JP3075167B2 - Laminated body with improved dimensional stability and heat resistance - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate having excellent heat resistance used for interior materials, tables, furniture tops, furniture-like cookers, floor materials, and the like. The laminate of the present invention is excellent in design properties and dimensional stability, has no board warpage, is easy to perform on site, and prevents burning of cigarettes and burning due to a high-heat cooker.

[0002]

2. Description of the Related Art In recent years, fires and burns due to high heat containers after cooking have occurred in interior materials, tables, furniture tops, furniture-style cookers, and the like used in daily life. It is occurring frequently. In addition, since vinyl chloride is currently used as the main material for flooring, its heat resistance is inferior in performance. To apply a UV curable paint to the final product or after the final application, to partially cross-link the surface layer, or to form a film forming the surface layer with a cross-linkable paste sol to improve heat resistance. But
In each case, the cigarette was scorched or deformed by fire, and none could fit on the floor of a game center or playground.

In order to further improve cigarette resistance,
Japanese Patent Application Laid-Open No. 2-116544 discloses an example in which a thermosetting resin is used as a surface layer and an aluminum foil is interposed between the substrate and the surface layer. Hard and non-flexible, woven fabric,
Nonwoven fabrics, such as prepregs in which a thermosetting resin is impregnated in a reinforcing sheet or cured sheets obtained by hot-press curing the prepregs, are only known for relatively thin sheets, and have a thickness such as PVC, rubber, etc. In addition, a flexible resin sheet was not used as a base material. And because the substrate is hard or thin in this way, deep embossing cannot be performed, for example, it is difficult to give a texture of natural stone with an uneven pattern on the surface, and in terms of design It was not satisfactory. In addition, when using a hard base material, cutting work with a cutter at the construction site can not be done easily, it takes time to construct the mosaic pattern at the site, and it can not be done on a curved surface, so there is a problem in the construction surface and it is improved Was desired.

[0004]

According to the present invention, (A) a thermosetting resin-impregnated prepreg layer forming a surface layer and (B) a flexible rubber or thermoplastic resin layer comprise (C)
It is a laminate characterized by being heat-pressed via a hot melt resin adhesive layer. However, the (A) layer is a prepreg impregnated with a thermosetting resin selected from diallyl phthalate resin, unsaturated polyester, phenol resin, amino alkyd resin, epoxy resin, acrylic urethane resin, and melamine resin, The rubber or resin of the layer (B) is chlorinated polyethylene, polybutene, ethylene-vinyl acetate copolymer, ethylene-propylene-
It is a rubber or a thermoplastic resin selected from a diene copolymer, a chloroprene polymer, a chlorosulfonated polyethylene, a styrene-butadiene copolymer, and polyvinyl chloride. The hot melt resin of the layer (C) has a melting point of 60 to 16
At 5 ° C. and a solubility parameter (SP value) of 7.4 to
10.9, a hot melt resin selected from ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, carboxylated polyethylene, polyurethane, polybutylene terephthalate, and modified ethylene-vinyl acetate copolymer It is.

Conventionally, it has been impossible to bond a thermosetting resin to a rubber or a thermoplastic resin, but by using a hot melt resin having a specific melting point and solubility parameter of the present invention, a laminate is obtained by thermocompression bonding. It became possible. By thermocompression bonding of a thermosetting resin layer and a flexible rubber or thermoplastic resin layer, having a deep embossed surface while taking advantage of the excellent heat resistance of the thermosetting resin, it has excellent design, In addition, it has become possible to manufacture a laminate that can be easily cut by a cutter knife or the like at a construction site.

The thermosetting resin-impregnated prepreg layer (A) used in the present invention may be a so-called overlay prepreg which forms a transparent layer after curing. As the prepreg layer (A), a material obtained by impregnating a thermosetting resin into an impregnated base material is used. The impregnated base material has a basis weight of 5 to 80 g / m ^2.
Japanese paper, mixed paper obtained by mixing mineral with thermal conductivity such as alumina, a basis weight of 5 to 80 g / m ² natural fibers and woven or non-woven synthetic fibers, or a basis weight of 30 to 200 g / m ²
In particular, the use of mixed paper is preferable because it prevents burning of cigarettes by fire and also improves abrasion resistance. The prepreg layer may be a single layer or a plurality of layers.However, by laminating an overlay prepreg on a pattern layer such as a pattern paper prepreg using a pattern paper impregnated base material, a pattern having a deep and excellent design can be obtained. As well as being formed, it is possible to improve the abrasion resistance and scratch resistance of the surface, and the prevention of tobacco stains from staining. The same effect as described above can be obtained by using an overlay prepreg layer as the layer (A) and interposing a pattern layer such as a vinyl chloride pattern paper between the layer (A) and the adhesive layer (C). In this case, the vinyl chloride pattern paper can be adhered to the overlay prepreg via the hot melt resin adhesive layer (C).

The thermosetting resin for impregnation of the prepreg layer (A) includes diallyl phthalate resin, unsaturated polyester, phenol resin, amino alkyd resin, epoxy resin, melamine resin, acrylic urethane resin and the like. The amount of thermosetting resin is the amount of resin impregnation (RC)
(Note 1) 40-90% by weight is appropriate. Note 1 Resin impregnation amount (RC) = Resin weight x 100 / (paper weight + resin weight) (%) When the thermosetting resin is diallyl phthalate resin, unsaturated polyester, amino alkyd resin, acrylic urethane resin, it is usually the above. A resin obtained by adding a crosslinking component and a peroxide to a resin is used as an impregnation liquid. As the crosslinking component, diallyl phthalate monomer, styrene monomer, N-methylolacrylamide, vinyltoluene, methyl methacrylate and the like can be used, and as the peracid, benzoyl peroxide, t-butyl perbenzoate and the like can be used. In the case of an epoxy resin, a solution obtained by dissolving a resin and a curing agent in a solvent is usually used as the impregnating liquid. As the curing agent, acid anhydrides and amine compounds such as triethylenetetramine, diethylenetriamine, and 4,4-diaminodiphenylmethane can be used. In the case of a melamine resin, paratoluenesulfonic acid or the like is added to the resin liquid as a catalyst and used as an impregnating liquid. In the case of a phenol resin, the resin is dissolved in a water-methanol system and used as an impregnating liquid.

The rubber or thermoplastic resin of the flexible layer (B) includes chlorinated polyethylene, polybutene, ethylene-vinyl acetate copolymer, ethylene-propylene-diene copolymer, chloroprene polymer, and chlorosulfonated polyethylene. Styrene-butadiene copolymer, polyvinyl chloride and the like, and the thickness is 1.5 to 3.0 m.
m. When a rubber or a thermoplastic resin is used as a crosslinked product, trithiocyanuric acid is used as a crosslinking agent in chlorinated polyethylene, polybutene, ethylene-vinyl acetate copolymer, ethylene-propylene-diene copolymer, chloroprene polymer, chlorosulfone. A peroxy acid such as dicumyl peroxide can be used for the functionalized polyethylene. Further, sulfur can be used for the styrene-butadiene copolymer.

The adhesive layer (C) may be a layer composed of only a hot melt resin, or may be a layer containing other components. The first mode of the adhesive layer (C) has a melting point of 6
A hot melt resin having a solubility parameter (SP value) of 7.4 to 10.9 at 0 to 165 ° C is used as it is. Examples of the hot melt resin include ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, carboxylated polyethylene, polyurethane, polybutylene terephthalate, and modified ethylene-vinyl acetate copolymer. Used as a polymer alloy. The thickness of the adhesive layer (C) is usually 3
５００500 μm, preferably 5-300 μm, especially 5-2
00 μm is used. In practice, it is laminated mainly as a polymer film, but is previously melted into a thermosetting resin-impregnated prepreg layer (A), a flexible rubber or thermoplastic resin layer (B), or a pattern layer such as vinyl chloride pattern paper. It may be dried after coating or after dissolving in an appropriate solvent.

When the melting point of the hot melt resin is less than 60 ° C., the use temperature of the laminate becomes low and is not practical. When the melting point exceeds 165 ° C., when the laminate is formed, the adherend may excessively flow in a high temperature atmosphere. In addition, not only a predetermined adhesive strength cannot be obtained, but also a predetermined product thickness cannot be maintained. Further, the flow deformation of the thermoplastic resin is large, which is not preferable. If the SP value is out of this range, the original laminated body cannot be obtained because it is separated from that of the adherend and is incompatible with each other. When the thermosetting resin layer contains a peroxide, it is preferable to add an antioxidant to the hot melt resin in order to prevent the hot melt resin adhesive layer from being deteriorated by peroxidation. As an antioxidant to be added, 2,6-di-t-butyl-p-cresol (hereinafter referred to as B
HT), 2,2'-methylenebis (4-methyl-
Phenols such as 6-t-butylphenol) and trinonylphenylphosphite, and phosphoric acids can be used, and these can be used alone or in combination of two or more. The appropriate amount of the antioxidant is usually 0.05 to 1.0% by weight based on the hot melt resin.

In a second embodiment of the adhesive layer (C) of the present invention, the adhesive layer is made of aluminum having a thickness of 10 to 200 μm;
A metal foil selected from iron, copper, zinc, and lead, a punched metal foil, or a plain woven net of ribbon-shaped metal thread is used as a reinforcing core material, and a hot melt resin is applied or laminated on both surfaces thereof. The thickness of the reinforcing core is 10 to 200 μm, preferably 20 to 50 μm. If the thickness is less than 10 μm, tearing or wrinkling occurs due to the pressure at the time of heat compression bonding. If it exceeds 200 μm, it is expensive and disadvantageous. In the practice of the present invention, the above-mentioned hot melt resin is applied or laminated on both surfaces of such a metal reinforcing core material. Hot melt resin layer to be applied or laminated is 3-10
A film thickness of 0 μm is preferred. If it is less than 3 μm, the adhesive strength is undesirably reduced. By interposing this metal foil between the thermosetting resin layer and the rubber or thermoplastic resin layer, the heat resistance of the laminate is improved, and the adhesion by the hot melt resin is ensured, and the adhesive layer (C) Can be made thinner. Thermosetting resin prepreg layer (A)
In addition to this, it is possible to prevent plate warpage due to thermal distortion of the rubber or thermoplastic resin layer (B), greatly contribute to dimensional stability, and shoulder droop at the time of cutting in secondary processing that is common in heterogeneous composites. (It is not perpendicular to the surface), and the occurrence of cracks at the small end (the occurrence of cracks at the surface of the cut end) can be prevented.

In a third embodiment of the adhesive layer (C) of the present invention, the adhesive layer (C) has a thermal conductivity of 1 W · M ⁻¹ · K ⁻¹ or more, preferably 5 W · M ⁻¹ · K ^−1. The heat resistance can also be improved by using a dispersion layer in which particles of the above-mentioned metal, metal compound or metal compound having water of crystallization are dispersed in a hot melt resin. When a metal compound having water of crystallization is used, it has an endothermic effect when heated, and heat resistance is improved. Examples of the metal or metal compound having a thermal conductivity of 1 W · M ⁻¹ · K ⁻¹ or more include the following metals, metal oxides, metal salts of acids, and silicon compounds. Metal: aluminum, copper, zinc Metal oxide: aluminum oxide, copper oxide, titanium oxide,
Metal salt of zirconium oxide: aluminum borate Silicon compound: silicon carbide Examples of the metal compound having water of crystallization include aluminum hydroxide, aluminum monophosphate, ammonium borate, and hydrotalcite. The amount of water of crystallization is usually 1 to 50 molecules, for example 1 to 5 molecules per molecule of the metal compound, and the particle size of the metal compound is usually 30 to 100 as an average particle size.
μm. If the amount of the metal compound is less than 100 parts by weight with respect to 100 parts by weight of the hot melt resin, the heat resistance is not sufficiently improved, and if it exceeds 500 parts by weight, the adhesive strength is reduced. The thickness of the adhesive layer in the above case is usually 10 to 300
μm, preferably 20 to 300 μm, is suitable. Outside this range, the adhesive strength is undesirably reduced. When the dispersion layer is used, it is more flexible than the case where a metal foil is used, and can be easily attached to an uneven portion or a curved surface, and the manufacturing process is simplified and economical.

The laminate of the present invention comprises a thermosetting resin impregnated prepreg layer (A) and a rubber or thermoplastic resin layer (B).
Can be manufactured by bonding under hot pressure by a press machine or a hot roll machine via a hot melt resin adhesive layer (C). At the time of heating and pressurizing, by using a pressing plate with a pre-designed uneven pattern,
A laminate having an embossed surface can also be obtained. When the layer (B) is a plastic resin or a non-crosslinked rubber, it is preferable to take it out of the press after cooling. By this step, the layer (A) and the layer (B) are adhered, and at the same time, the thermosetting resin-impregnated prepreg layer (A) is cured by heating to form a hard resin surface layer. At this time, when the rubber or thermoplastic resin layer (B) contains a crosslinking agent, a laminate in which the rubber or thermoplastic resin layer is also crosslinked at the same time is formed. The heating temperature is preferably from 130 to 165C. If it is lower than 130 ° C., the prepreg will not be cured. 165
When the temperature exceeds ℃, the adherend excessively flows in a high temperature atmosphere, so that not only a predetermined adhesion force cannot be obtained but also a predetermined thickness cannot be maintained. The normal pressure is 7 to 15 kg / cm ² , and the heating and pressurizing time is 10 to 40 minutes.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION A laminate of the present invention comprises a thermosetting resin-impregnated prepreg layer (A) and a rubber or thermoplastic resin layer (B) which are sandwiched between a hot melt resin adhesive layer (C) and a pressing machine. Alternatively, it can be manufactured by bonding under heat and pressure by a hot roll machine. The adhesive layer (C) was formed by coating or laminating a hot-melt resin on both sides of a metal foil or by dispersing a granular metal compound having good thermal conductivity or water of crystallization, in addition to the case of using only a hot-melt resin. It may be something. In order to enhance the design of the laminate, a pattern layer such as a vinyl chloride pattern paper may be interposed between the thermosetting resin layer (A) and the adhesive layer (C). Hereinafter, the present invention will be described with reference to Examples and Comparative Examples. The examples are illustrative and not limiting, but represent the present invention.

[0015]

EXAMPLES (A) Preparation of Prepreg Diallylphthalate prepolymer (molecular weight 10,000) 70 parts by weight Unsaturated polyester (condensate of isophthalic acid, maleic acid and ethylene glycol) 30 parts by weight Benzoyl peroxide 3.0 parts by weight Inside Release agent DR-20S (manufactured by Daiso Co., Ltd.) 0.03 parts by weight Hydroquinone 0.05 parts by weight An impregnating solution of 100 parts by weight of a solvent (toluene / acetone = 1/2) was prepared, and patterned paper (basis weight 80 g) was prepared. / M ² )
Was impregnated with the above impregnating solution, and impregnated and dried (80 to 90 ° C., 15 minutes) so that the resin amount (RC) became 50% by weight, to obtain a patterned paper prepreg (1). In addition, a polyester nonwoven fabric (having a basis weight of 40 g / m ² ) was impregnated in the same manner as the prepreg (1) to obtain a transparent overlay prepreg (1 ′) having a resin impregnation amount (RC) of 80% by weight. 13 of alumina
A weight-containing mixed paper (basis weight 30 g / m ² ) was impregnated and dried to obtain a transparent overlay prepreg (1 ″).

(B) Preparation of rubber or thermoplastic resin layer (starting sheet) Chlorinated polyethylene rubber (molecular weight 120,000, chlorine content 35% by weight) 100 parts by weight Heavy calcium carbonate 300 parts by weight Dioctyl phthalate 70 parts by weight Magnesium oxide 10 parts by weight Trithiocyanuric acid (Crosslinking agent) 2 parts by weight Methylpentamethylenedithiocarbamate Pipecoline (Crosslinking aid) 1 part by weight is kneaded with a double roll at 80 ° C., and a pale yellow thickness of 3.0 mm is obtained. A delivery sheet (2) was obtained. Next, vinyl chloride resin (degree of polymerization: 1000) 100 parts by weight Heavy calcium carbonate 200 parts by weight Plasticizer (DOP) dioctyl phthalate 50 parts by weight Tribasic lead sulfate 3 parts by weight Dibasic lead phosphite 1 part by weight Carbon 2 1 part by weight of bisamide was kneaded with a roll at 170 ° C., and the thickness was 3.0 mm.
(2 ') was obtained.

Example 1 Laminate having basic structure of the present invention (laminate of FIG. 1) Overlay paper prepreg (1 '), pattern paper prepreg (1), hot melt film (3'), thermoplastic resin layer or rubber Stepping sheet (2) as a layer is shown in FIG.
Put into a hot press with the structure of 150 ℃, pressure 10kg
/ Cm ² for 30 minutes, 3.1mm × 500mm × 50
A crosslinked laminate of 0 mm was obtained. As a hot melt film (3 ′), BH is used as an antioxidant having a thickness of 30 μm.
An ethylene-vinyl acetate copolymer (melting point 66 ° C., SP value 9.0) containing 0.2% by weight of T added to the resin was used. To check the heat resistance of this laminate, 18
The aluminum container (1 liter in volume) containing the vegetable oil at 0 ° C. was left for 20 minutes (JIS K6902), then removed and observed, but no change was observed on the surface.
As a wear resistance test, a Taber abrasion tester (JI
SK6902) was performed until the pattern of the patterned paper was half worn, and it was 3,200 revolutions. Also, let it stand in a gear oven at 80 ° C for 6 hours (JISA57
05) After the dimensional change is 0.2% vertical and 0.15% horizontal
Met. Regarding the plate sledding test, a laminated plate (500 mm × 500 mm) after molding was placed on a glass plate and placed at 20 ° C.
After standing for 24 hours, the warp was measured on the four sides around with a gap gauge, and the average value was taken as the plate sled value. With respect to this laminated board, the board sled shape was convex, and the board sled value was +1.0 mm. In the stain resistance test, the stain was wiped off with a cloth after 6 hours using a blue ink, a red ink, shoe ink (black), and a hair dye (Biken Crimtone 5G, Hoyu Co., Ltd.), but no stain was observed. Did not.

Example 2 Laminate of the present invention (laminate of FIG. 2) in which the adhesive layer was reinforced with metal foil or the like to prevent plate sledding (pattern prepreg (1)), hot melt resin on both sides of metal core material Extrusion sheet (2) as an adhesive layer (3), a thermoplastic resin layer or a rubber layer, which was extrusion-laminated, was heated at a temperature of 150 ° C. and a pressure of 13 kg / cm ² in the configuration of FIG.
Perform heat splitting press, 3.05mm × 500mm × 500
mm was obtained. The adhesive layer (3) has a thickness of 100
50 μm of a carboxylated polyethylene resin (Nack Ace GB201 manufactured by Nippon Unicar Co., melting point 93 ° C., SP value 7.9) is used on both sides of a 50 μm aluminum foil as a reinforcing core material.
What was extruded and laminated to a thickness of μm was used. When a heat resistance test was performed on the laminate according to JIS K6902 in the same manner as in Example 1, no change was observed on the surface. The dimensional change rate measured by JIS A5705 was 0.02% in height and 0.02% in width. About the board sled, it measured similarly to the method of Example 1. However, the shape of the board sled was convex and the board sled value was +0.5 mm.

Example 3 A laminate of the present invention (laminate of FIG. 3) in which a metal foil is inserted to reduce the board sledding and a vinyl chloride pattern paper is interposed as a pattern layer to enhance the design property (the laminate of FIG. 3) Pre-preg (1 '), step-out sheet (2') as thermoplastic resin layer or rubber layer, adhesive layer (3) coated with hot melt resin on both sides of metal core material, hot melt film (3 '), pattern The printed vinyl chloride patterned paper (thickness: 100 μm) (4) was hot-pressed at a temperature of 135 ° C. and a pressure of 13 kg / cm ² for 15 minutes in the configuration of FIG. 3 to obtain a laminate of 3.2 mm × 500 mm × 500 mm. Was. As the adhesive layer (3), an ethylene-vinyl acetate copolymer (melting point 66 ° C., SP value) having a 50 μm-thick aluminum foil as a reinforcing core material and BHT added to both surfaces at 0.2% by weight with respect to the resin was used. 9.0) of an acetone solution (50% by weight) coated with a gravure roll so that the thickness after drying becomes 3.5 μm, and the hot melt film (3 ′) contains 30 μm thick BHT having a thickness of 0 μm. An ethylene-vinyl acetate copolymer film (melting point 66 ° C., SP value 9.0) to which 0.2% by weight was added was used. When the surface characteristics of this laminate were measured in the same manner as in Example 1, no change was observed on the surface in the heat resistance test. The Taber abrasion test (JIS K6902) was performed until the printed vinyl chloride pattern was half worn, and it was 2,000 revolutions.

EXAMPLE 4 A laminate of the present invention (laminate of FIG. 3) in which a metal foil is inserted to reduce the board sledding and a vinyl chloride pattern paper is interposed as a pattern layer to enhance the design property. In place of using overlay paper prepreg (1 ') and hot melt film (3') in 3 above, 0.2% by weight of BHT with respect to the resin was added to the overlay paper prepreg (1 ') in advance as an antioxidant. A vinyl acetate copolymer (melting point 66 ° C., SP value 9.0)
A 3.2 mm × 500 mm × 500 mm laminate was obtained in the same manner as in Example 3 except that a melt-coated material having a thickness of 30 μm was extruded at 30 ° C. with a laminator. A heat resistance test was performed by the method of Example 1, but no change was observed on the surface. The Taber abrasion test (JIS K6902) was carried out until the printed pattern of the vinyl chloride patterned paper was worn by half.

Example 5 A laminate of the present invention (laminate of FIG. 4) in which a metal foil is inserted to reduce the board sledding and the pattern paper prepreg is interposed as a pattern layer to enhance the design property (the laminate of FIG. 4) (1 ″), a patterned paper prepreg (1), a stepping sheet as a thermoplastic resin layer or a rubber layer (2 ′), an adhesive layer (3) obtained by transferring a hot melt film to both surfaces of a metal core material with the configuration of FIG. Temperature 135 ° C,
A heat press is performed at a pressure of 13 kg / cm ² for 25 minutes.
A laminate of 5 mm × 500 mm × 500 mm was obtained. As the adhesive layer (3), an ethylene-acrylic acid copolymer hot melt film (melting point: 92 ° C., SP) containing a 30 μm-thick aluminum foil as a reinforcing core and 0.2% by weight of a 30 μm-thick BHT added thereto is used. The value 9.0) was transferred to both sides of an aluminum foil. When the surface characteristics of the laminate were determined in the same manner as in Example 1, no change was observed on the surface. Further, the tobacco fire was left for about 7 minutes, and the surface change after the fire was extinguished was observed, but no abnormality was found. Further, when the pattern of the patterned paper was half worn out in a Taber abrasion test (JIS K6902), it was 3,500 revolutions.

Example 6 Laminate Using Dispersion Layer as Adhesive Layer (Laminate in FIG. 1) Ethylene vinyl acetate copolymer (melting point 66 ° C., SP value 9.0) 100 parts by weight BHT as adhesive layer 3 ′ 0.3 parts by weight Alumina AL-30 (manufactured by Showa Denko) 250 parts by weight (average particle diameter 35 μm) Titanium oxide TITONE A-150 (manufactured by Sakai Chemical Industry) 100 parts by weight (average particle diameter 40 μm) Mixing dispersion Temperature 120 using a roll
(3 ″), which was mixed at 100 ° C. to form a film having a thickness of 100 μm, and (2 ′) was used as the thermoplastic resin layer or rubber layer in place of the stepping-out sheet (2).
Except for heating at 35 ° C. and a pressure of 13 kg / cm ² for 15 minutes, the same procedure as in Example 1 was carried out to obtain 3.1 mm × 500 mm ×
A laminate of 500 mm was obtained. This laminate had flexibility, and the surface characteristics of this laminate were evaluated in the same manner as in Example 1. As a result, no change was observed in the surface in terms of heat resistance. Further, the tobacco fire was left for 5 minutes and then removed, and the surface change was observed. No abnormality was found.

Comparative Example 1 The hot melt film of Example 1 was changed to a polyamide type (melting point: 172 ° C., SP value: 12.5) and the temperature was changed to 180.
Perform hot pressing at a pressure of 10 kg / cm ² for 20 minutes.
A laminate of 2.95 mm × 500 mm × 500 mm was obtained. When this laminate was cut and the cross section was observed, peeling was observed in the hot melt layer. Further, the rubber layer flowed too much by molding at a high temperature, and a laminate having a predetermined thickness could not be obtained.

Comparative Example 2 In Example 1, the hot melt film was changed to an ethylene-based terpolymer (H-2500 manufactured by Kurashiki Boseki Co., Ltd., SP value: 8.5, melting point: 94 ° C.) and the temperature was changed in the same configuration. 130
Hot pressing was performed at a temperature of 10 ° C. and a pressure of 10 kg / cm ² for 15 minutes, but the adhesion was poor.

[0025]

According to the present invention, heat resistance, abrasion resistance, scratch resistance, and the like can be obtained by laminating a rubber or thermoplastic resin layer and a thermosetting resin layer by hot pressing with a hot melt resin adhesive layer. It has excellent design properties, such as having a surface that can be deeply embossed while taking advantage of the excellent properties of thermosetting resin such as anti-contamination due to cigarette tarnish.Easy cutting work with a cutter knife at construction sites, and curved surface application Thus, it is possible to obtain a laminate excellent in workability that can perform the above-described steps. In addition, by interposing a reinforcing core material such as a metal foil in the adhesive layer, the slab of the laminate is eliminated and the dimensional stability is improved.
Further, in the laminate of the present invention, the formed emboss does not disappear even after long-term use.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a basic structure of a laminate of the present invention.

FIG. 2 is a schematic sectional view of a laminate of the present invention in which an adhesive layer is reinforced with a metal foil or the like to prevent plate sledding.

FIG. 3 is a schematic cross-sectional view of a laminate of the present invention in which design is enhanced by interposing a pattern layer.

FIG. 4 is a schematic cross-sectional view of a laminate of the present invention in which a metal foil is inserted in order to reduce board sled and a design property is enhanced by interposing a pattern layer.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Thermosetting resin impregnated pattern paper 1 ', 1 "Thermosetting resin impregnated transparent overlay paper 2, 2' Thermoplastic resin layer or rubber layer (starting sheet) 3 Adhesion which applied hot melt resin to both sides of metal core material Agent layer 3 'Hot melt film 3 "Hot melt film containing dispersion 4 Vinyl chloride patterned paper with printed pattern

Claims (7)

(57) [Claims] 1. A method of heating a (A) thermosetting resin-impregnated prepreg layer forming a surface layer and (B) a flexible rubber or thermoplastic resin layer via a (C) hot melt resin adhesive layer. A laminated body characterized by being crimped. However, the (A) layer is a prepreg impregnated with a thermosetting resin selected from diallyl phthalate resin, unsaturated polyester, phenol resin, amino alkyd resin, epoxy resin, acrylic urethane resin, and melamine resin, The rubber or resin of the layer (B) is chlorinated polyethylene, polybutene, ethylene-vinyl acetate copolymer, ethylene-propylene-diene copolymer, chloroprene polymer, chlorosulfonated polyethylene, styrene-butadiene copolymer, A rubber or a thermoplastic resin selected from vinyl chloride; the hot melt resin of the layer (C) has a melting point of 60 to 165 ° C. and a solubility parameter (SP value) of 7.4 to 10.9; Ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, carboxylated poly A hot-melt resin selected from either vinyl acetate copolymer - styrene, polyurethane, polybutylene terephthalate, modified ethylene. 2. The laminate according to claim 1, wherein the hot melt resin forming the adhesive layer (C) has an antioxidant added thereto. 3. A metal foil whose adhesive layer (C) is selected from aluminum, iron, copper, zinc, and lead having a thickness of 10 to 200 μm,
The laminate according to claim 1 or 2, wherein a flat woven net of a punched metal foil or a ribbon-shaped metal thread is used as a reinforcing core material, and a hot melt resin is applied or laminated on both surfaces thereof. 4. An adhesive layer (C) comprising a hot melt resin 100
100 to 5 granular metal or metal compound having a thermal conductivity of 1 W · M ⁻¹ · K ⁻¹ or more or having water of crystallization per part by weight.
The laminate according to claim 1 or 2, which comprises 00 parts by weight. 5. The laminate according to claim 1, wherein a pattern layer exists between the thermosetting resin-impregnated prepreg layer (A) and the adhesive layer (C). 6. The laminate according to claim 5, further comprising an adhesive layer (C) between the thermosetting resin-impregnated prepreg layer (A) and the pattern layer. 7. The prepreg layer (A) impregnated with a thermosetting resin is selected from Japanese paper, mixed paper mixed with a thermally conductive mineral, woven or nonwoven fabric of natural and synthetic fibers, patterned paper, and kraft paper. The laminate according to any one of claims 1 to 6, wherein the prepreg base material is impregnated with a thermosetting resin.