studies based on these findings.

That is, the present invention provides the inventions of the following aspects.

Item 1. In the method for manufacturing an embossed transfer resin plate, a resin-impregnated layer is provided on the front side (surface with unevenness) of a thermoplastic resin embossing matrix; A heat insulating means with a total thickness of 3 to 50 mm is provided between the heat plate (the surface with no unevenness) and the heat plate. A method for producing an embossed transfer resin plate, which is characterized by hot-pressure molding by heating and pressurizing from both sides of the back side (the surface without unevenness) of a plastic resin embossing matrix.
Item 2. In the method for manufacturing an embossed transfer resin plate, a resin-impregnated layer is provided on the front side (surface with unevenness) of a thermoplastic resin embossing matrix; Cushion paper, particle board, calcium silicate board, MDF, hardboard, insulation board, plywood, laminated wood, gypsum board, cement board, concrete board, volcanic glass composite board, etc. A heat insulating means with a total thickness of 3 to 50 mm, into which one or more members selected from layer plates, phenolic resin plates, unsaturated polyester resin plates, epoxy resin plates, melamine resin plates, and diallyl phthalate resin plates are inserted. Item 1. The method for producing an embossed transfer resin plate according to Item 1.
Item 3. In the method for manufacturing an embossing transfer resin plate, a resin-impregnated layer is provided on the front surface side (surface with unevenness) of a thermoplastic resin embossing matrix; It is characterized by hot-pressure molding by applying heat and pressure from the (surface with unevenness) and applying pressure without heating from the back side (surface without unevenness) of the thermoplastic resin embossing matrix. Method for manufacturing embossed transfer resin plate.
Item 4. The embossing according to any one of items 1 to 3, wherein the thermoplastic resin of the embossing matrix is at least one resin selected from polyvinyl chloride, polypropylene, polystyrene, and polyethylene. Method for manufacturing a transfer resin plate.
Item 5. The method for producing an embossed transfer resin plate according to any one of Items 1 to 3, wherein the pressure is 5 to 30 kgf/cm ² in the hot-press molding.
Item 6. Item 4. The method for producing an embossed transfer resin plate according to any one of Items 1 to 3, wherein the temperature in the hot-press molding is 120 to 190°C.
Section 7. A method for producing an embossed decorative board, characterized in that an embossed transfer resin board obtained by the production method according to any one of items 1 to 3 is used as a pressing plate.

According to the method for producing an embossed transfer resin plate for decorative laminate hot-pressing molding of the present invention, when a thermoplastic resin embossing matrix is used, an uneven pattern is formed during hot-pressing molding when producing an embossed transfer resin plate. An embossed transfer resin plate was obtained in which the uneven pattern of the embossing matrix was transferred in the opposite direction without being crushed, and the embossed transfer resin plate obtained by this manufacturing method was used as a pressing plate when producing a decorative board to perform embossing. When applied, an embossed decorative board with excellent reproducibility of the embossed uneven pattern can be obtained.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows one Embodiment of the manufacturing method of the emboss transfer resin board for decorative board hot-pressing molding of this invention. It is a schematic diagram which shows another embodiment of the manufacturing method of the emboss transfer resin board for decorative board hot-pressing molding of this invention. FIG. 2 is an enlarged view of the embossing matrix mainly viewed in the method of manufacturing an embossed transfer resin plate for decorative laminate hot-press molding of the present invention. FIG. 2 is a schematic diagram showing an embodiment of a method for manufacturing a decorative board having an embossed shape on the surface of a resin-impregnated layer.

The present invention involves stacking several sheets of resin-impregnated paper made of a specific composition, placing a protective film on top of the paper if necessary, and then forming an embossing matrix made of thermoplastic resin and having an uneven pattern on the surface. (the surface with unevenness) should be in contact with each other, and a certain thickness of insulation should be provided between the back side (the surface without unevenness) of the embossing mother mold and the heating plate, or the back side of the embossing mother mold ( Heat-pressing molding of a decorative laminate with the uneven pattern of the matrix reversely transferred, characterized in that the embossing matrix and the protective film are removed after the embossing matrix and the protective film are cured under heat and pressure by applying only pressure (from the surface with no irregularities) The present invention relates to a method for manufacturing an embossed transfer resin plate for use.
More specifically, a resin-impregnated layer is provided on the front side (surface with unevenness) of a thermoplastic resin embossing matrix, and a resin-impregnated layer is provided on the back side (surface without unevenness) of the thermoplastic resin embossing matrix. ) and the heating plate, a heat insulating means of a specific thickness is provided between the front side (surface with irregularities) of the thermoplastic resin embossing mother mold and the thermoplastic resin embossing mother mold. This is a method for manufacturing an embossed transfer resin plate, which is characterized by hot-pressure molding by heating and pressurizing from both sides of the back side (the side without irregularities). In another embodiment, in a method for manufacturing an embossed transfer resin plate, a resin-impregnated layer is provided on the front surface side (surface with unevenness) of a thermoplastic resin embossing matrix, Heat and pressure are applied from the front side of the mother mold (the surface with irregularities), and heat is applied from the back side (the surface without irregularities) of the thermoplastic resin embossing mother mold without heating. This is a method for manufacturing an embossed transfer resin plate, which is characterized by pressure molding.

[Resin-impregnated layer used for embossed transfer resin plate]
The embossed transfer resin plate is composed of a resin-impregnated layer containing resin-impregnated paper, and the resin-impregnated layer includes at least a thermosetting resin composition (or a cured product thereof) impregnated into an impregnated base material and an impregnated base material.

The resin-impregnated layer may be a single layer or a multilayer (laminate). Further, the resin-impregnated layer may have a single layer of a thermosetting resin composition, or may have a layer of a plurality of different thermosetting resin compositions (multi-laminate). It's okay.

The impregnated base material is not particularly limited as long as it can be impregnated with the thermosetting resin composition described below, but examples include impregnated paper cloth such as titanium paper, tissue paper, reinforced paper, kraft paper, and cellulose paper; polyester, rayon, etc. Examples include woven or nonwoven fabrics such as acrylic, vinylon, and glass nonwoven fabrics. The impregnated paper cloth may be printed. The impregnated base material may be a single layer or a multilayer.

The amount of the thermosetting resin composition described below impregnated into the impregnated base material is preferably 10 to 500 g/m ² , more preferably 100 to 300 g/m ² per area of the impregnated base material. If the amount of impregnation is 10 g/m ² or more, the amount of impregnation will be sufficient and the strength of the resin plate will be good. When the amount of impregnation is 500 g/m ² or less, costs can be reduced.

The thickness of the resin-impregnated layer is not particularly limited, but is, for example, 10 to 200 μm, preferably 20 to 100 μm. When the thickness is 10 μm or more, it is possible to suppress the occurrence of defects such as poor flow during hot-press molding. When the thickness is 200 μm or less, warping of the molded product due to resin contraction can be suppressed.

The resin-impregnated layer can be manufactured by a known or commonly used method, for example, as follows. First, a thermosetting resin composition is prepared. The thermosetting resin composition is obtained by mixing an unsaturated polyester resin and, if necessary, various components described below. When the thermosetting resin composition has a low viscosity, the impregnated base material can be impregnated by immersing it in a bath of the thermosetting resin composition. When the thermosetting resin composition is a highly viscous liquid or solid, dilute or dissolve the thermosetting resin composition in an appropriate solvent, such as an organic solvent such as acetone, toluene, or methyl ethyl ketone, to obtain an appropriate viscosity. The impregnated base material is immersed in a resin liquid, and then dried to evaporate the solvent. The impregnation temperature is, for example, 10 to 35°C, preferably 20 to 30°C. Although a method has been described in which the above-mentioned impregnated base material is immersed in the above-mentioned thermosetting resin composition bath, the above-mentioned impregnation is performed by applying the above-mentioned thermosetting resin composition on the surface of the above-mentioned impregnated base material and leaving it to soak in. You can go. The above-mentioned thermosetting resin composition can be produced by hardening the above-mentioned thermosetting resin composition by hot-pressing molding by a method detailed in the method for producing an embossed transfer resin plate described below.

[Thermosetting resin composition used for resin-impregnated paper]
The thermosetting resin composition of the present invention includes a resin composition having thermosetting properties (thermosetting resin composition) and a thermosetting resin (an unsaturated polyester-based prepolymer) in the thermosetting resin composition. This includes both compositions containing resins (thermocured resin compositions) obtained by curing resins, etc.). That is, the resin-impregnated layer has two types: one in which the thermosetting resin composition is impregnated into the impregnated base material (a layer before thermosetting, prepreg), and the other in which the thermosetting resin in the composition is cured (heat-cured layer). layer after curing).

The thermosetting resin composition of the present invention contains at least an unsaturated polyester resin.

The unsaturated polyester resin may be liquid or solid at room temperature. The above-mentioned unsaturated polyester resins may be used alone or in combination of two or more.

Examples of the unsaturated polyester resin include compounds containing a structural unit derived from a polybasic unsaturated acid and a structural unit derived from a polyhydric alcohol. Moreover, the unsaturated polyester resin may further contain a structural unit derived from a polybasic saturated acid. Each of the unsaturated acid, saturated acid, and polyhydric alcohol may be used alone or in combination of two or more.

Examples of the polybasic unsaturated acids include maleic acid, fumaric acid, itaconic acid, and phthalic acid monomers (orthophthalic acid, isophthalic acid, and terephthalic acid). Among these, the unsaturated acid preferably contains a phthalic acid monomer. Moreover, it is preferable that maleic acid is included.

Examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, and hydrogenated bisphenol A. The polyhydric alcohol component preferably contains propylene glycol, ethylene glycol and/or hydrogenated bisphenol A, among others.

Furthermore, an air-curable unsaturated polyester resin may be used as the unsaturated polyester resin. For example, a structural unit derived from an aliphatic cyclic unsaturated acid such as tetrahydrophthalic acid, 3,6-endomethylenetetrahydrophthalic acid, methyl-3,6-endomethylenetetrahydrophthalic acid as the unsaturated acid, Examples include polyester resins containing structural units derived from allyl glycidyl ether as a hydric alcohol.

The number average molecular weight (Mn) of the unsaturated polyester resin is 500 to 2,800, preferably 800 to 2,200. When the above-mentioned number average molecular weight is 500 or more, the fluidity of the resin composition can be maintained, and the impregnating property into the impregnated base material is excellent. When the number average molecular weight is 2,800 or less, the viscosity is reduced and handling is excellent. The above number average molecular weight is a value obtained by GPC measurement.

The weight average molecular weight (Mw) of the unsaturated polyester resin is not particularly limited, but is preferably from 2,500 to 7,000, more preferably from 3,500 to 5,500. When the weight average molecular weight is 2,500 or more, the fluidity of the resin composition can be maintained and the impregnating property into the impregnated base material is better. When the weight average molecular weight is 7,000 or less, the viscosity decreases and handling is excellent. The above weight average molecular weight is a value obtained by GPC measurement.

The molecular weight dispersity (Mw/Mn) of the unsaturated polyester resin is not particularly limited, but is preferably 1.5 to 4.5, more preferably 2.0 to 4.0.

The acid value of the unsaturated polyester resin is not particularly limited, but is preferably 5 to 30 KOHmg/g, more preferably 10 to 25 KOHmg/g.

The content ratio of the unsaturated polyester resin in the thermosetting resin composition of the present invention is preferably 10 to 60% by mass, more preferably The amount is 15 to 50% by weight, more preferably 20 to 40% by weight. When the content is 10% by weight or more, a resin-impregnated layer having sufficient strength can be obtained by hot-press molding.

The thermosetting resin composition of the present invention may contain monomers constituting the unsaturated polyester resin and oligomers (for example, 2 to 3 polymers) of the monomers. For example, it may contain a monomer that is a constituent unit of an unsaturated polyester resin.

The thermosetting resin composition of the present invention preferably contains a polymerization initiator (curing agent). By using the above-mentioned polymerization initiator, the curing speed becomes faster than when polymerizing the unsaturated polyester resin alone, and a resin-impregnated layer having a sufficient degree of curing can be obtained in a short time by hot-press molding. Examples of the polymerization initiator include organic peroxide curing agents such as benzoyl peroxide, tert-butyl perbenzoate, methyl ethyl ketone peroxide, and dicumyl peroxide.

The content of the polymerization initiator is preferably 2 to 10 parts by weight, more preferably 4 to 8 parts by weight, based on 100 parts by weight of the unsaturated polyester resin.

The thermosetting resin composition of the present invention may contain components other than the above-mentioned components. Other components listed above include thermosetting resins such as diallylphthalate resins (excluding unsaturated polyester resins), flame retardants such as aluminum hydroxide, curing catalysts, curing accelerators, polymerization inhibitors, and mold release agents. fillers such as silica, plasticizers, dispersants, thickeners, viscosity modifiers, colorants (pigments, dyes, etc.), antifoaming agents, preservatives, ultraviolet absorbers, depleting agents, antibacterial agents, leveling agents , silane coupling agents, etc. The above-mentioned other components may be used alone or in combination of two or more.

When the polymerization inhibitor is included, the reaction rate of the unsaturated polyester resin can be adjusted, and molding stability can be improved. As the polymerization inhibitor, known or commonly used ones can be used, such as hydroquinones such as hydroquinone, methylhydroquinone, p-tert-butylcatechol, and mono-tert-butylhydroquinone; hydroquinone monomethyl ether, di- Phenols such as tert-butyl-p-cresol; Quinones such as benzoquinone, p-benzoquinone, naphthoquinone, p-toluquinone; di-tert-butylhydroxytoluene, 2,6-di-tert-butyl-4-methylphenol , copper salts such as copper naphthenate; and phenothiazines. The above polymerization inhibitors may be used alone or in combination of two or more.

The content of the polymerization inhibitor is preferably 0.005 to 0.5 parts by mass, more preferably 0.05 to 0.3 parts by mass, and still more preferably 0.005 to 0.5 parts by mass, based on 100 parts by mass of the unsaturated polyester resin. .8 to 0.2 part by mass. When the content is within the above range, the molding stability of the embossed transfer resin plate is better.

[Embossed transfer resin board]
An embossing transfer resin plate can be produced using the resin-impregnated paper and the embossing matrix. The embossing transfer resin plate of the present invention is produced by stacking several sheets of the resin-impregnated paper, and placing a protective film thereon on the front surface ( Either the back side of the embossing mother mold (the surface with no unevenness) should face each other and be in contact with each other, and a specific thickness of heat insulation should be taken between the back surface of the embossing mother mold (the surface with no unevenness) and the heating plate; It is obtained by heat-pressure curing by applying only pressure from the surface (without the surface), and then removing the embossing matrix and the protective film. In addition, the "front side" of the embossing matrix as used in the present invention means the side that has an uneven pattern on the surface, and the "back side" of the embossing matrix means the side that does not have an uneven pattern on the surface. means the side of

An embossed transfer resin plate provided with a resin-impregnated layer produced using the thermosetting resin composition of the present invention has excellent reproducibility of an uneven pattern when embossing is performed using an embossing matrix.

The embossed transfer resin plate of the present invention may include other layers in addition to the resin-impregnated layer described above. Examples of the other layers include a protective film 24 for protecting the surface of the resin-impregnated layer, a thin paper between the circulating plate 23 and the resin-impregnated layer 22, and the like. In addition, after manufacturing the embossed transfer resin board, it is preferable to peel off the protective film 24 and then use it for manufacturing a decorative board, which will be described later.

As the above-mentioned protective film, any known or commonly used film used for decorative laminates can be used. Examples include mold-treated films and low-tack films. The protective film 24 is peeled off when a decorative board is manufactured using the embossed transfer resin plate 50' as a pressing plate.

[Method for manufacturing embossed transfer resin plate]
An embodiment of the method for manufacturing the embossed transfer resin plate will be described with reference to FIGS. 1 and 3. First, resin-impregnated paper is produced in the manner described above (paragraph number 0018).

Next, as shown in FIG. ), a protective film 24, a resin-impregnated layer 22 (several layers of the resin-impregnated paper produced above), and a circulating plate 23 are placed.

Next, using a press machine, thermo-pressure molding is performed by applying pressure while heating from the top and bottom of the laminate including the resin-impregnated layer 22 with the hot plates 25A and 25B, thereby forming the resin-impregnated layer 22. A heat-cured resin impregnated layer 22' is formed by curing, and an embossed transfer resin plate 50' having an embossed shape on the surface is obtained. As described above, it is preferable that the hot-press molding method is a laminated hot-press molding method, that is, the resin-impregnated layer 22 and the embossing matrix 20 are stacked on top of each other, placed in a mold, and then hardened under hot pressure.

The above hot pressure molding can be carried out, for example, preferably at a pressure of 5 to 30 kgf/cm ² , more preferably 10 to 25 kgf/cm ² , and most preferably 12 to 20 kgf/cm ² .

The above-mentioned hot-press molding can be carried out preferably at a temperature of 120 to 190°C, more preferably 130 to 170°C, and most preferably 140 to 160°C.

The above hot-pressure molding can be carried out preferably under conditions of 30 seconds to 20 minutes, more preferably between 45 seconds and 18 minutes, and most preferably between 60 seconds and 15 minutes.

The embossed transfer resin plate 50' obtained after hot-press molding includes a layer in which a protective film 24 provided on the embossing matrix 20 and a thermoset resin-impregnated layer 22' are laminated. Thereafter, the protective film 24 is removed, and an embossed transfer resin plate 50' is obtained.

Another embodiment of the method for manufacturing the embossed transfer resin plate will be described with reference to FIGS. 2 and 3. First, resin-impregnated paper is produced in the manner described above (paragraph number 0018).

Next, as shown in FIG. 2, the moving plate 23, the embossing matrix 20 (the front surface side of the embossing matrix 20; the embossing matrix 20A faces the resin-impregnated layer 22), and the protection A film 24, a resin-impregnated layer 22 (several sheets of the resin-impregnated paper described above), and a circulating plate 23 are placed.

Next, using a press machine, hot pressure molding is performed by heating and applying pressure from above and below the laminate including the resin-impregnated layer 22. At this time, the heater of the hot platen 25A is turned on. Heating and pressurization: Only pressurize without turning on the heater of heating plate 25B'. The resin-impregnated layer 22 is cured to form a thermoset resin-impregnated layer 22', and an embossed transfer resin plate 50' having an embossed shape on the surface is obtained. As described above, it is preferable that the hot-press molding method is a laminated hot-press molding method, that is, the resin-impregnated layer 22 and the embossing matrix 20 are stacked on top of each other, placed in a mold, and then hardened under hot pressure.

The above hot pressure molding can be carried out, for example, preferably at a pressure of 5 to 30 kgf/cm ² , more preferably 10 to 25 kgf/cm ² , and most preferably 12 to 20 kgf/cm ² .

The above hot pressure molding can be carried out at a temperature of preferably 120 to 190°C, more preferably 130 to 170°C, and most preferably 140 to 160°C with respect to the hot platen 25A. Note that it is preferable that the heating plate 25B' not be heated.

The above hot-pressure molding can be carried out preferably under conditions of 30 seconds to 20 minutes, more preferably between 45 seconds and 18 minutes, and most preferably between 60 seconds and 15 minutes.

The embossed transfer resin plate 50' obtained after hot-press molding includes a layer in which a protective film 24 provided on the embossing matrix 20 and a thermoset resin-impregnated layer 22' are laminated. Thereafter, the protective film 24 is removed, and an embossed transfer resin plate 50' is obtained.

As the member used for the heat insulating means 21, general materials that can withstand hot pressure molding can be used, such as cushion paper, particle board, MDF, hard board, insulation board, plywood, laminated wood, gypsum board, and cement. Boards, concrete boards, calcium silicate boards, volcanic glass multilayer boards, phenolic resin boards, unsaturated polyester resin boards, epoxy resin boards, melamine resin boards, diallyl phthalate resin boards, etc. can be used. Preferred members include cushion paper, particle board, calcium silicate board, MDF, hard board, insulation board, plywood, laminated wood, volcanic glass multi-layer board, phenol resin board, unsaturated polyester resin board, and epoxy resin board. , melamine resin board, diallyl phthalate resin board, and more preferable members include cushion paper, particle board, calcium silicate board, MDF, hard board, insulation board, plywood, laminated wood, and volcanic glass multilayer board. . Among them, cushion paper, particle board, and calcium silicate board are most preferred from the viewpoint of ease of handling and availability.

The member used for the heat insulating means 21 is preferably one with low thermal conductivity. That is, it is preferable to use a material that maintains its rigidity (does not become soft) at temperatures of 120 to 190°C. Specifically preferred ranges of thermal conductivity include 0.01 to 4, more preferably 0.02 to 3, still more preferably 0.03 to 2. Among them, 0.03 to 2 is most preferable from the viewpoint of heat insulation properties and material availability.

The thickness of the entire member used for the heat insulating means 21 is not limited as long as it exhibits heat insulating properties, but a thickness of 3 to 50 mm can be suitably used, for example. More preferably 3.5 to 40 mm, still more preferably 4 to 30 mm. Among them, from the viewpoint of ease of handling, 4 to 30 mm is most preferable.

The heat insulating means 21 may be a single layer or a multilayer (laminate). Further, the heat insulating means may be a layer of a single material or may have layers of a plurality of different materials (multi-laminate). Further, in the case where the heat insulating means 21 has a plurality of layers of different materials, there is no restriction on the order in which the layers of each material are placed, and any order may be used.

As the embossing matrix 20, known or commonly used ones used for commonly available wallpaper embossing sheets and floor embossing tiles can be used. These are inexpensive and available in various types of embossed products (commercially available). For example, there are Sangetsu's floor tiles, Earth Works' 1811, and Asahipen's repair wallpaper, among which Sangetsu's floor tiles are the most preferred from the viewpoint of a wide variety of embossed types.

The embossing matrix 20 is made of commonly used materials such as polyvinyl chloride, polypropylene, polystyrene, polyethylene, AS resin, ABS resin, acrylic resin, methacrylic resin, PET resin, PVA resin, polyvinylidene chloride, and polyvinylidene fluoride. Among them, from the viewpoint of cost and availability, polyvinyl chloride, polypropylene, polystyrene, and polyethylene are preferred, and polyvinyl chloride is most preferred.

As described above, the embossed transfer resin plate 50' equipped with the resin-impregnated layer 22' obtained using the thermosetting resin composition of the present invention has excellent reproducibility of the uneven pattern of the matrix embossing, and the protective film 24 After peeling off, it can be used as a pressing plate when making a decorative board as described below.

Next, an embossed decorative board manufactured using the above-mentioned embossed transfer resin board 50' as a pressing plate will be explained. The embossed decorative board of the present invention comprises a decorative sheet impregnated with a decorative board composition and a base material.

[Resin composition for decorative board]
In the decorative sheet used for the embossed decorative board produced using the embossed transfer resin board 50' of the present invention as a pressing plate, the resin composition for the decorative board impregnated into the decorative sheet is diallylphthalate resin, unsaturated polyester resin, etc. It contains at least a resin and aluminum hydroxide.

The diallyl phthalate resin is a prepolymer having an allyl group in the molecule, and is a thermosetting resin (thermosetting resin).

The diallyl phthalate resin contains at least a structural unit derived from a diallyl phthalate monomer. Examples of the diallyl phthalate monomer include diallyl orthophthalate, diallyl isophthalate, and diallyl terephthalate. The above-mentioned diallylphthalate monomers may be used alone or in combination of two or more. Further, the diallylphthalate resin may be used alone or in combination of two or more. The weight average molecular weight of the diallyl phthalate resin determined by GPC is preferably 10,000 to 50,000.

The unsaturated polyester resin may be liquid or solid at room temperature. The above-mentioned unsaturated polyester resins may be used alone or in combination of two or more.

Examples of the unsaturated polyester resin include compounds containing a structural unit derived from a polybasic unsaturated acid and a structural unit derived from a polyhydric alcohol. Moreover, the unsaturated polyester resin may further contain a structural unit derived from a polybasic saturated acid. Each of the unsaturated acid, saturated acid, and polyhydric alcohol may be used alone or in combination of two or more.

Examples of the polybasic unsaturated acids include maleic acid, fumaric acid, itaconic acid, and phthalic acid monomers (orthophthalic acid, isophthalic acid, and terephthalic acid). Among these, the unsaturated acid preferably contains a phthalic acid monomer. Moreover, it is preferable that maleic acid is included.

Examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, and hydrogenated bisphenol A. The polyhydric alcohol component preferably contains propylene glycol, ethylene glycol and/or hydrogenated bisphenol A, among others.

Furthermore, an air-curable unsaturated polyester resin may be used as the unsaturated polyester resin. For example, a structural unit derived from an aliphatic cyclic unsaturated acid such as tetrahydrophthalic acid, 3,6-endomethylenetetrahydrophthalic acid, methyl-3,6-endomethylenetetrahydrophthalic acid as the unsaturated acid, Examples include polyester resins containing structural units derived from allyl glycidyl ether as a hydric alcohol.

The number average molecular weight (Mn) of the unsaturated polyester resin is 500 to 2,800, preferably 800 to 2,200. When the above-mentioned number average molecular weight is 500 or more, the fluidity of the resin composition can be maintained, and the impregnating property into the impregnated base material is excellent. By having the above-mentioned number average molecular weight of 2,800 or less, the resin composition has high fluidity when the embossed transfer resin plate (press plate) having an uneven shape is superimposed on the resin-impregnated layer, and the curing speed is relatively slow. This promotes the movement of colored pigments and provides excellent synchronization. Further, the number average molecular weight is more preferably 1,600 to 2,200 from the viewpoint of further promoting the flow of the colored pigment during embossing and providing better synchronization. The above number average molecular weight is a value obtained by GPC measurement.

The weight average molecular weight (Mw) of the unsaturated polyester resin is not particularly limited, but is preferably from 2,500 to 7,000, more preferably from 3,500 to 5,500. When the weight average molecular weight is 2,500 or more, the fluidity of the resin composition can be maintained and the impregnating property into the impregnated base material is better. When the weight average molecular weight is 7000 or less, the fluidity of the resin composition is high when the embossed transfer resin plate (press plate) having an uneven shape is superimposed on the resin-impregnated layer, and the curing speed is relatively slow. This promotes the movement of colored pigments and tends to improve synchronization. The above weight average molecular weight is a value obtained by GPC measurement.

The molecular weight dispersity (Mw/Mn) of the unsaturated polyester resin is not particularly limited, but is preferably 1.5 to 4.5, more preferably 2.0 to 4.0.

The acid value of the unsaturated polyester resin is not particularly limited, but is preferably 5 to 30 KOHmg/g, more preferably 10 to 25 KOHmg/g.

The mass ratio of diallyl phthalate resin to unsaturated polyester resin (former: latter) in the resin composition for decorative boards is preferably 20:80 to 90:10, more preferably 30:70 to 70:30. be. From the viewpoint of even better nonflammability, the ratio is more preferably 30:70 to 40:60.

The total content of diallyl phthalate resin and unsaturated polyester resin in the resin composition for decorative laminates is 20 to 90% by mass based on the total amount (100% by mass) of the resin composition for decorative laminates. It is preferably 30 to 85% by weight, and even more preferably 40 to 80% by weight. When the content ratio is 20% by mass or more, a resin-impregnated layer having sufficient strength can be obtained by hot-press molding.

The resin composition for a decorative board may contain a monomer constituting a diallyl phthalate resin or an unsaturated polyester resin, or an oligomer (for example, 2 to 3 polymers) of the monomer. For example, the above-mentioned diallyl phthalate monomer, which is a constituent unit of the diallyl phthalate resin, may be included.

The resin composition for a decorative board contains aluminum hydroxide. By containing aluminum hydroxide, the embossed decorative board has nonflammability. The shape of aluminum hydroxide is not particularly limited, and examples include cylindrical, acicular, and spherical shapes. Aluminum hydroxide may be used alone or in combination of two or more.

The average particle size of aluminum hydroxide in the resin composition for decorative laminates is 3 μm or less, preferably 2 μm or less, and more preferably 1.5 μm or less. Since the above average particle diameter is 3 μm or less, when the embossed transfer resin plate (press plate) having an uneven shape is superimposed on the resin-impregnated layer, the movement of the colored pigment is not inhibited in the thin part of the resin composition. It is assumed that this is due to the fact that it has excellent synchrony. Furthermore, it has excellent transparency. The average particle diameter is, for example, 0.2 μm or more, and may be 0.3 μm or more, or 0.5 μm or more. The above average particle diameter can be measured using a laser diffraction/scattering particle size distribution measuring device, or can be actually measured from an electron micrograph, and furthermore, can be calculated from the electron micrograph using an image processing device. You can also do it. Usually, the average particle diameter is measured by laser diffraction method.

Aluminum hydroxide may be surface-treated. The surface treatment improves the dispersibility in the resin composition for decorative laminates. Examples of compounds for surface treatment include silane coupling agents and titanium coupling agents.

Examples of the silane coupling agent include organosilicon compounds having two or three alkoxy groups in the molecule. Examples of the organosilicon compounds include vinylsilanes such as vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris(β-methoxyethoxy)silane; β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-glysilane. Epoxysilanes such as sidoxypropyltrimethoxysilane; aminosilanes such as γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane; γ-mercaptopropyltrimethoxysilane; γ -Chloropropyltrimethoxysilane and the like.

The content of aluminum hydroxide is preferably 5 to 90 parts by mass based on 100 parts by mass of the diallyl phthalate resin and the unsaturated polyester resin. When the content is 5 parts by mass or more, the nonflammability is more excellent. From the viewpoint of improving synchronization during embossing, the amount is more preferably 7 to 50 parts by mass, and even more preferably 10 to 40 parts by mass.

The resin composition for a decorative board may contain a crosslinking agent for crosslinking the diallyl phthalate resin or the unsaturated polyester resin. When a crosslinking agent is used, the hardness of the resin-impregnated layer after thermosetting can be improved, and the mold releasability, image clarity, and gloss become better. Examples of the crosslinking agent include polyfunctional monomers having at least two polymerizable functional groups having unsaturated carbon-carbon double bonds such as (meth)acryloyl groups or vinyl groups, and polymers of the polyfunctional monomers. Examples include polyfunctional compounds. The above crosslinking agents may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include hexanediol di(meth)acrylate, dodecanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, and (poly)propylene glycol. Di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetra Polyfunctional (meth)acrylate such as methylolmethane tri(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butyl di(meth)acrylate, hexyl di(meth)acrylate, etc. Examples include acrylate. Among the above-mentioned polyfunctional compounds, poly(meth)acrylate of dipentaerythritol having three or more (meth)acryloyl groups in the molecule is preferred.

The content of the crosslinking agent is preferably 0.6 to 20 parts by weight, more preferably 1 to 16 parts by weight, based on a total of 100 parts by weight of diallylphthalate resin and unsaturated polyester resin. When the content is within the above range, the hardness of the resin-impregnated layer after thermosetting becomes more appropriate.

It is preferable that the above-mentioned resin composition for decorative laminates contains a polymerization initiator (curing agent). By using the above polymerization initiator, the curing speed becomes faster than polymerization using diallyl phthalate resin or unsaturated polyester resin alone, and a resin-impregnated layer with a sufficient degree of curing can be obtained in a short time by hot pressure molding. I can do it. Examples of the polymerization initiator include organic peroxide curing agents such as benzoyl peroxide, tert-butyl perbenzoate, methyl ethyl ketone peroxide, and dicumyl peroxide.

The content of the polymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on a total of 100 parts by mass of diallylphthalate resin and unsaturated polyester resin. .

The resin composition for a decorative board may contain components other than the above components. Other components mentioned above include thermosetting resins other than diallylphthalate resins and unsaturated polyester resins, flame retardants other than aluminum hydroxide, curing catalysts, curing accelerators, polymerization inhibitors, mold release agents, silica, etc. Fillers, plasticizers, dispersants, thickeners, viscosity modifiers, colorants (pigments, dyes, etc.), antifoaming agents, preservatives, ultraviolet absorbers, depleting agents, antibacterial agents, leveling agents, silane coupling agents Examples include. The above-mentioned other components may be used alone or in combination of two or more.

When the resin composition for decorative laminates is to have excellent synchronization during embossing, it is preferable that the resin composition for decorative laminates contains a colored pigment. As the above-mentioned colored pigment, known or commonly used ones can be used, and pearl pigments are preferred among them. The content of the coloring pigment is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on a total of 100 parts by weight of diallylphthalate resin and unsaturated polyester resin.

Other flame retardants other than the above aluminum hydroxide include metal oxides such as magnesium hydroxide. When the above-mentioned resin composition for decorative laminates is made to have excellent synchronicity when embossed, it is necessary to use other materials in addition to aluminum hydroxide from the viewpoint of ensuring excellent synchronization and sufficient nonflammability. Preferably, it contains a flame retardant. The above-mentioned other flame retardants may be used alone or in combination of two or more.

The average particle diameter of the other flame retardants mentioned above is such that when an embossed transfer resin plate (pressing plate) having an uneven shape is overlaid on a resin-impregnated layer, the movement of the colored pigment is more inhibited in the thinner part of the resin composition. From the viewpoint of making the synchronization more excellent without reducing the noise, the thickness is preferably 4 μm or less, more preferably 3 μm or less, and even more preferably 2 μm or less. The average particle diameter is, for example, 0.2 μm or more, and may be 0.3 μm or more, or 0.5 μm or more. The average particle size of the other flame retardants mentioned above is determined by the same method as the average particle size of the aluminum hydroxide.

The content of the other flame retardants mentioned above is appropriately set according to the content of all the flame retardants in the resin composition for decorative laminate. The content of the flame retardant in the resin composition for decorative laminates is preferably 10 to 90 parts by mass, more preferably 20 to 70 parts by mass, based on the total of 100 parts by mass of diallyl phthalate resin and unsaturated polyester resin. parts, more preferably 30 to 60 parts by mass.

When the above-mentioned mold release agent is included, the mold releasability from the embossed transfer resin plate (press plate) will be better. Examples of the mold release agent include fluorine mold release agents, silicone mold release agents, wax mold release agents, and the like. The above-mentioned mold release agents may be used alone or in combination of two or more.

The content of the above mold release agent is preferably 0.1 to 8 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the diallyl phthalate resin and unsaturated polyester resin. . When the content is 0.1 part by mass or more, the releasability from the embossed transfer resin plate (pressing plate) will be better. When the content is 8 parts by mass or less, the adhesion between the resin-impregnated layer and the base material in the embossed decorative board will be good.

When the polymerization inhibitor is included, the reaction rate of diallylphthalate resin and unsaturated polyester resin can be adjusted, and molding stability can be improved. As the polymerization inhibitor, known or commonly used ones can be used, such as hydroquinones such as hydroquinone, methylhydroquinone, p-tert-butylcatechol, and mono-tert-butylhydroquinone; hydroquinone monomethyl ether, di- Phenols such as tert-butyl-p-cresol; Quinones such as benzoquinone, p-benzoquinone, naphthoquinone, p-toluquinone; di-tert-butylhydroxytoluene, 2,6-di-tert-butyl-4-methylphenol , copper salts such as copper naphthenate; and phenothiazines. The above polymerization inhibitors may be used alone or in combination of two or more.

The content of the polymerization inhibitor is preferably 0.005 to 0.5 parts by mass, more preferably 0.05 to 0.3 parts by mass, based on a total of 100 parts by mass of diallylphthalate resin and unsaturated polyester resin. Part by weight, more preferably 0.8 to 0.15 part by weight. When the content is within the above range, the molding stability of the embossed decorative board is better.

The viscosity (rotation speed: 6 rpm) of the 50% by mass acetone solution of the resin composition for decorative boards at 20° C. is preferably 110 to 800 mPa·s, more preferably 150 to 700 mPa·s. Further, the viscosity (rotation speed: 60 rpm) of the 50% by mass acetone solution of the resin composition for decorative boards at 20° C. is preferably 30 to 200 mPa·s, more preferably 40 to 120 mPa·s. The above-mentioned viscosity is a value measured using a B-type viscometer for a solution obtained by adding acetone to the above-mentioned resin composition for a decorative board until the solid content concentration becomes 50% by mass.

The thixotropic index (TI) of an acetone solution of the resin composition for decorative boards at 20° C. with a solid content of 50% by mass is preferably 3 to 8, more preferably 4 to 7. When the TI is 3 or more, the thixotropy is high and the impregnating property to the impregnated base material is more excellent. When the TI is 8 or less, the resin composition has appropriate fluidity when impregnated into the impregnated base material, and the impregnating property into the impregnated base material is more excellent. The above TI is a value determined by [viscosity (6 rpm)/viscosity (60 rpm)] based on the viscosity of the 50% by mass solid content acetone solution at 20°C.

[Cosmetic sheet]
A decorative sheet and an embossed decorative board can be produced using the resin composition for a decorative board. The decorative sheet has a resin-impregnated layer including an impregnated base material and a thermosetting resin composition impregnated into the impregnated base material, and the thermosetting resin composition is the resin composition for decorative board or its like. Examples include decorative sheets that are cured products.

The decorative board resin composition is a thermosetting resin composition. The thermosetting resin composition includes a thermosetting resin composition (thermosetting resin composition) and a thermosetting resin (prepolymer diallylphthalate resin) in the thermosetting resin composition. It includes both compositions (thermocured resin compositions) containing resins obtained by curing thermoplastic and unsaturated polyester resins, etc.). That is, the resin-impregnated layer includes a layer in which the thermosetting resin composition is impregnated into an impregnated base material (a layer before thermosetting, prepreg), and a layer in which the thermosetting resin in the composition is cured (heat-cured layer). layer after curing).

The resin-impregnated layer is a layer in which an impregnated base material is impregnated with the resin composition for decorative laminates or a cured product of the resin composition. The resin-impregnated layer may be a single layer or a multilayer (laminate). Further, the resin-impregnated layer may have a single layer of a resin composition for decorative laminates, or may have layers of a plurality of different resin compositions for decorative laminates (multilayer laminate). It's okay.

The impregnated base material is not particularly limited as long as it can be impregnated with the resin composition for decorative laminates, but examples include impregnated paper cloth such as titanium paper, thin paper, reinforced paper, kraft paper, and cellulose paper; polyester, rayon, Examples include woven or nonwoven fabrics such as acrylic and vinylon. The impregnated paper cloth may be printed. The impregnated base material may be a single layer or a multilayer.

The amount of the thermosetting resin composition impregnated into the impregnated base material is preferably 10 to 500 g/m ² , more preferably 100 to 300 g/m ² per area of the impregnated base material. When the amount of impregnation is 10 g/m ² or more, the amount of impregnation is sufficient and the adhesion to the base material increases. When the amount of impregnation is 500 g/m ² or less, costs can be reduced.

The thickness of the resin-impregnated layer is not particularly limited, but is, for example, 10 to 200 μm, preferably 20 to 100 μm. When the thickness is 10 μm or more, it is possible to suppress the occurrence of defects such as poor flow during hot-press molding. When the thickness is 200 μm or less, warping of the molded product due to resin contraction can be suppressed.

The resin-impregnated layer can be manufactured by a known or commonly used method, for example, as follows. First, a resin composition for a decorative board, which is a thermosetting composition, is prepared. The resin composition for a decorative board is obtained by mixing a diallyl phthalate resin, an unsaturated polyester resin, and aluminum hydroxide, and, if necessary, the various components described above. When the resin composition for decorative laminates has a low viscosity, the impregnated base material can be impregnated by immersing it in a bath of the resin composition for decorative laminates. If the resin composition for decorative laminates is a high viscosity liquid or solid, dilute or dissolve the resin composition for decorative laminates in an appropriate solvent, such as an organic solvent such as acetone, toluene, or methyl ethyl ketone, to obtain an appropriate viscosity. The impregnated base material is immersed in a resin liquid, and then dried to evaporate the solvent. The impregnation temperature is, for example, 10 to 35°C, preferably 20 to 30°C. Although a method has been described in which the above-mentioned impregnated base material is immersed in the above-mentioned resin composition bath for decorative laminates, the above-mentioned impregnation is carried out by applying the above-mentioned resin composition for decorative laminates on the surface of the impregnated base material and leaving it to soak in. You can go. When the thermosetting resin composition is a cured product of the resin composition for decorative laminates, the resin composition for decorative laminates can be formed by hot-pressure molding by the method detailed in the method for producing embossed decorative laminates described below. It can be made by curing things.

[Decorative board]
An embossed decorative board can be produced using the above decorative sheet. The embossed decorative board includes, for example, a base material and the decorative sheet provided on one surface of the base material. More specifically, the embossed decorative board has at least a structure in which a base material and a decorative sheet including a resin-impregnated layer in which the base material is impregnated with the resin composition for decorative board are laminated.

In the embossed decorative board, the surface of the resin-impregnated layer (that is, the surface opposite to the base material) may have an embossed shape. A decorative board including a resin-impregnated layer produced using the resin composition for a decorative board of the present invention exhibits synchronicity depending on the thickness of the resin-impregnated layer when embossing is performed.

The embossed decorative board may include other layers in addition to the layers described above. Examples of the other layers include a primer layer for improving the adhesion between the resin-impregnated layer and the base material, a core layer for imparting shape stability to the embossed decorative board, and the above-mentioned Examples include a protective film for protecting the surface of the resin-impregnated layer.

FIG. 4 shows an embodiment of the embossed decorative board. The embossed decorative board 10 shown in FIG. 4 includes a base material 1, a resin-impregnated layer 2', and a protective film 3. The resin-impregnated layer 2' is a layer obtained by impregnating an impregnated base material with a cured product of a resin composition for a decorative board, and is obtained by thermosetting the resin-impregnated layer 2.

Examples of the base material include known or commonly used base materials used for embossed decorative boards. Examples of the base material include organic base materials and inorganic base materials. Examples of the organic base material include wood veneer, plywood, laminated wood, particle board, medium density fiberboard (MDF), high humidity fiberboard, kenaf board, etc.; paperboard, woven fabric, non-woven fabric; Fibrous base materials such as resin-impregnated paper and resin-impregnated cloth; acrylic resin board, styrene resin board, ABS resin board, polycarbonate resin board, nylon resin board, polystyrene resin board, polypropylene resin board, polyester resin board, glass fiber reinforced plastic Examples include synthetic resin base materials such as plates. Examples of the above-mentioned inorganic base materials include metal plate base materials such as aluminum plates, stainless steel plates, duralumin plates, steel plates, and brass plates; magnesium oxide plates, aluminum hydroxide plates, aluminum oxide plates, silicon oxide plates, and titanium oxide plates. , magnesium chloride board, calcium silicate board, volcanic glass material board, gypsum (calcium sulfate) board, slag gypsum board, limestone (calcium carbonate) board, wood wool cement board, slag cement board, lightweight aerated concrete board, glass fiber Examples include inorganic base materials such as reinforced concrete plates. The base material may be a single layer or a laminate of the same or different layers. Further, the base material may be subjected to an adhesion-facilitating treatment such as a sealer treatment or a primer treatment to improve adhesion with the resin-impregnated layer.

The thickness of the base material is not particularly limited, but is preferably 3 to 50 mm, more preferably 4 to 30 mm. When the thickness is 2 mm or more, it has sufficient strength and is difficult to break. When the thickness is 50 mm or less, it is lightweight and easy to handle.

As the protective film, any known or commonly used film used for embossed decorative boards can be used, such as plastic films such as polyethylene terephthalate film (PET film), polypropylene film, polybutylene terephthalate film (PBT film), etc. Examples include films that have been subjected to mold release treatment and low-tack films. The protective film is peeled off when the embossed decorative board is used.

[Method for manufacturing embossed decorative board]
An embodiment of the method for manufacturing the decorative board will be described with reference to FIG. 4. First, as mentioned above, an impregnated base material is impregnated with a thermosetting decorative laminate resin composition prepared by diluting or dissolving with a solvent, and then dried as necessary to volatilize the solvent. The resin impregnated layer 2 is prepared by impregnating the impregnated base material with the thermosetting resin composition for decorative laminate. Then, if necessary, a releasable base material such as a polyethylene film is laid on the resin-impregnated layer 2 to obtain a decorative sheet. When using a releasable base material, the releasable base material may be temporarily adhered to the decorative sheet by using a small amount of volatile solvent at the edges.

Next, the decorative sheet is placed on the base material 1 so that the resin-impregnated layer 2 is on the base material 1 side, and if it has a releasable base material, the releasable base material is peeled off, and the resin-impregnated layer 2 is placed on the base material 1 side. The embossed transfer resin plate 50' is superimposed on the layer 2 to obtain a laminate in which the embossed decorative board 10 and the embossed transfer resin plate 50' are laminated. The surface of the embossed transfer resin plate 50' facing the resin-impregnated layer 2 has a shape for transferring the uneven pattern.

Next, using a press machine, heat and pressure are applied from above and below the laminate including the embossed decorative board 10 to perform hot-pressure molding to harden the resin-impregnated layer 2 to form a thermoset resin. An impregnated layer 2' is formed to obtain a laminate in which an embossed decorative board 10' and an embossed transfer resin board 50' are laminated. As described above, as the method of hot-pressing molding, it is preferable to use the laminated hot-pressing molding method, that is, the resin-impregnated layer 2 and the base material 1 are stacked on top of each other, placed in a mold, and then hardened under hot pressure. The above-mentioned hot-press molding can be preferably carried out under the conditions of, for example, a pressure of 10 to 25 kgf/cm ² , a temperature of 120 to 190° C., and a time of 30 seconds to 15 minutes.

The laminate obtained after hot-press molding includes an embossed decorative board 10' in which a base material 1 and a thermoset resin-impregnated layer 2' provided on the base material 1 are laminated. Thereafter, the embossed transfer resin board 50' is removed, and an embossed decorative board 10' having an embossed shape on the surface of the resin-impregnated layer 2' is obtained.

When producing an embossed decorative board 10' having an embossed shape on the surface of the resin-impregnated layer 2', an embossed transfer resin board 50' having an uneven shape on the surface facing the resin-impregnated layer 2 is used. Then, as shown in FIG. 4, when the embossed transfer resin plate 50' is superimposed on the resin-impregnated layer 2, an uneven shape corresponding to the above-mentioned uneven shape is formed on the surface of the resin-impregnated layer 2. That is, the resin-impregnated layer 2 includes a thick film portion 2a and a thin film portion 2b. When the uneven shape is formed on the surface of the resin-impregnated layer 2, a higher pressure is applied to the region that will become the thin film portion 2b than the region that will become the thick film portion 2a. When the resin-impregnated layer 2 contains a colored pigment, the colored pigment flows from the region that becomes the thin film portion 2b to the region that becomes the thick film portion 2a when pressure is applied. At this time, since the average particle diameter of aluminum hydroxide is small, the flow of the colored pigment is not hindered and can flow smoothly. As a result, in the resin-impregnated layer 2', the amount of colored pigment per unit area in the thick film portion 2a is greater than the amount in the thin film portion 2b, and synchronism is obtained. Thereafter, it is subjected to hot pressure molding using a press machine to obtain an embossed decorative board 10' having an embossed shape on the surface of the resin-impregnated layer 2'.

A protective film such as a PET film may then be attached to the surface of the resin-impregnated layer 2' of the embossed decorative board 10'. The embossed decorative board can be manufactured in the manner described above.

As mentioned above, the embossed decorative laminate including the resin-impregnated layer obtained using the resin composition for decorative laminates of the present invention is nonflammable because it contains aluminum hydroxide whose average particle size is within a specific range. Excellent in Furthermore, when a resin-impregnated layer is prepared by blending a colored pigment into the resin composition for decorative laminates, and the surface of the resin-impregnated layer is embossed, synchronization is developed according to the thickness of the resin-impregnated layer. .

The present invention will be explained in more detail below based on Examples, but the present invention is not limited only to these Examples.

[Manufacture example 1]
<Preparation of resin-impregnated paper 1 used for embossed transfer resin plate>
142 parts of unsaturated polyester, 160 parts of surface-treated aluminum hydroxide (product name ``BE043STM'', manufactured by Nippon Light Metal Co., Ltd.), magnesium hydroxide (product name ``Mugseeds W-H4'', manufactured by Kamishima Chemical Industry Co., Ltd.) 40 parts, hydroquinone (polymerization inhibitor, manufactured by Kawaguchi Chemical Co., Ltd.) 0.16 parts, benzoyl peroxide 3 parts (manufactured by Kawaguchi Pharmaceutical Co., Ltd.), polymerization initiator (trade name "Perhexa (registered trademark) C"), A resin solution was prepared by dissolving 3 parts of Yuka Sangyo Co., Ltd. and 2 parts of dry silica (trade name: ``Rheolo Seal (registered trademark)'', manufactured by Tokuyama Co., Ltd.) in acetone, and a glass of 30 g/m ² was prepared. A resin-impregnated paper 1 for use in an embossed transfer resin plate of 170 g/m ² was obtained by impregnating a nonwoven fabric (Gravest, model number "SAS-030", manufactured by Olivest Co., Ltd.).

<Production of embossed transfer resin plate 1>
Example 1
On top of the circulation board, 5 sheets of cushion paper (the thickness of 5 sheets of cushion paper is 5 mm), PVC embossing style (manufactured by Earth Works, model number "1811"), PBT film, and the resin-impregnated paper obtained in Production Example 1 1 was placed in this order on the tissue paper and on the circulation board. The PVC embossing tile had an uneven shape, and was placed with the uneven side facing the PBT film side. Then, pressure was applied using a press machine and heat was applied to perform hot pressure molding. The hot pressure molding was performed at a temperature of 150° C. and a pressure of 11 kgf/cm ² for 15 minutes. Thereafter, the pressure was released, and the laminate of the rotating plate, cushion paper, PVC embossed tile, and decorative sheet was taken out from the press and cooled to room temperature to obtain an embossed transfer resin plate 1.

<Production of decorative sheet 1 for evaluation decorative board>
Diallyl orthophthalate prepolymer (methyl ethyl ketone 50% by mass solution viscosity (30°C) 96.5 mPa・s, manufactured by Osaka Soda Co., Ltd.) 38 parts by mass, unsaturated polyester (trade name "DH-2000B", manufactured by DIC Materials Corporation) 81 parts by mass, 5 parts by mass of dipentaerythritol hexaacrylate, 37.5 parts by mass of aluminum hydroxide (trade name "BF013STM", average particle diameter 1 μm, surface treated, manufactured by Nippon Light Metal Co., Ltd.), magnesium hydroxide (trade name "Magsies N-6", 12.5 parts by mass (average particle size 1.3 μm), 3 parts by mass of benzoyl peroxide, 1 part by mass of internal mold release agent (trade name "ZELEC UN", manufactured by DuPont), hydroquinone (polymerized inhibitor) 0.05 parts by mass, 3 parts by mass of fine powder silica (trade name "Carplex", manufactured by Shionogi & Co., Ltd.), 3 parts by mass of pearl pigment (trade name "Iriodin 520", manufactured by Merck & Co., Ltd.), and A resin composition solution was prepared by dissolving 0.15 parts by mass of an antifoaming agent in 100 parts by mass of acetone. A 60 g/ ^m2 dark printed patterned paper serving as an impregnated substrate was immersed in the above resin composition solution at 25°C to impregnate it with the above resin composition, and then heated in a hot air circulation oven at 105°C for 90 seconds to remove the solvent. was evaporated to obtain a decorative sheet 1 made of 160 g/m ² impregnated paper (impregnated amount: 167 parts by mass relative to 100 parts by mass of printed pattern paper).

<Production of embossed decorative board 1 for evaluation>
A base material (trade name "Dilite", manufactured by Daiken Kogyo Co., Ltd., thickness 3 mm, noncombustible material) is placed on the circulating board, and the decorative sheet 1 is placed on the base material, and impregnated paper is placed on top of the base material. It was placed so that it was in contact with the base material. Then, using a press machine, pressure was applied so that the heating plate on which the pressing plate was set was placed on the impregnated paper side, and the other heating plate was placed on the circulating plate side, and heated to perform hot-press molding. At this time, the embossed transfer resin plate obtained in <Preparation of embossed transfer resin plate 1> was used as the pressing plate. Incidentally, the surface of the pressing plate facing the impregnated paper has an uneven shape for providing an embossed shape. The above hot-press molding was performed at a temperature of 150° C. and a pressure of 16 kgf/cm ² for 3 minutes. Thereafter, the pressure was released, and the laminate of the rotating plate, the base material, and the decorative sheet was taken out from the press and cooled to room temperature to obtain the embossed decorative board 1 for evaluation.

<Production of embossed transfer resin plate 2>
Example 2
A vinyl chloride embostyle (manufactured by Earth Works, model number "1811"), a PBT film, 10 sheets of impregnated paper, tissue paper, and a circulating plate were placed on the circulating plate in this order. The PVC embossing tile had an uneven shape and was placed with the uneven side facing the PBT film side. Then, pressure was applied using a press machine and heat was applied to perform hot pressure molding. The hot pressure molding was performed at a temperature of 150° C. and a pressure of 11 kgf/cm ² for 15 minutes. At this time, the heating plate on the PVC embossing tile side was set to apply only pressure without heating. Thereafter, the pressure was released, and the laminate of the circulating plate, PVC embossed tile, and decorative sheet was taken out from the press and cooled to room temperature to obtain an embossed transfer resin plate 2.

<Production of embossed decorative board 2 for evaluation>
Example except that a decorative sheet for evaluation decorative board was produced in the same manner as in paragraph number 0123, and the embossed transfer resin board 2 obtained in Example 2 <Preparation of embossed transfer resin board 2> was used as the pressing plate. Embossed decorative board 2 for evaluation was obtained in the same manner as in Example 1.

<Production of embossed transfer resin plate 3>
Example 3
On top of the circulating board, a 15 mm thick particle board (manufactured by Nippon Steel Tex Engine Co., Ltd.), a PVC embossing style (manufactured by Earth Works, model number "1811"), a PBT film, and the resin-impregnated paper 1 obtained in Production Example 1 were placed. 10 sheets, tissue paper, and a rotating plate were placed in this order. The PVC embossing tile had an uneven shape and was placed with the uneven side facing the PBT film side. Then, pressure was applied using a press machine and heat was applied to perform hot pressure molding. The hot pressure molding was performed at a temperature of 150° C. and a pressure of 11 kgf/cm ² for 15 minutes. Thereafter, the pressure was released, and the laminate of the circulating plate, particle board, PVC embossed tiles, and decorative sheet was taken out from the press and cooled to room temperature to obtain an embossed transfer resin plate 3.

<Production of embossed decorative board 3 for evaluation>
Example except that a decorative sheet for evaluation decorative board was produced in the same manner as in paragraph number 0123, and the embossed transfer resin board 3 obtained in Example 3 <Preparation of embossed transfer resin board 3> was used as the pressing plate. Embossed decorative board 3 for evaluation was obtained in the same manner as in Example 1.

<Production of embossed transfer resin plate 4>
Example 4
On top of the circulating plate, a 12 mm thick 0.8 calcium silicate plate (Hilac, manufactured by A&A Materials Co., Ltd.), a PVC embostyle (manufactured by Earth Works, model number "1811"), PBT film, obtained in Production Example 1 were placed. Ten sheets of the resin-impregnated paper 1 were placed on the thin paper and the circulation plate in this order. The PVC embossing tile had an uneven shape and was placed with the uneven side facing the PBT film side. Then, pressure was applied using a press machine and heat was applied to perform hot pressure molding. The hot pressure molding was performed at a temperature of 150° C. and a pressure of 11 kgf/cm ² for 15 minutes. Thereafter, the pressure was released, and the laminate of the circulating plate, calcium silicate plate, vinyl chloride embossed tile, and decorative sheet was taken out of the press and cooled to room temperature to obtain an embossed transfer resin plate 4.

<Production of embossed decorative board 4 for evaluation>
Example except that a decorative sheet for evaluation decorative board was produced in the same manner as in paragraph number 0123, and the embossed transfer resin board 4 obtained in <Preparation of embossed transfer resin board 4> of Example 4 was used as the pressing plate. Embossed decorative board 4 for evaluation was obtained in the same manner as in Example 1.

<Production of embossed transfer resin plate 5>
Comparative example 1
A vinyl chloride embostyle (manufactured by Earth Works, model number "1811"), a PBT film, 10 sheets of impregnated paper, tissue paper, and a circulating plate were placed on the circulating plate in this order. At this time, no heat insulating means made of cushion paper was provided between the PVC embossing tile and the circulating plate. The PVC embossing tile had an uneven shape and was placed with the uneven side facing the PBT film side. Then, pressure was applied using a press machine and heat was applied to perform hot pressure molding. The hot pressure molding was performed at a temperature of 150° C. and a pressure of 16 kgf/cm ² for 10 minutes. Thereafter, the pressure was released, and the laminate of the rotating plate, the PVC embossed tile, and the decorative sheet was taken out of the press and cooled to room temperature to obtain the embossed transfer resin plate 5.

<Production of embossed decorative board 5 for evaluation>
Example except that a decorative sheet for evaluation decorative board was produced in the same manner as in paragraph number 0123, and the embossed transfer resin board 5 obtained in Comparative Example 1 <Preparation of embossed transfer resin board 5> was used as the pressing plate. Embossed decorative board 5 for evaluation was obtained in the same manner as in Example 1.

<Production of embossed transfer resin plate 6>
Comparative example 2
On top of the rotating board, 2.5 mm thick MDF (manufactured by Daiken Kogyo Co., Ltd.), PVC embossing style (manufactured by Earth Works, model number "1811"), PBT film, and resin-impregnated paper 1 obtained in Production Example 1 10 sheets of paper, tissue paper, and a rotating board were placed in this order. The PVC embossing tile had an uneven shape and was placed with the uneven side facing the PBT film side. Then, pressure was applied using a press machine and heat was applied to perform hot pressure molding. The hot pressure molding was performed at a temperature of 150° C. and a pressure of 11 kgf/cm ² for 15 minutes. Thereafter, the pressure was released, and the laminate of the rotating plate, MDF, PVC embossed tile, and decorative sheet was taken out from the press and cooled to room temperature to obtain an embossed transfer resin plate 6.

<Production of embossed decorative board 6 for evaluation>
Example except that a decorative sheet for evaluation decorative board was produced in the same manner as in paragraph number 0123, and the embossed transfer resin board 6 obtained in Comparative Example 2 <Preparation of embossed transfer resin board 6> was used as the pressing plate. Embossed decorative board 6 for evaluation was obtained in the same manner as in 1.

<Evaluation>
The surface of the resin-impregnated layer of each decorative board obtained in Examples 1 to 4 and Comparative Examples 1 to 2 was visually observed and judged according to the following criteria, and the results are summarized in Table 1.

［判定基準］
〇（良好）：凹部と凸部の着色の濃淡の差が大きく、エンボス形状との同調がはっきりとしている。
×（不良）：凹部と凸部の着色の濃淡の差が小さく、エンボス形状との同調が感じられない。

[Judgment criteria]
○ (Good): There is a large difference in the shade of color between the concave and convex portions, and the synchronization with the embossed shape is clear.
× (Poor): The difference in the shade of coloring between the concave portions and the convex portions is small, and synchronization with the embossed shape is not felt.

Examples 1 and 3 to 4, which have sufficient insulation to the PVC embossing matrix, and Example 2, which only applies pressure from the back side (surface without unevenness) of the PVC embossing matrix, have excellent synchronization. It was rated as being On the other hand, in Comparative Example 1, in which no insulation measures were taken for the PVC embossing matrix, and in Comparative Example 2, in which the overall thickness of the insulation means was thin and the insulation of the PVC embossing matrix was insufficient, the embossing was crushed. Synchrony was rated as poor because the difference in shading was small.

1 Base material 2 Resin-impregnated layer (before thermosetting, prepreg)
2a Thick film part 2b Thin film part 2' Resin-impregnated layer (thermally cured)
10,10' Embossing decorative board 20 Embossing matrix 20A Embossing matrix front surface (surface with unevenness)
20B Embossing matrix back side (surface without unevenness)
21 Heat insulation means 22 Resin-impregnated layer (before thermosetting, prepreg)
22' Resin impregnated layer (thermally cured)
23 Swivel plate 24 Protective film 25A, 25B Heat plate 25B' Heat plate (pressure only)
50 Embossed transfer resin plate (before thermosetting, prepreg)
50' Embossed transfer resin plate (thermally cured)

Claims (7)

In the method for manufacturing an embossed transfer resin plate, a resin-impregnated layer is provided on the front side (surface with unevenness) of a thermoplastic resin embossing matrix; A heat insulating means with a total thickness of 3 to 50 mm is provided between the heat plate (the surface with no unevenness) and the heat plate. A method for producing an embossed transfer resin plate, which is characterized by hot-pressure molding by heating and pressurizing from both sides of the back side (the surface without unevenness) of a plastic resin embossing matrix. In the method for manufacturing an embossed transfer resin plate, a resin-impregnated layer is provided on the front side (surface with unevenness) of a thermoplastic resin embossing matrix; Cushion paper, particle board, calcium silicate board, MDF, hardboard, insulation board, plywood, laminated wood, gypsum board, cement board, concrete board, volcanic glass composite board, etc. A heat insulating means with a total thickness of 3 to 50 mm, into which one or more members selected from layer plates, phenolic resin plates, unsaturated polyester resin plates, epoxy resin plates, melamine resin plates, and diallyl phthalate resin plates are inserted. The method for manufacturing an embossed transfer resin plate according to claim 1, comprising: In the method for manufacturing an embossing transfer resin plate, a resin-impregnated layer is provided on the front surface side (surface with unevenness) of a thermoplastic resin embossing matrix; It is characterized by hot-pressure molding by applying heat and pressure from the (surface with unevenness) and applying pressure without heating from the back side (surface without unevenness) of the thermoplastic resin embossing matrix. Method for manufacturing embossed transfer resin plate. 4. The thermoplastic resin of the embossing matrix is at least one resin selected from polyvinyl chloride, polypropylene, polystyrene, and polyethylene, according to any one of claims 1 to 3. Method for manufacturing embossed transfer resin plate. The method for producing an embossed transfer resin plate according to any one of claims 1 to 3, wherein the pressure in the hot-press molding is 5 to 30 kgf/cm ² . The method for producing an embossed transfer resin plate according to any one of claims 1 to 3, wherein the temperature in the hot-press molding is 120 to 190°C. A method for producing an embossed decorative board, characterized in that the embossed transfer resin board obtained by the production method according to any one of claims 1 to 3 is used as a pressing plate.

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