JP3998739B2 - Cosmetic material and method for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a decorative material used for surface cosmetics such as an interior material of a building, a cabinet of furniture and various household appliances, and a manufacturing method thereof. More specifically, the present invention relates to a decorative material having surface properties comparable to the performance of a thermosetting resin decorative board and capable of substituting the thermosetting resin decorative board, and a manufacturing method thereof.
[0002]
[Prior art]
Conventionally, cosmetic materials used for surface makeup include, for example, a polyvinyl chloride cosmetic material using a polyvinyl chloride film as a base material. According to this cosmetic material, the adhesive is used to attach to a substrate. Although a decorative board can be manufactured easily, surface physical properties, such as surface hardness, solvent resistance, and heat resistance, are inferior.
[0003]
In contrast, thermosetting resin decorative boards such as high-pressure melamine decorative boards, low-pressure melamine decorative boards, diallyl phthalate decorative boards, or polyester resin decorative boards that use decorative materials printed on titanium paper, thin paper, etc. It has excellent surface properties such as hardness, solvent resistance, and heat resistance, but requires hot press molding in the manufacturing process, requires high heat and a long time for manufacturing, and has poor production efficiency.
[0004]
Therefore, as a cosmetic material having excellent surface properties equivalent to those of a thermosetting resin decorative board and a polyester resin decorative board and capable of easily manufacturing a decorative board simply by sticking to a base material, for example, by the present applicant Japanese Examined Patent Publication No. 1-55991 proposes a decorative paper in which a base paper for decorative paper that has been printed is impregnated with an ionizing radiation curable resin that is cured with an electron beam.
[0005]
[Problems to be solved by the invention]
However, in conventional thermosetting resin decorative boards, it is possible to form a concave portion corresponding to a conduit groove on the surface during hot pressing to make a decorative board with higher design, but ionizing radiation curing is applied to the base paper for decorative paper. In the decorative paper impregnated with the functional resin, the surface layer of the ionizing radiation curable resin is cured immediately after the coating, so that the concave portion on the surface cannot be formed, and the design expression is limited. In addition, the composition of ionizing radiation curable resin to be coated needs to consider the suitability of impregnation into base paper for decorative paper, and is ideal for expressing desired surface properties by forming a layer on the base paper for decorative paper In some cases, it is contrary to the correct composition.
Therefore, the purpose of the decorative material of the present invention and the manufacturing method thereof is to provide high-performance surface properties and high design feeling by surface shaping of conventional thermosetting resin decorative boards and polyester resin decorative boards, and to manufacture them. It is also easy to provide a decorative material that can be a substitute product for a thermosetting decorative board.
[0006]
[Means for Solving the Problems]
In order to solve the above problems, the decorative material of the present invention, on the base paper for decorative paper, pattern layer, the first ionizing radiation curable resin comprising formed from the heated melt, the heating the melt thereon By forming the second ionizing radiation curable resin formed into a layered structure, the first ionizing radiation curable resin is suitable for application to base paper for decorative paper, suitability for impregnation, or mechanical physical properties of the cosmetic material, The second ionizing radiation curable resin can exhibit surface properties and excellent surface properties and the like as a result of being functionally separated and set. Further, since the ionizing radiation curable resin is laminated in two layers, a thick overcoat layer is possible. In addition, by making the base paper for decorative paper contain the first ionizing radiation curable resin that has entered the interior, the space between the base paper fibers is filled with this resin, and a decorative material having high peel strength is obtained. Further, the first and second ionizing radiation curable resins are made non-adhesive and solid at room temperature in an uncured state, so that the surface layer is embossed and recessed using the thermoplastic state before curing. In addition to the formation, the first and second ionizing radiation curable resins can be applied off-line. Moreover, the surface physical properties, such as abrasion resistance, are improved by adopting a configuration in which fine particles are contained in the second ionizing radiation curable resin. Moreover, a high design feeling can be expressed by having a concave portion and a colored layer inside the concave portion on the surface of the layer made of the second ionizing radiation curable resin. The colored layer can be made into a cosmetic material having excellent surface properties by using an ionizing radiation curable resin as a main component.
[0007]
On the other hand, the method for producing a decorative material of the present invention comprises impregnating or applying a heated melt of a first ionizing radiation curable resin to a base paper for decorative paper to which a pattern layer has been applied. A production in which the first ionizing radiation curable resin is cured by irradiating with ionizing radiation after applying a heated melt of the second ionizing radiation curable resin to the surface of the resin layer. Is the method.
[0008]
Another method for producing a decorative material according to the present invention is the heating of a first ionizing radiation curable resin that is non-adhesive and solid at room temperature in an uncured state on a decorative paper base paper provided with a pattern layer. melt the impregnation or coating, the surface layer of the first ionizing radiation curable resin, the second heat melt of ionizing radiation-curable resin which is a non-tacky and solid at room temperature in the uncured state After forming the recesses on the surface of the layer made of the second ionizing radiation curable resin, the first and second ionizing radiation curable resins are simultaneously cured by irradiating with ionizing radiation, After providing a colored layer in the recess by wiping, the colored layer was cured by irradiation with ionizing radiation. As a result, thermosetting is not required, and the first and second ionizing radiation curable resins are cured at the same time, and since the curing is performed by ionizing radiation, a cosmetic material can be easily manufactured in a short time. Since the ionizing radiation curable resin is applied in two steps, the surface properties are the second ionizing radiation curable resin, the suitability for coating and impregnation on the base paper for decorative paper, the flexibility of the cosmetic material, etc. The mechanical suitability can be designed and manufactured in a functionally separated manner from that of the first ionizing radiation curable resin. In addition, since the first and second ionizing radiation curable resins that are non-adhesive and solid at room temperature in the uncured state are used, a recess is formed in the surface layer by embossing using the thermoplastic state before curing. In addition, it is a production method that can give excellent surface properties after curing.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the decorative material of the present invention and the manufacturing method thereof will be described in detail.
[0010]
FIG. 1 is a longitudinal sectional view showing an embodiment of the decorative material of the present invention. In the figure, the decorative material 1 has a pattern layer 3 formed on a base paper 2 for decorative paper, and a first ionizing radiation curable resin 4 and a second ionizing radiation curable resin 5 are laminated thereon, Furthermore, the surface of the layer made of the second ionizing radiation curable resin 5 is a decorative material having a concave portion 6 and a colored layer 7 inside the concave portion 6. In the same figure, the base paper 2 for decorative paper is almost completely impregnated with the first ionizing radiation curable resin, and the first ionizing radiation curable resin 4 penetrates almost the entire interior of the base paper 2 for decorative paper. However, some of them remain on the pattern layer and the base paper for decorative paper. After the first and second ionizing radiation curable resins are laminated, they are cured by irradiation with ionizing radiation. .
[0011]
FIG. 2 is a longitudinal section showing another embodiment of the decorative material of the present invention in which the first ionizing radiation curable resin is impregnated into a part of the base paper 2 for decorative paper in the configuration of FIG. FIG.
[0012]
The base paper 2 for decorative paper is a base paper that is usually used for decorative paper. Examples of the base paper include thin paper, inter-paper reinforcing paper, high-quality paper, Japanese paper, non-woven fabric, and craft paper.
[0013]
The pattern layer 3 is formed by a known printing means such as gravure printing using a printing ink using a mixed resin obtained by mixing a nitroserose resin or a alkyd resin as a resin component of a vehicle, which is usually used for decorative paper. To do.
[0014]
As the first ionizing radiation curable resin 4 and the second ionizing radiation curable resin 5, known ionizing radiation curable resins that are cured by ionizing radiation such as ultraviolet rays or electron beams can be used. However, in particular, in the configuration having a concave portion on the surface of the decorative material, the ionizing radiation curable resin is non-adhesive at room temperature in an uncured state so that the concave portion does not remain attached to a shaping mold such as an embossing roll when shaping. It is desirable that it is solid. Further, when impregnating the base paper for decorative paper, the first ionizing radiation curable resin needs to have a low viscosity so that the base paper can be impregnated by heating or solvent dilution at least during the impregnation. .
[0015]
As an ionizing radiation curable resin that is non-adhesive and solid at room temperature in an uncured state, for example, polyester acrylate, polyether acrylate, urethane acrylate, epoxy acrylate, silicone acrylate, etc., by adjusting the molecular weight, And a solid, non-adhesive thermoplastic prepolymer. In addition, when the following compounds (1) to (8) are polymerized or copolymerized, radically polymerizable unsaturated groups are introduced by the methods (a) to (d) described later, and the glass transition temperature is 0 to 0. The prepolymer which has a radically polymerizable unsaturated group in a 250 degreeC polymer is mentioned.
[0016]
(1) Monomer having a hydroxyl group such as N-methylol (meth) acrylamide, (2) Monomer having a carboxyl group such as (meth) acrylic acid, (3) Epoxy group such as glycidyl (meth) acrylate A monomer having an aziridinyl group such as (4) 2-aziridinylethyl (meth) acrylate, a monomer having an amino group such as (5) (meth) acrylamide, Monomers having a sulfone group such as (meth) acrylamide-2-methylpropanesulfonic acid, (7) 1 mol to 1 mol adduct of 2,4-toluene diisocyanate and 2-hydroxyethyl (meth) acrylate, etc. Monomer having an isocyanate group, such as an adduct of a diisocyanate and a radically polymerizable monomer having active hydrogen, (8) methyl (meth) acrylate, etc. Monomers other than the above (1) to (7) that are copolymerizable with the above monomers (1) to (7) (polymers or copolymers obtained from the above monomers (1) to (7)) Used as a copolymerization component for adjusting the glass transition point of the polymer and the surface properties of the ionizing radiation curable resin after curing).
[0017]
Next, the polymer or copolymer obtained as described above is reacted by the following methods (a) to (d) to introduce radically polymerizable unsaturated groups. (a) In the case of a polymer or copolymer of a monomer having a hydroxyl group, the monomer having a carboxyl group described in (2) is subjected to a condensation reaction. (b) In the case of a polymer or copolymer of a monomer having a carboxyl group or a sulfone group, the above-mentioned monomer having a hydroxyl group of (1) is subjected to a condensation reaction. (c) In the case of a polymer or copolymer of a monomer having an epoxy group, an isocyanate group or an aziridinyl group, the monomer having the hydroxyl group (1) or the carboxyl group (2) is subjected to an addition reaction. . (d) In the case of a polymer or copolymer of a monomer having a hydroxyl group or a carboxyl group, the monomer having the epoxy group of (3) or the aziridinyl group of (4), or of (7) A monomer having an isocyanate group such as a one-to-one molar adduct of a diisocyanate compound and a hydroxyl group-containing acrylate monomer is subjected to an addition reaction.
[0018]
Alternatively, for example, monomers having a melting point of 20 to 250 ° C., such as stearyl (meth) acrylate, triacrylic isisoannulate, cyclohexanediol di (meth) acrylate, spiroglycol diacrylate, spiroglycol (meth) acrylate, etc. It is done.
[0019]
Moreover, the above thing can also be mixed and used, Furthermore, another radically polymerizable monomer can be added and used with respect to them. Moreover, in order to adjust suitably the flexibility of a hardened | cured material, non-adhesiveness, the solvent drying property at the time of setting it as a solvent solution, you may add a non-crosslinked thermoplastic resin.
[0020]
The ionizing radiation curable resin can be sufficiently cured by an electron beam, but when cured by ultraviolet irradiation, thioxanthones such as benzophenone, benzoin alkyl ethers such as benzoin and benzoin methyl ether, halogenated acetophenone, etc. Known photopolymerization initiators that generate radicals upon irradiation with ultraviolet rays, such as acetophenones and diacetyls, and further, if necessary, known photosensitizers such as amines such as n-butylamine and triethylamine, and tri-n-butylphosphine. Sensitizers can be used. In addition, a known polymerization inhibitor such as hydroquinone can be added to prevent the impregnation suitability from decreasing due to an increase in viscosity due to polymerization before coating.
[0021]
In order to adjust flexibility or non-adhesiveness in an uncured state, as a non-crosslinked thermoplastic resin that is an ionizing radiation non-curable resin, for example, urethane resin, A butyral resin, a cellulose resin, a polyester resin, an acrylic resin, or the like may be added as appropriate.
[0022]
The ionizing radiation curable resin may be colored by adding a known coloring material as necessary.
[0023]
In order to apply the first and second ionizing radiation curable resins to the base paper for decorative paper, the ionizing radiation curable resin is made into a coating solution diluted with a solvent by an appropriate method, for example, or heated to be a melt. The coating may be performed by known coating means such as roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, smooth coating, and comma coating.
The coating amount of the ionizing radiation curable resin is usually about 1 to 100 g / m ² (including the amount impregnated in the base paper for decorative paper) with the first ionizing radiation curable resin, and the second ionizing radiation. It is about 5-30 g / m < ² > with curable resin.
[0024]
Further, the degree of impregnation of the first ionizing radiation curable resin into the decorative paper base paper is the air permeability of the base paper, the viscosity of the ionizing radiation curable resin coating liquid, and when the coating liquid is heated, By appropriately adjusting the temperature and the time until cooling, the time from application to irradiation with ionizing radiation and curing, and the like, it is controlled whether the whole area or a part of the base paper for decorative paper is used.
[0025]
In addition, since the second ionizing radiation curable resin forms a layer that is the outermost layer of the decorative material, surface properties such as abrasion resistance and scratch resistance are appropriately included in the resin as necessary. In order to improve or adjust the gloss of the surface, fine particles may be added. Examples of such fine particles include inorganic fine particles such as silica and alumina for improving wear resistance.
[0026]
The cosmetic material obtained from the above base paper for decorative paper, the pattern layer, the first ionizing radiation curable resin, and the second ionizing radiation curable resin is the basic structure of the cosmetic material of the present invention. In the case of materials, after applying the pattern layer and the first and second ionizing radiation curable resins to the decorative paper base paper, the first and second ionizing radiation curable resins are cured simultaneously by irradiating with ionizing radiation. Can be obtained.
[0027]
And when providing the recessed part which expresses a wood grain conduit pattern etc. on the surface of a decorative material, before irradiating with ionizing radiation, from the 2nd ionizing radiation hardening resin used as the outermost layer by shaping means, such as an embossing roll, A recess is formed on the surface of the layer to be formed, and then ionizing radiation is irradiated. If the ionizing radiation curable resin is made non-adhesive and solid at room temperature in an uncured state, it becomes tack-free even before curing with ionizing radiation, and can be handled by the machine. Deformed (appropriately heated to a temperature at which the resin becomes flexible and develops the desired embossability as needed) to form concave portions on the surface.
[0028]
Even if the concave portion on the surface is left as it is, the design feeling can be expressed with a specific three-dimensional pattern on the surface, but by forming a colored layer with, for example, dark matte ink in the concave portion, the wood grain pipe pattern is extremely realistic Can be expressed. The colored layer can be formed by wiping with a normal thermosetting ink such as a two-component reaction type ink. As the ink, an ionizing radiation curable resin that cures the resin component of the vehicle with ultraviolet rays or an electron beam. If the ink containing the main component is used, it is possible to obtain a cosmetic material having better surface properties in combination with the first and second ionizing radiation curable resins in the lower layer.
[0029]
Such an ink mainly composed of an ionizing radiation curable resin is obtained by diluting an ionizing radiation curable resin that is non-adhesive and solid at room temperature in an uncured state as described above with a solvent, or not yet. An ionizing radiation curable resin that is liquid at room temperature in a cured state can be used as it is without being diluted with a solvent. A known color material, matting agent, dispersant and the like can be added to such a vehicle made of a resin component.
[0030]
In addition, the formation of the colored layer in the surface recess by wiping is not impossible even if the second ionizing radiation curable resin is performed in an uncured state, but since it becomes soft, it is better after curing. Easy to wipe.
[0031]
Thus, the decorative material of the present invention, which skillfully uses ionizing radiation curable resin, can be obtained.
[0032]
And, by adhering this decorative material to the surface of a woody base material such as particle board, fiber board, plywood, etc. through a known woody adhesive such as vinyl acetate resin, excellent surface properties A decorative board having a design feeling can be produced efficiently in a short time without requiring a high temperature and a long time such as a hot press method. Of course, you may manufacture a decorative board by the hot press method depending on a use.
[0033]
For the curing of the first and second ionizing radiation curable resins and the colorant mainly composed of the ionizing radiation curable resin, ionizing radiation such as ultraviolet rays or electron beams is usually applied from the coated surface side. Do. For example, ultraviolet rays include ultra-high pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, carbon arc, xenon arc, black light, metal halide lamps, and other light sources. An electron beam having an energy in the range of 50 to 1000 keV, preferably 100 to 300 keV by various electron beam accelerators such as a transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type is used. Moreover, continuous curing can be achieved by using an electron beam that is continuously irradiated in a curtain form from a linear filament.
[0034]
【Example】
Next, the present invention will be described more specifically by implementation.
[0035]
"Example"
As a base paper for decorative paper, a pattern layer having a wood grain pattern was formed by gravure printing on one side of a thin paper having a basis weight of 50 g / m ² . Next, as the first ionizing radiation curable resin, the following composition is heated to 100 ° C. as a melt, and coated on the base paper for decorative paper at a rate of 50 g / m ² with a roll coater, The base paper for decorative paper was impregnated. Further, from above, as the second ionizing radiation curable resin, the following composition is heated to 100 ° C. and applied as a melt with a roll coater at 20 g / m ² , and then cooled by blowing cold air. After making it tack-free, the embossing roll embossed the conduit pattern of the grain. Next, the first and second ionizing radiation curable resins were simultaneously cured by irradiating the electron beam with 5 Mrad. Next, a wiping ink having an ionizing radiation curable resin having the following composition as a main component of a vehicle and a coloring material added thereto is wiped with a knife coater in a concave portion of the surface formed by embossing, and then irradiated with an electron beam at 5 Mrad. Then, the colored layer formed in the recess was cured.
[0036]
Composition for first ionizing radiation curable resin Acrylate oligomer (viscosity at 100 ° C. of 50 cps or less) 100 parts by weight
Composition for second ionizing radiation curable resin 100 parts by weight of acrylate-based oligomer (viscosity at 100 ° C. of 500 cps or less)
Filler: Alumina fine particles (average particle size 15 μm) 30 parts by weight
Main component of vehicle for wiping ink Multifunctional acrylate monomer and oligomer 100 parts by weight Matting material: Silica fine particles (average particle size 5 μm) 10 parts by weight
【The invention's effect】
As described in detail above, according to the decorative material of the present invention, the first ionizing radiation curable resin is suitable for application to the base paper for decorative paper, suitability for impregnation, mechanical suitability such as flexibility of the decorating material, Since the ionizing radiation curable resin can be provided with surface properties and functions separated, it is possible to design free surface properties, which is comparable to conventional thermosetting resin decorative sheets and polyester resin decorative sheets. A decorative material having excellent surface properties such as hardness, solvent resistance and heat resistance can be obtained. Further, since the ionizing radiation curable resin is laminated in two layers, a thick overcoat layer can be obtained and a rich feeling of painting can be expressed. And with this decorative material, a decorative board with excellent performance can be obtained by simply sticking to a decorative base material such as particle board with an adhesive without using a hot press method.
[0040]
In addition, by impregnating the base paper for decorative paper with the first ionizing radiation curable resin, after the decorative material is attached to the base material, the surface of the base paper for decorative paper is less likely to cause cohesive peeling and has a strong peeling strength. Makeup is obtained.
In addition, since the first and second ionizing radiation curable resins are non-adhesive and solid at room temperature in an uncured state, the second ionization serving as the outermost layer of the decorative material before the curing of these resins. A concave portion such as a conduit groove can be formed by embossing on the surface of the layer made of the radiation curable resin, and a three-dimensional design expression of the surface is also possible. Moreover, since the coating surface is not wet after coating, it is not necessary to continuously apply the first and second ionizing radiation curable resins in-line, on the manufacturing apparatus, in terms of process control, etc. More free manufacturing becomes possible.
[0041]
In addition, if fine particles are contained in the second ionizing radiation curable resin, surface physical properties such as abrasion resistance can be further improved. In the application of one kind of ionizing radiation curable resin, decorative paper is obtained by containing fine particles. Although it is necessary to consider the influence on the suitability of impregnation into the base paper, more excellent surface properties can be obtained by using two types of ionizing radiation curable resins.
Further, if a colored layer is applied to the concave portion formed on the surface of the outermost layer, a more realistic design expression such as a conduit groove can be realized.
[0042]
And according to the manufacturing method of the cosmetics of this invention, the cosmetics which have the outstanding surface physical property and design property which were mentioned above can be manufactured easily in a short time, and production efficiency is good.
In addition, a cosmetic material having excellent surface properties due to the layer made of the ionizing radiation curable resin and a high design feeling due to surface shaping can be obtained.
[Brief description of the drawings]
FIG. 1 is a longitudinal sectional view of one embodiment of a decorative material of the present invention.
FIG. 2 is a longitudinal sectional view of another embodiment of the decorative material of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Cosmetic material 2 Base paper for decorative paper 3 Picture layer 4 1st ionizing radiation curable resin 5 2nd ionizing radiation curable resin 6 Recessed part 7 Colored layer

Claims (8)

On the base paper for decorative paper, a first ionizing radiation curable resin formed from a heated melt and a pattern layer were laminated with a second ionizing radiation curable resin formed from a heated melt . A cosmetic material characterized by that.   2. The decorative paper according to claim 1, wherein the base paper for decorative paper contains a first ionizing radiation curable resin therein.   The cosmetic material according to claim 1 or 2, wherein the first and second ionizing radiation curable resins are non-adhesive and solid at room temperature in an uncured state.   4. The cosmetic material according to claim 1, wherein the second ionizing radiation curable resin contains fine particles.   The cosmetic material according to claim 1, 2, 3 or 4, wherein the surface of the layer made of the second ionizing radiation curable resin has a concave portion and a colored layer inside the concave portion.   6. The cosmetic material according to claim 5, wherein the colored layer contains an ionizing radiation curable resin as a main component. A base paper for decorative paper to which a pattern layer has been applied is impregnated or coated with a heated melt of the first ionizing radiation curable resin , and a second ionizing radiation is applied to the surface of the layer made of the first ionizing radiation curable resin. A method for producing a cosmetic material, comprising applying a heated melt of a radiation curable resin and then irradiating with ionizing radiation to cure the first and second ionizing radiation curable resins. The base paper for decorative paper to which the pattern layer has been applied is impregnated or coated with a heated melt of a first ionizing radiation curable resin that is non-adhesive and solid at room temperature in an uncured state, and the first ionizing radiation From the second ionizing radiation curable resin , after applying a heated melt of the second ionizing radiation curable resin that is non-adhesive and solid at room temperature in an uncured state to the surface of the layer made of the curable resin, After forming a recess on the surface of the layer, the first and second ionizing radiation curable resins are simultaneously cured by irradiating with ionizing radiation, and then a colored layer is provided in the recess by a wiping method, followed by ionization. A method for producing a cosmetic material, which comprises irradiating radiation to cure a colored layer.

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