JPH0760910A - Thermosetting resin decorative panel, production thereof and decorative sheet used therein - Google Patents

Abstract

PURPOSE:To eliminate the rupture or strain deformation of a laminated decorative sheet and the flow or irregularity of patterns. CONSTITUTION:An uncured thermosetting resin soln. 5 is applied to or infiltrated into a fibrous base material 3 and a decorative sheet obtained by providing patterns 2 to a thermoplastic resin sheet 1 whose load bending temp. at the load of 18.5kg/cm<2> of JIS-K-7202 is 75 deg.C or higher is laminated to the layer of the resin soln. 5 to form a laminate which is, in turn, pressed or pressed under heating to cure the thermosetting resin soln. to be integrally bonded.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin decorative board suitably used as a surface material for furniture, kitchen appliances, building interior materials, light electric equipment cabinets, etc., a method for producing the same, and a decorative sheet used therefor.

[0002]

2. Description of the Related Art Conventionally, when a decorative sheet is further laminated and adhered to the surface of a thermosetting resin decorative plate, it is difficult to bond the decorative sheet to the resin layer that has been once hardened. It was laminated and bonded. For example, a decorative sheet made of a thermoplastic resin is laminated and bonded simultaneously with molding via an adhesive layer, an easy-adhesion primer layer, etc., if necessary (for example, JP-A-60-122149, JP-A-3-218832). JP-A No. 4-37508, etc.) and a decorative sheet using heat-resistant and dimensional-stable paper that is laminated and adhered simultaneously with molding (for example, Japanese Patent Publication No. 26-4540). , JP-A-53-
No. 9872, JP-A No. 62-152733, etc.) are known.

[0003]

In the former case described in the prior art, since the thermoplastic resin is softened by heating, the decorative sheet is deformed by heat and stress during molding of the thermosetting resin decorative plate. The pattern often collapses or becomes uneven. This phenomenon varies depending on variations in molding conditions and sheet lots, so that the quality is not stable.

In the latter case, distortion or flow of the picture pattern does not occur, but on the other hand, it is not possible to print as sharply and delicately as in the former case due to the unevenness and absorption of the fibers of the paper, and uneven texture of the paper. Therefore, the pattern is likely to be uneven. This tendency is particularly pronounced when the pattern is entirely solid. In addition, there is also a problem in that the resulting decorative plate has neither flexibility nor flexibility, and is likely to crack or break when a force such as a bending force or an impact force is applied.

Therefore, it is conceivable to use a decorative sheet made of a thermosetting resin, but the cured thermosetting resin sheet has no chemical reactivity, and therefore has insufficient adhesiveness with other layers of the decorative board. In addition, the whole decorative plate is harder than the above, and there is no one that reinforces or releases stress, so that cracks or splits easily occur due to bending and the like, so there is no possibility of practical application.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a thermosetting resin having no distortion or unevenness in a pattern and no cracks or cracks. A resin decorative board, a method for producing the same, and a decorative sheet used for the same are provided.

[0007]

In order to achieve the above object, the present inventor has wondered why such a defect is caused in a decorative sheet in which a decorative sheet made of a thermoplastic resin is laminated,
As a result of diligent examination of what should be managed to prevent such a defect, the deflection temperature under load (JI
It was found that there is a correlation between S-K-7202), the flow of the pattern on the decorative sheet, and the strain deformation, and the present invention was completed by focusing on this point. And specifically, the thermosetting resin decorative board of the present invention is 18.5 of JIS-K-7202.
A decorative sheet in which a pattern is provided on a thermoplastic resin sheet having a deflection temperature under load of 75 kg / cm ² under a load of kg / cm ^{2 and a} layer in which a thermosetting resin is impregnated or applied to a fibrous base material layer and cured and integrated in order. It is characterized by being laminated and integrally bonded.

The reason why the deflection temperature under load is set to 75 ° C. or higher as described above is as follows. That is, the thermosetting resin used for the decorative board is heated to 40 to 150 ° C. by the heat generated by the curing reaction not only when it is heated but also when it is not heated.
Although the temperature is about the same, at that time, as a necessary condition for preventing the flow of the pattern ink due to the deformation of the thermoplastic resin decorative sheet which is brought into contact with this and heated and heated, and the strain deformation, as a result of the experiment, the load deflection This is because it was found that the temperature should be 75 ° C. or higher.

The required performance of the thermoplastic resin sheet is as follows.
Post-processing of thermosetting resin decorative board (Actual size 15-3112)
Being flexible and flexible enough to absorb, absorb, or disperse the bending stress and impact force applied during so-called V-cut processing, cutting, etc.) or during use as disclosed in Japanese Patent Laid-Open No. 2 etc. , Having sufficient chemical affinity and reactivity to be able to sufficiently bond with thermosetting resin, having surface smoothness such as gravure printing, tensile strength, ink transferability, wetting index, thermosetting It is mentioned that the resin has heat resistance and dimensional stability that the pattern does not flow or distort due to heat and pressure during the curing and molding of the resin.

Among these, those satisfying the performances (1) to (7) include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and ethylhexyl (meth) acrylate. Acrylic resins such as homopolymers or copolymers (note that (meth) acrylic ester means "acrylic ester or methacrylic ester"), polyethylene terephthalate, polybutylene terephthalate, isophthalate / terephthalate copolymer Polyesters such as coalesce, polyvinyl chloride with a plasticizer addition amount of about 5 to 30 parts by weight, vinyl chloride / acrylic copolymer, vinyl chloride / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ethylene / vinyl acetate copolymer Vinyl resins such as polymers, polystyrene, acrylonitrile Styrene copolymers, styrene resins such as acrylonitrile-butadiene-styrene copolymer, a resin such as polycarbonate selected. further,
JIS-K from the above resins to satisfy the performance of
-7202 whose deflection temperature under load at 18.5 kg / cm ² load is 75 ° C. or higher is selected. The thickness of this thermoplastic resin sheet is usually 25 to 200 μm.
Use the thing of about m.

When a desired pattern is applied to the thermoplastic resin sheet, the thermoplastic resin sheet may be printed on the side in contact with the thermosetting resin, or on the opposite side or both sides. Alternatively, the same or different thermoplastic resin sheets may be laminated and adhered to each other, and a pattern may be formed between both sheets (on the back of the upper sheet or on the lower sheet). In this case, the printing method may be gravure, offset, silk screen or the like, and the pattern ink used is a resin binder to which a colorant such as a pigment or dye is added. As the binder, cellulose acetate, cellulose acetate propionate, fibrin resin such as nitrified cotton,
Acrylic resins such as homo- or copolymers of (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, vinyl chloride vinyl acetate As a pigment, one or a mixture of two or more kinds such as a copolymer is used as a pigment, red iron oxide, cadmium red, yellow lead, ultramarine blue, titanium white,
Inorganic pigments such as carbon black, organic pigments such as quinacridone, polyazo, isoindolinone, and phthalocyanine blue are used. The pattern to be printed is a grain pattern,
Natural products such as stone patterns, cloth patterns, geometric patterns, letters,
It may be any of symbols and the like.

As the thermosetting resin, a melamine resin, a diallyl phthalate resin, a guanamine resin, an unsaturated polyester resin, an epoxy resin, a polyurethane resin or the like is added with a polymerization initiator, a cross-linking agent, an extender pigment or the like, if necessary. Use one.

As the fibrous base material layer, paper, non-woven fabric, woven fabric, felt, mat or the like is used. Among these, titanium paper, high-quality paper, kraft paper, Japanese paper, etc. can be used as paper, and as non-woven fabric, woven fabric, felt or mat, glass fiber, asbestos, potassium titanate fiber, alumina fiber, silica fiber, carbon fiber It is possible to use those made of inorganic fibers such as, and organic resins such as polyester and vinylon.

In the method for producing a thermosetting resin decorative board of the present invention, an uncured thermosetting resin liquid is applied or impregnated on a fibrous base material layer, and JIS-K-7202 is applied onto the resin liquid. Of 1
Deflection temperature under load of 8.5 kg / cm ² is 75
After laminating a decorative sheet provided with a pattern on a thermoplastic resin sheet having a temperature of not less than 0 ° C., the laminate is pressed or heated to cure the thermosetting resin liquid, and the laminate is bonded and integrated.

Impregnation of a state in which the resin is filled in the fibrous base material layer by penetrating into the fibrous base material layer, and does not penetrate into the fibrous base material layer at all or reaches the back surface even if it penetrates. When the state where no coating is applied is defined as coating, either coating or impregnation may be used in the above method. Then, as specific means for applying or impregnating, there are roll coating, flow coating, comma coating, dipping, brush printing, pouring and the like.

As a concrete means for applying pressure or heat to cure the thermosetting resin liquid and adhering and integrating the laminate, a fibrous base material layer between two flat plates and an uncured thermosetting resin are used. A laminated body of resin and decorative sheet is sandwiched and both flat plates are pressed or heat-pressed, and biaxially stretched in a □ -shaped form as is conventionally done in the manufacture of unsaturated polyester decorative plates. A method in which a polyethylene terephthalate film is tensioned and attached, and the four corners are fixed to a mold, and the film surface is placed on the surface of the uncured resin and pressed, in the cavity between the male and female molds. A so-called stamping molding in which a laminated body is inserted and pressure or heat and pressure is applied by both molds is used. The heating is performed to start or accelerate the crosslinking of the thermosetting resin or the polymerization reaction itself, and may be omitted if heating is not required. In addition, the temperature for heating depends on the type of resin,
Although it is determined by the composition, it is usually about 40 to 150 ° C.

The shape of the thermosetting resin decorative plate may be a flat plate, a curved plate or the like. Further, if necessary, various base materials may be lined and laminated on the back surface (opposite surface of the decorative sheet) of the decorative plate of the present invention. As the backing substrate, a plate or sheet made of synthetic resin, metal, wood, FRP or the like is appropriately used.

[0018]

Embodiments of the present invention will be described below with reference to the drawings.

The thermoplastic resin sheet 1 has a thickness of 0.2.
mm acrylic sheet (methyl polymethacrylate, made by Mitsubishi Rayon: HBS clear), 25 μm thick biaxially oriented polyethylene terephthalate film (made by Dia foil Hoechst: S type), 0.2 mm thick acrylic sheet (polymeta Methyl acrylate, Mitsubishi Rayon, M
(BS clear) three types (A to C) are prepared, and as shown in FIG. 1, a pattern 2 of a coloring ink made of a urethane-based or acrylic-based binder and a urethane-based anchor layer are gravure-printed on the back side thereof, respectively. Then, three types of decorative sheets were created.

Using the above-mentioned three types of decorative sheets, thermosetting resin decorative plate samples (1) to (1) to
(3) was created.

Titanium paper (basis weight 80 g) as the fibrous base material 3
/ M ² ) is prepared, and this is adhered onto the plywood (thickness 2.5 mm) which is the backing substrate 4. Next, unsaturated polyester resin oligomer (manufactured by Showa High Polymer: Rigolac 200
1) Using 100 parts by weight of thermosetting resin liquid 5 containing 0.5 parts by weight of cobalt naphthenate and 1 part by weight of methyl ethyl ketone peroxide, this was applied onto titanium paper, and the above-mentioned solution was applied onto it. Laminate decorative sheets (Fig. 2). Then, after applying pressure by squeezing with a roller by hand, by heating at 60 ° C. for 30 minutes to cure, a decorative sheet in which a pattern 2 is provided on the thermoplastic resin sheet 1 as shown in FIG. 3, A thermosetting resin decorative board is obtained in which the cured thermosetting resin 6 and the fibrous base material layer 3 are sequentially laminated and bonded together and the backing base material 4 is laminated on the back surface.

Table 1 shows the evaluation results of these samples (1) to (3). Here, the case where the ink flow or the pattern is distorted was evaluated as x, and the case where there was no distortion was evaluated as o. The deflection temperature under load in the table is "JIS-K" of each of the thermoplastic resin sheets A to C used for the decorative plates of Samples (1) to (3).
-7202 shows the deflection temperature under load at a load of 18.5 kg / cm ² .

[0023]

[Table 1]

As is clear from Table 1, sample (1)
The ink flow and the distortion of the pattern were generated in Sample Nos., But this did not appear at all in Samples (2) and (3).

[0025]

Since the thermosetting resin decorative board of the present invention is constructed as described above, it is possible to prevent the laminated decorative sheet from breaking.
There is no distortion and deformation, and therefore the quality is stable and excellent without the flow and unevenness of the design.

Further, according to the method for producing a thermosetting resin decorative board of the present invention, the decorative sheets can be laminated and adhered simultaneously with the molding of the decorative board, and the decorative sheet is deformed by heat and stress during molding. Since it does not occur, the decorative board can be manufactured without causing the collapse of the design.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a decorative sheet.

FIG. 2 is a schematic cross-sectional view showing a laminated state.

FIG. 3 is a schematic cross-sectional view of a decorative board provided with a backing base material.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Thermoplastic resin sheet 2 Design 3 Fibrous base material 4 Backing base material 5 Thermosetting resin liquid 6 Thermosetting resin

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area B29K 105: 08 C2

Claims (3)

[Claims] 1. A JIS-K-7202 18.5 kg /
A thermoplastic resin sheet having a flexure temperature of 75 ° C. or more under a cm ² load is provided with a decorative sheet, and a fibrous base material layer is impregnated with or applied to a fibrous base material layer and cured and integrated to form a layer. A thermosetting resin decorative board characterized by being integrally bonded. 2. An uncured thermosetting resin liquid is applied or impregnated on the fibrous base material layer, and JIS-K-7 is applied on the resin liquid.
202. A decorative sheet provided with a pattern is laminated on a thermoplastic resin sheet having a deflection temperature under load of 18.5 kg / cm ² under a load of 75 ° C., and then the laminate is pressed or heated to press the thermosetting resin liquid. A method for producing a thermosetting resin decorative board, characterized in that the laminated body is adhered and integrated while being cured. 3. JIS-K-7202 18.5 kg /
A decorative sheet characterized in that a pattern is provided on a thermoplastic resin sheet having a deflection temperature under load of cm ² of 75 ° C. or higher.