JPH081797A - Composite member and manufacturing method thereof - Google Patents

Abstract

PURPOSE:To obtain a composite member improved in impact resistance as compared with a conventional composite member and good in scratch resistance by successively covering the surface of a core material with an impact-resistant plastic material and a hard coat decorative sheet. CONSTITUTION:A composite member 1 having layered constitution is obtained by successively laminating an impact-resistant plastic material 3 and a hard coat decorative sheet 4 to the surface of a core material 2. As the core material 2 of the composite member 1, plywood, particle board or plastic such as a natural or synthetic resin can be used. As a resin forming the impact-resistant plastic material 3, hard polyvinyl chloride, polyvinylidene chloride, polyacetal or nylon can be used. As a base material sheet of the hard coat decorative sheet 4, polyolefin such as polyethylene or polyporopylene, a styrenic resin such as an ABS resin, polycarbonate or nylon can be used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite member for use on a horizontal surface which requires impact resistance and scratch resistance, such as a skid, a sill, a sill, a counter, and a floor material, and a method for producing the same.

2. Description of the Related Art Conventionally, composite members having colored or patterned core materials have been used as building materials and daily-use members. For example, there is known a composite member in which a veneer is attached to a core member, a composite member in which a printed pattern is applied to the core member by lamination or transfer, and the like. There is also known a composite member in which a layer made of an ionizing radiation curable resin is provided on the composite member so as to have scratch resistance.

However, in the above-mentioned conventional composite members, all of them have poor impact resistance, and especially when used on horizontal surfaces such as slides, stiles, sills, counters, floors, etc., the surface strain caused by the impact. Further, due to the cracks, there is a problem that the core material is seen from the surface, the decorative sheet provided on the surface is peeled off, and the aesthetic sense is impaired.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to eliminate the poor impact resistance of the conventional composite member and to provide a composite member having good scratch resistance.

[0004]

In order to achieve the above object, the present invention provides a composite member characterized in that the surface of a core material is sequentially coated with an impact resistant plastic material and a hard coat decorative sheet. To do.

According to the second aspect of the present invention, after the hard coat decorative sheet is attached to the outer surface of the impact resistant plastic material extruded in the shape of a cylinder notched in the longitudinal direction by heating and pressing, There is provided a method for manufacturing a composite member, characterized in that a core material is fitted into an inner portion of the impact resistant plastic material.

The present invention will be described in detail below with reference to the drawings. FIG. 1 is a three-dimensional perspective view of a composite member according to the present invention. The layer structure is such that the impact resistant plastic material 3 and the hard coat decorative sheet 4 are sequentially laminated on the surface of the core material 2. FIG. 2 is a schematic representation of a method for manufacturing a composite member according to the present invention.

The core material 2 of the composite member of the present invention is made of plywood, LV.
L, MDF, particle board, wood such as Ramin, iron,
A metal such as aluminum, and a plastic such as a cellulose derivative, a styrene copolymer, an acrylic resin, a vinyl polymer, a rosin ester resin, or a natural or synthetic resin can be used.

As a resin forming the impact resistant plastic material 3 of the composite member of the present invention, hard polyvinyl chloride, polyvinylidene chloride, polyacetal, nylon, ethyl cellulose, cellulose nitrate, propyl cellulose, cellulose acetate, polycarbonate, polyethylene terephthalate, Trifluoroethylene chloride, vinylidene fluoride, 4
Fluorinated ethylene, polyurethane, impact resistant polymethylmethacrylate, impact resistant polypropylene, glass fiber reinforced polyurethane, glass fiber reinforced unsaturated polyester and the like can be used. The most preferred resin is rigid polyvinyl chloride. For example, Izod impact value 10k
A resin of gcm / cm or more, preferably 30 kgcm / cm or more is used.

As the hard coat of the hard coat decorative sheet 4, a printed pattern layer is provided on a substrate sheet, and impact-resistant resin fine particles or synthetic resin beads are contained on the printed pattern layer and cured by ionizing radiation. It is most preferable to provide a layer formed by a curing reaction of a composition mainly composed of a mold resin by ionizing radiation because of excellent scratch resistance. Further, a thermosetting resin, a two-component curable resin, or the like applied and cured can also be used.

As the base material sheet of the hard coat decorative sheet 4, a synthetic resin sheet is most preferable in terms of moldability and coating suitability. For example, polyethylene, polyolefin such as polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer vinyl resin,
Polyester such as polyethylene terephthalate and polybutylene terephthalate, polystyrene, acrylic styrene copolymer, styrene resin such as ABS resin, polycarbonate, nylon, ionomer resin and the like can be used.
Among these, particularly a semi-rigid polyvinyl chloride having a thickness of 50 to 300 μm and a plasticizer part number of 8 to 30 parts by weight, or a resin sheet having the same plasticity and elastic properties as those of the decorative sheet has excellent moldability and Good in impact resistance and scratch resistance.

Examples of the other substrate include paper such as thin paper and wood free paper, and cloth such as woven cloth and non-woven cloth.

On the surface of the base sheet, for example, wood grain,
Prints are applied to express stones, surface patterns of natural leather, cloth, abstract patterns, etc., and in addition to recesses imitating the conduit part of wood grain, it has a shape similar to stone, leather squeezing, cloth etc. The concave portions may be shaped by combining the above-mentioned printed patterns.

As the base material for the decorative sheet having the concave portion, the one having the concave portion directly formed on the above-mentioned printed surface, or the printed surface of the thermoplastic synthetic resin sheet on which printing is applied On the other hand, a laminated sheet obtained by so-called doubling embossing, which is obtained by laminating a separately manufactured thermoplastic synthetic resin sheet by thermal bonding and shaping the laminated sheet surface by embossing, is a decorative sheet base. It can be used as a material.

Printing methods on a decorative sheet substrate include intaglio printing such as gravure and gravure offset, letterpress printing such as letterpress and flexo, lithographic offset printing, lithographic printing such as dailin, silk screen printing, electrostatic printing and ink jet printing. Etc. plateless printing is applied.

The impact resistant resin fine particles contained in the ionizing radiation curable resin of the hard coat decorative sheet 4 have a particle size of 0.1.
Use a ˜50 μm one. For making the impact resistant resin into fine particles, a method such as a pulverization method, a polymerization method, or a solubility difference method for the impact resistant resin is used.

Impact resistant resin has an Izod impact value of 10K.
Resin of gcm / cm or more, preferably 30 Kgcm / cm or more is used. Izod impact value 10 Kgcm
When a resin of less than 1 / cm is used, the particles themselves become rapidly weak against impact and scratch, and the coating film containing the particles loses resistance to impact and scratch. Further, the suitability for molding such as bending of the coating film is deteriorated, and cracks and the like during molding are likely to occur. The shape of the impact-resistant resin fine particles is preferably a sphere or a similar shape. However, other shapes may be used as long as they do not impair the scratch resistance, moldability and matteness of the coating film.

Resins having an Izod impact value of 10 kgg / cm or more include hard polyvinyl chloride, polyvinylidene chloride, polyacetal, nylon, ethyl cellulose,
Cellulose acetate, propyl cellulose, cellulose acetate, polycarbonate, polyethylene terephthalate,
Ethylene trifluoride chloride, vinylidene fluoride, tetrafluoroethylene, polyurethane, impact resistant polymethylmethacrylate, impact resistant polypropylene, glass fiber reinforced polyurethane, glass fiber reinforced unsaturated polyester, etc. can be used. . Among them, polycarbonate is the most preferable.

The impact-resistant resin fine particles may be dispersed in the ionizing radiation-curable resin by a dry method such as a jet crusher or the like.
A wet method such as a roll mill, a ball mill or a sand mill is used.

As the synthetic resin beads contained in the ionizing radiation curable resin layer of the hard coat decorative sheet 4, synthetic resin beads having at least a surface of a porous structure can be used. As a result, after the liquid ionizing radiation-curable resin before curing has entered the porous structure of the synthetic resin beads, the ionizing radiation-curable resin is cured and a strong bond is obtained. As the resin forming the synthetic resin beads having a porous structure, a resin having a good affinity with an ionizing radiation curable resin is preferable in that a strong adhesive force is easily obtained, but due to the wedge effect caused by the porous structure. There is no particular limitation because a strong bond can be obtained by adhesion. For example, acrylic resin, styrene resin, polycarbonate resin, polyamide resin, epoxy resin, phenol resin,
Melamine resin etc. are mentioned. In the case of dry blending, synthetic resin beads may be composed of a plurality of resins. The particle size of the synthetic resin beads is 0.
A range of about 5 to 100 μm, preferably 3 to 50 μm is good. If it is less than 0.5 μm, scratch resistance is lowered, and if it exceeds 100 μm, aesthetics is impaired. The compounding amount of the synthetic resin beads is 1 to 30 with respect to the ionizing radiation curable resin.
About wt% is preferable. Less than 1 wt% and 30 wt%
If it exceeds, scratch resistance is deteriorated, which is not preferable.

The ionizing radiation-curable resin for the hard coat decorative sheet 4 includes a polymerizable unsaturated bond in the molecule, or
Prepolymer, oligomer, and / or epoxy group-containing prepolymer
Alternatively, a composition in which monomers are appropriately mixed is used. Examples of the prepolymer and ologomers include unsaturated polyesters such as a condensation product of an unsaturated dicarboxylic acid and a polyhydric alcohol,
Methacrylates such as polyester methacrylate, polyol methacrylate and melamine methacrylate, acrylates such as polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate and melamine acrylate are available. Examples of the monomer include styrene,
Styrene monomers such as α-stillyl styrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, methoxybutyl acrylate, etoxymethyl methacrylate, phenyl methacrylate, methacrylic acid esters such as lauryl methacrylate. , Acrylic acid-
Substituted amino alcohol esters of unsaturated acids such as 2- (N, N-dimethylamino) ethyl, 2- (N, N-dibenzylmino) ethyl methacrylate, and 2- (N, N-dimethylamino) propyl methacrylate. Unsaturated carboxylic acid amides such as methacrylic acid, methacrylamide, methacryl amod, etc.
Compounds such as ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, propylene glycol dimethacrylate, etc. Polyfunctional compound and / or 2 in the molecule
There are polythiol compounds having at least one thiol group, for example, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, pentaerythritol tetrathioglycol and the like.

Further, other additives, for example, a polymerization inhibitor such as hydroquinone monomethyl ether for preventing curing before irradiation with ionizing radiation, or a urethane resin, within a range that does not interfere with curing by ionizing radiation, Ionizing radiation-curable thermoplastic resins such as cellulosic resins, polyester resins, acrylic resins, vinyl chloride resins, vinyl acetate resins, butyral resins, and lubricants such as silicone and polyethylene wax may be added.

A method for forming the ionizing radiation curable resin composition on the surface of the decorative sheet is, for example, coating. A coat, a flow coat, a comma coat, a dip coat, a Wheeler coat, a spinner coat, a spray coat, a silk screen, a pouring coat, a brush coat and the like are applied.

The ionizing radiation includes visible light, ultraviolet light,
Electromagnetic waves such as X-rays and electron beams or particle beams are used.
Mainly used in practice are ultraviolet rays or electron beams. As the ultraviolet ray source, a light source such as a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light, and a metal halide lamp can be used.

As the electron beam source, various electron beam accelerators such as Cockloft-Walton type, Van de Graft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type and high frequency type are used. ~ 1000 Ke
Those which irradiate with electrons having an energy of V, preferably 100 to 30 KeV can be used. Usually, the irradiation dose is about 0.5 to 30 Mrad.

Next, a method for manufacturing the composite member of the present invention will be described below. The method for producing a composite member of the present invention comprises the steps of applying a hard coat decorative sheet to the outer surface of an impact-resistant plastic material extruded into a tubular shape notched in the longitudinal direction by heating and pressing, and then applying the impact resistance. The present invention is characterized in that a core material is fitted into the inner part of the flexible plastic material.
As shown in FIG. 2, the extrusion molding of the impact-resistant plastic material and the method of manufacturing the laminate of the impact-resistant plastic material and the hard coat decorative sheet 4 in the same process are effective in improving the adhesion between the impact-resistant plastic material and the hard coat decorative sheet. This is preferable because it also increases the productivity. Moreover, you may perform in another process.

An embodiment of the method for manufacturing the composite member of the present invention will be described with reference to FIG. A material of impact-resistant plastic material is supplied to the extruder 5, the material is extruded into a cooled first mold 6, and the molded product removed from the mold is spread by a guide roller 7 into a planar shape. Then, the hard coat decorative sheet 4 wound on a roll body is thermo-bonded to the molded product by a pressing machine 8 to form the molded product into a mold shape in the cooled second mold 9. After the molded product detached from the mold is passed through the belt press 10, the step of cutting with a cutting machine 11 to a desired size (referred to as a post-process) is performed in the same step to obtain a final molded article of impact resistant plastic material. can get. The first and sixth molds 6 and 9 are cylindrical ones cut out in the longitudinal direction. The cooling temperature in the mold is preferably around 15 ° C., and it is preferable to use a cooling device. As the first mold 6, a mold having a notch at a bending portion so that it can be easily molded when a molded product is molded into a plate by a guide roller later is used. The pressing roll is made of rubber or metal, and the roll temperature at the time of pressing is preferably around 180 ° C.

The composite material 1 of the present invention is prepared by inserting the core material 1 by pushing it inside the final molded product of the impact resistant plastic material.
And A three-dimensional perspective view of the composite member 1 is illustrated in FIG.

[0028]

【Example】

(Example 1) As a base material sheet of the hard coat decorative sheet 4, a vinyl chloride sheet having a thickness of 0.1 m / m was printed with a print pattern layer of wood grain by a gravure rotary press, and then a transparent vinyl chloride sheet 0.1 m was formed. A sheet doubled with / m was prepared. The following ionizing radiation-curable resin coating liquid was applied onto the sheet by gravure reverse, and the high-pressure mercury monument lamp (160 W × 20 m /
(min x 2 lights) for 2 seconds for curing to obtain a hard coat decorative sheet 4. A material of impact-resistant plastic material is supplied to the extruder 5, the material is extruded into a cooled first mold 6, and the molded product removed from the mold is spread by a guide roller 7 into a planar shape. Then, the hard coat decorative sheet 4 wound on a roll body is thermocompression-bonded to the molded product with a pressing roll 8 to form the molded product into a mold shape in the cooled second mold 9. After passing the molded product detached from the mold 9 through the belt press 10, the step of cutting to a desired size with a cutting machine 11 (referred to as a post-process) is performed in the same step to obtain a final impact-resistant plastic material molded product. Is obtained. As the first and second molds, those having a tubular shape with a notch in the hand direction are used. The cooling temperature in the mold is 15
A temperature of around 0 ° C is preferable, and a cooling device is preferably used.
In addition, the first mold is one in which the guide roller 7 is used to form a plate-like product, and the mold is also provided with a cut so that it can be bent at a position where it can be easily bent. The pressing roll 8 is made of rubber or metal, and the roll temperature at the time of pressing is preferably around 180 ° C.

Final molded product of the above impact resistant plastic material
The composite material 1 of the present invention
And A three-dimensional perspective view of the composite member 1 is illustrated in FIG.Impact resistant plastic sheet composition Vinyl chloride resin 100 parts by weight Ionizing radiation curable resin layer coating liquid Urethane acrylate prepolymer 29 parts by weight Polyethylene glycol diacrylate 6 parts by weight Ethyl carbitol acrylate 8 parts by weight 2-Ethylhexyl acrylate 7 parts by weight Photopolymerization initiator (methyl benzoyl formation) 2 parts by weight Solvent (isopropyl alcohol etc.) 44 parts by weight Impact-resistant resin fine particles (spherical fine particles having a particle distribution of 0.1 to 50 μm made of a bisphenol type polycarbonate resin having an Izod impact value of 70 Kgcm / cm) 4 parts by weight Silicon acrylate 0.5 parts by weight (Example 2) Ionization of Example 1 Radiation curable resin coating liquid
Formed in the same manner as in Example 1 except that it was formed with the following composition
The composite member 1 of the present invention was formed.Ionizing radiation curable resin layer coating liquid Porous polycarbonate resin beads 5 parts (Sekisui Plastics Industry Co., Ltd. average particle size 8 μm, maximum particle size 20 μm) Urethane acrylate monomer 35 parts Acrylate monomer 15 parts Solvent (isopropyl alcohol / ethyl acetate = 1/1) 45 parts

(Comparative Example 1) A hard coat decorative sheet 6 is prepared in the same manner as in Example 1 and is wrapped with MDF as a core material.

Table 1 shows impact resistance and scratch resistance of the composite member thus constructed. The impact resistance test is performed by a DuPont type impact test, and the depth of the recess under impact in a 3 mmφ metal fitting with a load of 1 kg from a height of 50 cm is measured. The depth of the depression is the length measured from the surface of the member to the bottom of the depression of the unevenness. Scratch test and abrasion resistance test are based on JIS K
Done according to -6902.

[0032]

[Table 1]

[0033]

INDUSTRIAL APPLICABILITY As described above, the present invention provides a composite member having impact resistance and scratch resistance, which can be used on a horizontal surface.

[Brief description of drawings]

FIG. 1 is a three-dimensional perspective view showing an example of a composite member of the present invention.

FIG. 2 is an explanatory view showing an example of the method for producing a composite member of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Composite member 2 Core material 3 Impact resistant plastic material 4 Hard coat decorative sheet 5 Extruder 6 1st die 7 Guide roller 8 Pressing roller 9 2nd die 10 Belt press 11 Cutting machine

Claims (2)

[Claims] 1. A composite member in which the surface of a core material is sequentially coated with an impact resistant plastic material and a hard coat decorative sheet. 2. An impact-resistant plastic material extruded into a tubular shape cut out in the longitudinal direction, and a hard coat decorative sheet is attached to the outer surface of the impact-resistant plastic material by heating and pressing, and then the inside of the impact-resistant plastic material. A method for manufacturing a composite member, comprising fitting a core material into the portion.