JP3028429B2 - Cosmetic material and manufacturing method thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to, for example, furniture, walls,
The present invention relates to a cosmetic material used for cosmetics on a surface such as a floor surface, and provides a cosmetic material having a top coat layer which is rich in depth and has a good touch feeling and a method for producing the cosmetic material.

[0002]

2. Description of the Related Art Many conventional decorative materials are provided with a top coat layer having a surface protecting effect and a gloss adjusting effect. For example, a transparent coating material such as a vinyl chloride resin, an acrylic resin, or an epoxy resin is used. A decorative material provided with a top coat layer made of an engineered layer is used.

[0003]

Among the conventional cosmetic materials having a top coat layer, those having a top coat layer made of a vinyl chloride resin cannot be wiped off the inexpensive image made of the vinyl chloride resin. Since the surface having a top coat layer is hard and smooth on the surface, it is inevitable to receive a cold touch as compared with a touch received from, for example, leather or cloth.

[0004] On the other hand, the present invention provides a cosmetic material which has an excellent effect on the three-dimensional effect and has a good touch feeling and a method for producing the cosmetic material.

[0005]

According to the present invention, in order to solve the above-mentioned problems, a top coat layer on the surface of a base material layer is provided with an ionizing radiation-curable resin serving as a soft segment and an ionizing radiation-curable resin serving as a hard segment. It is formed of a mixed resin with a resin, and also utilizes a resin layer having a concave portion on the surface as a base material layer, and synergistically utilizes a technique of filling a colored resin layer in the concave portion of the base material layer. .

[0006] That is, the decorative material of the present invention comprises a base material layer comprising a resin layer having a concave portion on the surface, a colored resin layer filled in the concave portion of the base material layer, The entire surface is transparent to be formed so as to cover the colored resin layer filled in the concave portion of the base material layer.
Having a translucent top coat layer, and wherein the transparent to translucent top coat layer is a resin mixed with an ionizing radiation-curable resin to be a soft segment and an ionizing radiation-curable resin to be a hard segment. It has a configuration that has been formed.

Further, another decorative material according to the present invention is the decorative material according to the first aspect, wherein the base material layer comprises a transparent resin layer,
It has a configuration in which a colored base material layer is backed and laminated on the back surface of the base material layer.

The method for producing a decorative material according to the present invention comprises the steps of obtaining a base material layer comprising a resin layer having a concave portion on the surface, filling the concave portion on the surface of the base material layer with a colored resin layer, A colored resin filled in a concave portion of the base material layer with a coating agent of a mixed resin of an ionizing radiation-curable resin serving as a segment and an ionizing radiation-curable resin serving as a hard segment with respect to the entire surface of the base material layer By coating so as to cover the layer, by further irradiating with ionizing radiation,
Curing the coating layer.

Further, another method for producing a decorative material according to the present invention comprises:
A step of obtaining a laminated member of a substrate layer made of a transparent resin layer having a concave portion on the surface and a colored substrate layer laminated on the back surface of the substrate layer; and a colored resin in the concave portion of the surface of the laminated member. A step of filling the layer, a coating agent of a mixed resin of an ionizing radiation-curable resin serving as a soft segment and an ionizing radiation-curable resin serving as a hard segment, with respect to the entire surface of the base layer, a concave portion of the base layer. Coating so as to cover the colored resin layer filled therein, and further irradiating with ionizing radiation to cure the coating layer.

In the decorative material of the present invention having the above-described structure and the method of manufacturing the same, a colorless, colored transparent or colored opaque resin layer is used as the base material layer composed of the resin layer having concave portions on the surface. When a colored base layer is lined with a material layer, a base layer made of a transparent resin layer is used. As a base layer made of these resin layers, a thermoplastic resin layer having a thickness of about 25 to 300 μm having embossing suitability is suitable, and examples thereof include polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, and the like. Vinyl resins such as polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polymethyl methacrylate, polymethyl acrylate, polymethacrylic acid Acrylic resin such as ethyl, polystyrene,
Acrylic nitrile-butadiene-styrene copolymer (A
Films and sheets made of BS), cellulose triacetate, cellophane, polycarbonate and the like are used.

In the decorative material according to the second aspect of the present invention, the base material layer made of a transparent resin layer is provided so that the backed colored base material layer can be seen through the base material layer. The layer may be composed of a coating layer formed by coating or the like.

In the decorative material according to the second aspect of the present invention, the colored base layer backed and laminated on the base layer made of a transparent resin layer may be transparent or opaque.
A resin layer is used, for example, tissue paper, kraft paper,
Paper such as titanium paper, high quality paper, coated paper, art paper, glassine paper, non-woven fabric or woven fabric of synthetic fiber, inorganic fiber, natural fiber, etc., metal foil or metal plate, ceramic plate, vinyl steel plate, wood plate, etc. Is done.

The back of the transparent substrate layer, the surface of the colored substrate layer,
Furthermore, a pattern by printing is provided on the surface of the colored opaque substrate layer or the like as required, for example, a wood pattern such as a cedar pattern, a stone pattern such as marble, a cloth pattern, a leather pattern, or the like. A solid color solid pattern or the like is attached to the entire surface.

Further, in the second invention, the lamination between the substrate layer composed of a transparent resin layer and the colored substrate layer may be performed by, for example, a heat fusion method or a dry lamination method. Alternatively, a method of forming a coating layer by a coating method on the surface of the colored base material layer is used.

The shape of the concave portion on the surface of the resin layer constituting the base material layer is arbitrary. However, when a pattern by printing is provided on the back surface of the base material layer or the surface of the colored base material layer, the printed pattern is formed. Usually, a concave portion having a shape matching the shape is formed.For example, when the printed pattern is a wood grain pattern, a concave portion representing a conduit groove or a hairline of a plate material, and a printed pattern represents leather. When the printed pattern expresses a grain, a concave portion shaped to express a grain or a stucco, when the printed pattern expresses a stone, and when the printed pattern expresses a cloth, Is formed with a concave portion having a shape representing a stitch of a cloth or the like.

The concave portion on the surface of the base material layer is, for example, an embossed plate having an embossed pattern of a conduit obtained by copying an uneven state such as a wood surface by electroforming, or a photoengraving method based on the uneven state of the wood surface. Is formed by using an original plate copied and prepared by using an embossing plate or the like in which an embossed pattern of a conduit is formed by a photo etching method.

In the decorative material according to the second aspect of the present invention, a laminated member of a base material layer made of a transparent resin layer having a concave portion on the surface and a colored base material layer stacked on the back surface of the base material layer It is preferable to use a so-called doubling embossing method in which a base layer made of a transparent resin layer is laminated on the colored base layer and at the same time a concave portion is formed by embossing on the surface.

The colored resin layer filled in the recesses on the surface of the base material layer is, for example, a natural resin such as shellac, corval, dammar, rosin, rosin ester or a modified resin thereof, nitrocellulose, acetylcellulose, or the like.
Cellulose derivatives such as ethylcellulose and benzylcellulose, phenolic resins, urea resins, phthalic resins, maleic resins, melamine resins, polyvinyl acetate resins, polyvinyl chloride resins, acrylic resins, polyvinyl alcohol, Polyvinyl butyral, epoxy resin, silicone resin, polyester resin, polyamide resin, polyurethane resin, other synthetic resins, rubber derivatives such as chloride rubber, cyclized rubber, synthetic rubber, or polymerizable unsaturated in the molecule Acrylate having a bond,
One or a mixture of two or more known ionizing radiation-curable resins composed of prepolymers and / or monomers such as polyesters and epoxies are used as vehicles, and coloring agents such as dyes and pigments and extender pigments such as precipitated barium sulfate are used. It is formed by a colored ink or a paint in which a plasticizer or the like is mixed. In addition,
When using an ionizing radiation-curable resin as a vehicle as the coloring ink or paint, a predetermined electron beam or ultraviolet irradiation treatment is performed following the wiping step, and the thermosetting resin is used as a vehicle. When using a material, a thermosetting treatment is performed. In particular, in the case of using a colored ink or paint using an ionizing radiation-curable resin as a vehicle, the quality can be stabilized and the production efficiency can be improved.

In order to fill the colored resin layer made of the above-described colored ink or paint into the concave portion on the surface of the base material layer, the colored ink or paint is applied to the entire surface of the base material layer by, for example, roll coating or knife coating. After coating, a so-called wiping method is used in which a doctor blade or wiping paper is used to scrape off the paint and leave only the colored paint or ink in the recess. In this wiping step, only the inside of the concave portion of the surface of the base material layer is filled with the coloring paint or ink, so that it remains.
It is necessary to adjust the viscosity of the paint to ink, the number of rotations of the roll, the angle of the doctor, the thickness, the sheet speed, the speed of the wiping paper, the hardness of the rubber roll, and the like.

The color tone of the colored resin layer filled in the recess is
In the case of a decorative material expressing a grain pattern, a material exhibiting a color tone of a wood channel groove is used, and in the case of a decorative material expressing a grain pattern, a material exhibiting a color tone of a crack in a stone is used. .

A transparent to translucent top coat layer formed so as to cover the entire surface of the base material layer with the colored resin layer filled in the concave portion on the surface of the base material layer, It is made of a colored or colorless cured resin layer of a mixed resin of an ionizing radiation-curable resin serving as a soft segment and an ionizing radiation-curable resin serving as a hard segment, and has a soft, flexible and wet feel.

As the ionizing radiation-curable resin serving as the soft segment used for forming the top coat layer, an urethane acrylate oligomer or prepolymer is used. As the ionizing radiation-curing resin serving as the hard segment, acrylic resin is used. And the like, and a tactile sensation improver such as a lubricant is preferably added to a coating agent containing these resins. The properties such as flexibility and flexibility of the top coat layer are adjusted by the number of the urethane acrylate functional groups, the molecular weight of the diol portion, the amount of the monomer mixed, and the like.

The top coat layer is coated with a coating agent containing the above-mentioned ionizing radiation-curable resin as the soft segment and the ionizing radiation-curable resin as the hard segment by a known coating machine such as a gravure coater. After processing, it is obtained by curing with ionizing radiation such as ultraviolet rays and electron beams. On the surface of the top coat layer, a concave portion can be formed at a position corresponding to the concave portion due to the influence of the concave portion formed on the surface of the base material layer, and the top coat layer having the concave portion on the surface can be formed. In this case, since the matte uneven surface is formed, the soft and wet feel of the top coat layer is further enhanced.

As the urethane acrylate resin used as the ionizing radiation-curable resin serving as the soft segment, those having an average molecular weight of about 500 to 50,000 are used. Specifically, an isocyanate compound having two or more isocyanate groups is used. A polyester prepolymer having a weight average molecular weight of 200 to 3000 having 1 to 4 hydroxyl groups in one molecule and an acrylate compound having a hydroxyl group at a terminal and having a radical polymerizable unsaturated group in a solvent or A urethane acrylate resin obtained by reacting in the absence of a solvent in the presence of a reaction catalyst such as an amine or an organotin compound and a polymerization inhibitor such as hydroquinone, that is, a urethane group and a radical polymerizable compound in the molecule. Oligomer or prepolymer of urethane acrylate having unsaturated group There are utilized.

As the isocyanate compound having two or more isocyanate groups, an aliphatic or aromatic isocyanate compound, for example, isophorone diisocyanate, hexamethylene diisocyanate or the like is used.
Examples of the polyester prepolymer having 1 to 4 hydroxyl groups in one molecule include an addition reaction product of a diol compound having an aromatic or spiro ring skeleton with a lactone compound or a derivative thereof or an epoxy compound, and phthalic acid. Condensation products of polybasic acids and polyols such as ethylene glycol; polyester diols such as ring-opened polyester compounds derived from cyclic ester compounds; polyether diols such as polytetramethylene ether glycol, polyethylene glycol and polypropylene glycol; Polycarbonate diol and the like, and a single or a mixture of two or more of them are used. In addition, 1
The polyester prepolymer having 1 to 4 hydroxyl groups in the molecule preferably has a weight average molecular weight in the range of 200 to 3000 from the viewpoint of abrasion resistance and hardness.
Those having 500 to 1500 are more preferable.

The acrylic monomer used as the ionizing radiation-curable resin serving as the hard segment includes an acrylate compound having a hydroxyl group at the terminal in one molecule and having at least one radically polymerizable unsaturated group, For example, hydroxylated derivatives of (meth) acrylic acid esters such as hydroxyethyl acrylate and hydroxypropyl methacrylate and epoxy acrylates are used.

The tactile sensation enhancer, which is optionally added to the coating agent for forming the top coat layer, serves to further improve the tactile sensation on the surface of the top coat layer. Lubricating agents such as resin-based resins, polyolefin-based resins, matting agents such as silica, calcium carbonate, barium sulfate, etc., and tactile sensation improvers comprising one or a mixture of two or more such as beads made of glass, silicon resin, etc. It is used at a ratio of about 0.05 to 15 parts by weight based on 100 parts by weight of the total amount of the ionizing radiation-curable resin to be used and the ionizing radiation-curable resin to be a hard segment.

When the top coat layer is cured by ultraviolet irradiation, the photopolymerization initiator to be added to the coating agent is, for example, acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime ester , Tetramethylmeuram monosulfide, thioxanthone and the like are used. Further, n-butylamine, triethylamine, tri-n-butylphosphine and the like are used as a photosensitizer added as needed.
Further, in the coating agent for forming the top coat layer, as necessary, a diluting solvent, a coloring agent such as a dye or a pigment which does not inhibit the curing by ionizing radiation, a stabilizer and the like are appropriately added.

The coating agent for forming the top coat layer includes, for example, roll coat, curtain flow coat, wire bar coat, reverse coat, gravure coat, gravure reverse coat, air knife coat, kiss coat, blade coat, smooth coat, comma coat By coating, the entire surface of the substrate layer is applied so as to cover the colored resin layer in the concave portion of the surface of the substrate layer, and the thickness of the cured top coat layer is 0.1 to 100 μm. It is applied so as to have a degree.

In order to particularly provide a soft and wet touch feeling in the top coat layer, the above-mentioned tactile sensation improver is harder than the inside of the top coat layer in the process of curing the coating agent for forming the top coat layer. It is preferable that the particles are distributed and fixed on the surface at high density, and the following means described below are adopted. A coating agent diluted with a solvent is applied to the surface of the base layer, and in the process of drying the solvent in the coating layer, the tactile sensation improver is applied by the action of the solvent moving to the surface of the coating layer. After moving to the surface of
The tactile sensation enhancer is fixed by curing the coating layer by irradiation with ionizing radiation. When the coating layer is cured by irradiation with ionizing radiation, the first irradiation cross-links a part of the coating layer and incompletely cures it, thereby reducing the volume of the space between molecules such as prepolymers and monomers whose volume has been reduced. After squeezing and moving the tactile sensation enhancer to the surface of the coating layer,
The second irradiation completely crosslinks and cures the coating layer, and fixes the tactile sensation improver. After applying the coating agent on the surface of the base material layer, the back surface of the base material layer is heated, and the tactile sensation improver is moved to the surface of the coating layer by convection in the liquid coating material, and then, The coating layer is cured by irradiation with ionizing radiation,
Fix the tactile enhancer.

Further, ionizing radiation is used for curing the top coat layer, and ultraviolet light from a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, and a metal halide lamp is used. As the electron beam, various electron accelerators such as Cockloft-Walton type, Bande graph type, Resonant transformer type, Insulated core transformer type, Linear type, Dynamitron type, High frequency type, etc. are used, and 100 to 1000 KeV is preferable. Represents an electron having an energy of 100 to 300 KeV,
It is preferable to irradiate to an irradiation dose of about 0.5 to 30 Mrad.

[0032]

The cosmetic material of the present invention has an excellent effect on the three-dimensional effect, and the top coat layer has a soft, flexible and moist touch. In addition to abrasion resistance, stain resistance, the surface protection function of the wiping ink, etc., it has an extremely excellent effect on the touch feeling.

Further, in the method of manufacturing a decorative material according to the present invention, a decorative material having the above-described characteristics can be easily and accurately manufactured.

[0034]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the concrete constitution of the decorative material of the present invention and the method for producing the same will be described based on production examples.

Example 1 Surface of a 0.09 mm-thick polyvinyl chloride film "RIKEN VINYL CO., LTD .; W-500" colored in a yellowish brownish color similar to the lightest color in colored natural leather. Was printed with a colored leather pattern by a gravure printing method. This printing is performed under the following conditions: printing pressure: 1 t or less (linear pressure); rubber roll hardness: 80 degrees; ink used: vinyl chloride / vinyl acetate copolymer resin ink Showa Ink ".

Next, on the printed surface of the colored leather pattern of the polyvinyl chloride film described above, another transparent polyvinyl chloride film having a thickness of 0.06 mm [RIKEN VINYL CO., LTD .; W-5
A base layer made of a transparent resin layer having a concave portion on the surface, and a back surface of the base layer by a so-called doubling embossing method for forming a concave portion by embossing on the surface of the polyvinyl chloride film. And a laminated member corresponding to the colored base material layer laminated on the substrate was obtained. The doubling embossing described above uses an electroformed embossing plate obtained by copying a leather drawing pattern from the surface of a colored natural leather, and has a sheet surface temperature of 150 ° C, a linear pressure of 1t, and a sheet feeding speed. .... 1
The test was performed at 0 m / min.

Furthermore, a brownish wiping ink "Moroboshi Ink Co., Ltd .; wiping ink" is coated on the entire surface (embossed surface) of the above transparent polyvinyl chloride film, and then is coated with a doctor blade and wiping paper. The treatment was sequentially performed to remove the ink adhering to the flat portion other than the concave portion, thereby leaving only the ink adhering in the concave portion. The viscosity of the wiping ink is adjusted by mixing a pigment into a paint made of acrylic resin / salt / vinyl acetate resin (Iwata formula,
(25 ° C.) for 12 seconds was used. The doctor blade having a thickness of about 3 mm was used, and the wiping treatment by the doctor blade was performed such that the doctor blade was always held at 90 degrees to the sheet. Next, heating was performed at 60 ° C. for 30 seconds to cure the wiping ink remaining in the concave portions.

Subsequently, a urethane acrylate resin [PR-2]
02: trade name, Mitsubishi Kasei Co., Ltd.] 60 parts by weight and urethane acrylate resin [Biscoat 190: trade name, Osaka Organic Chemical Industry Co., Ltd.] 40 parts by weight were obtained by heating to 40 ° C. After a curable coating agent having a viscosity of 500 centipoise is applied to the entire surface of the wiping-treated surface by an extrusion nozzle method, a thickness of 25 mm is immediately applied to the surface of the coating layer.
The release film having been subjected to the matting treatment of μ was contacted.

Further, the obtained laminated sheet was subjected to 230 kV by an electron curtain type electron beam (EB) irradiation device.
After the coating layer was cured by irradiating the coating layer with an electron beam of 5 Mrad at an accelerating voltage of, a release material film was peeled off to obtain a desired decorative material having a 15 μm-thick top coat layer.

In the embodiment, the top coat layer is formed in the same manner as in FIG. 1 except that the base layer after the wiping ink is cured and the colored base layer laminated on the back surface of the base layer. While traveling between the pair of nip rolls 3 and 4, the nip rolls 3 and 4
4 is used as a coating agent pool, a coating agent 5 injected by an extrusion nozzle method is applied to the entire surface of the wiping processing surface in a relatively large amount, and a nip roll 3 is formed. Excess coating agent is extruded by the pressure of the nip rolls 3 and 4 at the outlet of the gap between the coating layers 4 and 4, and the surface of the coating layer is immediately subjected to the release treatment of PE.
The top coat layer is cured by contacting the matted film 6 made of T, irradiating an electron beam with the electron beam irradiation device 7 in this state, and curing the coating layer. And a step of obtaining the intended decorative material 1.

According to the method for forming the top coat layer according to the above-described embodiment, the wiping surface is completely covered with the coating agent in the step of forming the top coat layer, and the coating layer before curing and the air are cured. Since there is no contact between the top coat layer and the top coat layer, a high quality top coat layer free of air is formed in the top coat layer.

The obtained decorative material clearly shows a three-dimensional effect due to the colored resin layer filled in the concave portion on the surface of the transparent polyvinyl chloride film, and the top coat layer has: A soft, flexible and moist touch feeling was obtained, and the inexpensive image received from a conventional cosmetic material having a top coat layer of vinyl chloride resin was wiped out.

[0043]

According to the cosmetic material of the present invention, the top coat layer formed on the surface of the cosmetic material has a soft, flexible and moist feel, and is therefore similar to, for example, leather or cloth. A feeling of touch is obtained, and the feeling of unevenness due to the concave portion formed on the surface of the base material layer and the colored resin layer filled in the concave portion is extremely sharply expressed. It will be an excellent cosmetic material and will have a high use value.

Further, the method for producing a decorative material according to the present invention can accurately produce a decorative material having the above-mentioned characteristics using a conventional production apparatus.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing steps of one embodiment of a method for producing a decorative material according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Cosmetic material having a top coat layer 3, 4 Nip roll 5 Coating agent for forming a top coat layer 7 Ionizing radiation irradiation device

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B32B 33/00 B32B 27/00

Claims (6)

(57) [Claims] 1. A base material layer comprising a resin layer having a concave portion on the surface, a colored resin layer filled in the concave portion of the base material layer, and a base material layer formed on the entire surface of the base material layer. A transparent to translucent top coat layer formed so as to cover the colored resin layer filled in the concave portion, wherein the transparent to translucent top coat layer is ionizing radiation serving as a soft segment. A decorative material comprising a cured resin layer of a mixed resin of a curable resin and an ionizing radiation curable resin serving as a hard segment. 2. The decorative material according to claim 1, wherein the base material layer is made of a transparent resin layer, and a colored base material layer is backed and laminated on the back surface of the base material layer. 3. The decorative material according to claim 1, wherein the surface of the top coat layer corresponding to the colored resin layer filled in the concave portion of the base material layer is formed in a concave shape. 4. The decorative material according to claim 1, wherein the surface of the top coat layer has a flat surface. 5. After filling a colored resin layer in a concave portion of a base material layer composed of a resin layer having a concave portion on the surface, an ionizing radiation curable resin serving as a soft segment and an ionizing radiation curable resin serving as a hard segment are formed. Applying a coating agent of a mixed resin to the entire surface of the base material layer so as to cover the colored resin layer filled in the recesses of the base material layer, and then irradiating with ionizing radiation A method for producing a cosmetic material, characterized by comprising: 6. After obtaining a laminated member of a base material layer made of a transparent resin layer having a concave portion on the surface and a colored base material layer laminated on the back surface of the base material layer, Filling the concave portion with the colored resin layer, further, a coating agent by a mixed resin of an ionizing radiation-curable resin to be a soft segment and an ionizing radiation-curable resin to be a hard segment, for the entire surface of the base layer, A method for producing a decorative material, which comprises applying a coating so as to cover a colored resin layer filled in a concave portion of a base material layer, and thereafter irradiating with ionizing radiation.