JPH11348193A - Surface reinforced decorative paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface reinforced decorative paper holding the adhesion of a decorative paper base material and a topcoat resin layer even with respect to repeated cellophane tape release operation and having various characteristics excellent in water repellency or chemical resistances. SOLUTION: In a surface reinforced paper for the decorative panel on a decorative substrate, internal crosslinked silcone particles (c) are included in the thermosetting or active energy curable topcoat resin (layer 1b) applied to a decorative base material (a). As the decorative base material (a), decorative paper with a basis wt. of 30-120 g/m<2> is pref. There is especially no limit in a thermosetting or active energy ray curable resin forming a topcoat resin layer and, as the active energy curable resin, a resin imparting an ultraviolet or electron beam cured film can be arbitrarily used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-reinforced decorative paper for decorative boards used for furniture, household equipment, etc., and more particularly, to the adhesiveness between a decorative paper substrate and a topcoat resin layer and the surface of decorative paper. The present invention relates to a surface-reinforced decorative paper having excellent physical properties such as water repellency and chemical resistance.

[0002]

2. Description of the Related Art Conventionally, a decorative paper base material for a decorative board used for furniture, housing equipment and the like is coated with a resin. It is known that a silicone molecule is used as a compound mixed in order to impart various physical properties such as cellophane tape releasability, water repellency and chemical resistance of a decorative paper surface. The silicone molecules mixed in the resin solution bleed on the surface of the coating layer when the solvent is dried after the topcoat resin solution is coated on the decorative paper substrate. It is known that the non-adhesive property of the methyl group in the silicone molecule exposed on the surface of the coating layer to the cellophane tape adhesive imparts cellophane tape peeling resistance, water repellency and chemical resistance. However, the silicone molecules mixed in the topcoat resin layer on the decorative paper base material, especially during the repeated peeling operation of the cellophane tape, gradually capture the silicone molecules on the adhesive surface of the cellophane tape and maintain its effect. It was difficult.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems required for surface-reinforced decorative paper. Maintains the adhesion of the coat resin layer,
Another object of the present invention is to provide a surface-reinforced decorative paper having excellent properties such as excellent water repellency and chemical resistance.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a surface-reinforced paper for a decorative board laminated on a decorative base, wherein a thermosetting or active energy ray-curable topcoat resin applied on a decorative substrate is used. And a surface-reinforced decorative paper containing internally crosslinked silicone particles.

[0005] The present invention is the surface-reinforced decorative paper according to the above invention, wherein the particle size of the internally crosslinked silicone particles is 0.05 μm to 50 μm.

[0006]

The present invention relates to a surface-reinforced paper for decorative board laminated on a decorative base, wherein internally crosslinked silicone particles are contained in a thermosetting or active energy ray-curable topcoat resin applied on a decorative substrate. Is mixed into the topcoat resin layer to maintain the adhesion between the decorative paper substrate and the topcoat resin layer even after repeated cellophane tape peeling operations, as well as excellent water repellency and chemical resistance. Characterized by the following characteristics. According to the internally crosslinked silicone particles according to the present invention, the silicone compound present in the topcoat resin layer takes the shape of spherical particles due to internal crosslinking, so that the resin component of the portion buried in the topcoat resin layer and The effect of entanglement and fixation is increased as compared with silicone molecules, and an effect of preventing the silicone particles from being caught by the cellophane tape adhesive even in repeated cellophane tape peeling operations is provided. By mixing the internally crosslinked silicone particles having these characteristics, durability against repeated cellophane tape peeling operation can be provided. Similarly, due to the effect of increasing the entanglement with the resin component, the internally cross-linked silicone particles have various properties, such as water repellency and chemical resistance, as compared with the molecular silicone compound, and thus have better resistance. it can. As described above, in the surface-reinforced paper for decorative sheets laminated on the decorative base, the topcoat resin applied on the decorative base contains the internally crosslinked silicone particles, so that the decorative paper base and the top It is possible to provide a surface-reinforced decorative paper having excellent properties such as adhesion to a coat resin layer, water repellency of the decorative paper surface, and chemical resistance. More preferably, the particle size of the internally crosslinked silicone particles mixed into the top coat resin layer is 0.05 μm to 50 μm.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The surface-reinforced decorative paper of the present invention will be described in detail based on embodiments. FIG. 1 is a schematic cross-sectional view of the layer structure of the surface-reinforced decorative paper of the present invention, in which (a) is a decorative paper substrate, (b) is a top coat resin layer, and (c) is a Internally crosslinked silicone particles.

The decorative paper substrate (a) used in the present invention is
30 g / m2^Two~ 120g / m ^TwoBase paper for decorative paper
Is preferred, but a urethane-based resin or a vinyl-based resin is used in advance.
Base paper for decorative paper that has been subjected to sealer treatment, etc.
No. Whether to print this with oil or water based ink
Color the entire surface.

There is no particular limitation on the thermosetting or active energy ray-curable resin forming the top coat resin layer (b) used in the present invention. Any given resin can be used.

As the thermosetting resin, for example, in the case of a urethane resin, polyester, polyether, acrylic, and epoxy polyols can be used as main components. As the curing agent, diisocyanates such as triresin isocyanate, xylylene diisocyanate, 1,5-naphthalenediisocyanate, and hexamethylene diisocyanate can be used, and 5 to 30 parts are mixed with respect to 100 parts of the resin solid content. Other examples include an acrylic resin, a polyester resin, a phenol resin, and an epoxy resin.

[0011] Examples of the ultraviolet curing resin include, for example,
Polyfunctional acrylate resin such as acrylic acid or methacrylic acid ester of polyhydric alcohol, polyfunctional urethane acrylate resin synthesized from diisocyanate, polyhydric alcohol and hydroxy ester of acrylic acid or methacrylic acid, and the like. be able to.
Further, a polyether resin, a polyester resin, an epoxy resin, an alkyd resin, a spiroacetal resin, a polybutadiene resin, a polythiolpolyene resin, or the like having an acrylate-based functional group can be suitably used as necessary. The reaction diluents for these resins include 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and hexanediol (meth) having relatively low viscosity. Bifunctional or higher functional monomers and oligomers such as acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, neopentyl glycol di (meth) acrylate, and monofunctional monomers Can be used.

In the present invention, when the active energy ray is ultraviolet light, it is necessary to add a photosensitizer (radical polymerization initiator), and benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Benzoin and its alkyl ethers, such as benzylmethyl ketal and acetophenone;
Acetophenones such as 2-dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexylphenyl ketone; anthraquinones such as methylanthraquinone, 2-ethylanthraquinone and 2-aminoanthraquinone; thioxanthone, 2,4-diethylthioxanthone and 2,4- Thioxanthones such as diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone and 4,4-bismethylaminobenzophenone; and azo compounds. The amount of the organic peroxide or the photopolymerization initiator to be used is 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the polymerization component of the resin composition.

The internally crosslinked silicone particles (c) used in the present invention may be obtained, for example, by polymerization of terminally modified dimethylsilicone oil having both ends modified with a reactive group such as a vinyl group or a methacryloxy group, or at one end and at both ends. It can be synthesized by copolymerization of those modified with a reactive group as described above. As the polymerization initiator, benzoyl peroxide, potassium persulfate or the like can be used, and 0.1 to 5 parts are mixed with respect to 100 parts by weight of the terminally modified silicone oil solids. As the polymerization method, known synthesis methods such as emulsion polymerization, suspension polymerization, solution polymerization, dispersion polymerization, microsuspension polymerization, and seed polymerization can be used as appropriate.

For example, in the case of emulsion polymerization, emulsifiers include general surfactants such as sodium dodecyl sulfate and sodium dodecylbenzenesulfonate, formalin condensates such as sodium naphthalenesulfonate formalin condensates, and ethers such as polyoxyethylene alkyl ethers. And so on. The emulsifier is mixed in an amount of 0.1 to 5 parts with respect to 100 parts by weight of the solid content of the modified silicone oil. The emulsification method conforms to a general emulsion polymerization method. After mixing all the components, water is added. If necessary, a heating operation and a solvent are added, and the mixture is stirred with a stirring blade. After the dispersion, cooling, removal of the solvent, and the like are performed.
The synthesized internally crosslinked silicone particles are mixed in a resin solution in an amount of 0.5 to 10 parts based on 100 parts by weight of the resin solid content. The method of coating on the decorative paper is optional, but in the production stage, it is common to use a roll coater, a reverse roll coater, a gravure coater, a knife coater, or the like.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to specific embodiments.

<Example 1> Synthesis of internally crosslinked silicone particles: weight average molecular weight (Mw) 5000 having a methacryloxy group at one end
Modified methacryloxy-modified dimethyl silicone oil 90
Parts, methacryloxy-modified dimethyl silicone oil having a weight average molecular weight (Mw) of 3000 having methacryloxy groups at both ends of 10 parts, sodium alkylbenzenesulfonate 0.5 part as an emulsifier, and benzoyl peroxide 1.5 parts as a polymerization initiator were ionized. Replace distilled water with 40
The mixture was added to a glass reaction vessel containing 0 parts, kept at 80 ° C., and stirred with a double helical stirring blade at a rotation speed of 200 rpm for 12 hours. Thereafter, distilled water as a solvent was removed by suction under reduced pressure and hot drying in an oven. As a result, an electron micrograph of the obtained dry powder was taken, and it was confirmed that spherical particles having an average particle size of 1.4 μm and Mn / Mw = 1.1 were generated.

Preparation of resin solution: The internally crosslinked silicone particles obtained by the above method were mixed with a urethane thermoplastic resin (UR222: trade name, manufactured by Toyo Ink Mfg. Co., Ltd.).
0 parts and 25 parts of a curing agent (Sumidule L-75: trade name of Toyo Ink Mfg. Co., Ltd.) were mixed in 8 parts. Preparation of decorative paper and decorative board: An oak-like woodgrain pattern is printed on a decorative paper base material having a basis weight of 60 g / m ² using an oil-based ink (manufactured by Toyo Ink Mfg. Co., Ltd.), dried, and then dried. The above-prepared resin solution was coated on a base ink layer with a wire bar so as to have a thickness of about 5 μm when dried, and dried in an oven at 60 ° C. for 3 days. The surface-reinforced decorative paper thus obtained was bonded to a particle board with a urea / vinyl acetate adhesive to form a decorative plate.

<Comparative Example 1> The same method and conditions as in Example 1 except that the dimethyl silicone oil having a weight average molecular weight (Mw) of 5000 was used instead of the internally crosslinked silicone particles incorporated in the formulation of Example 1 Adjust the paint with
After forming a coating film on the oil-based ink layer of the decorative paper substrate, it was dried by heating.

Evaluation method of decorative board: The performances of the decorative boards obtained in Example 1 and Comparative Example 1 were evaluated by the following methods and are summarized in Table 1. [1] Cellophane tape resistance; standard specifications for printed plywood and color plywood (Japan Printed Plywood and Color Plywood Industry Association)
Was peeled off (using CitiTape (trademark), manufactured by Nichiban Co., Ltd., after 2 hours at 40 ° C. ± 3 ° C.), and the surface condition was observed.

[2] Solvent resistance: Rubbing was performed under a load of 500 g / cm ² while 2-butanone was dropped on the surface of the decorative board sample, and damage to the coating film surface by the solvent was observed. Then, the number of rubbings until damage of the coating film surface was confirmed was measured. [3] Stain resistance: According to the standards of the JAS Soil A test, a line having a width of 10 mm was formed on the coating surface of the decorative board using an oil-based ink, a water-based ink, and crayon, left for 4 hours, and then wiped off with methanol. The condition was observed.

[4] Acid resistance: After acetic acid (5% aqueous solution) was dropped on the coating film, it was covered with a watch glass, and after 6 hours, the surface condition was evaluated by visual observation. [5] Alkali resistance: After dropping sodium carbonate (1% aqueous solution) on the coating film, it was covered with a watch glass, and after 6 hours, the surface condition was evaluated by visual observation. [6] Contact angle measurement: The contact angle was measured using an automatic contact angle meter (manufactured by Kyowa Interface Chemical Co., Ltd.).

Evaluation results: As shown in Table 1, when the decorative paper according to Example 1 was applied, compared with the case where the decorative paper according to Comparative Example 1 was applied, the cellophane tape peeling resistance was particularly improved. Is confirmed. Also, chemical resistance was improved. Further, from the contact angle measurement results, it can be confirmed that the decorative paper according to Example 1 shows better water repellency than the decorative paper according to Comparative Example 1.

[0023]

[Table 1]

[0024]

As is clear from the above-described embodiments, in the surface-reinforced paper for a decorative board laminated on a decorative base according to the present invention, the inside of the top coat resin applied on the decorative base material is included. By containing the crosslinked silicone particles, it is possible to provide a surface-reinforced decorative paper excellent in various properties such as adhesion between the decorative paper base material and the topcoat resin layer, and water repellency and chemical resistance of the decorative paper surface. Was. In particular, when used for furniture and household equipment, the mixing of the internally crosslinked silicone particles makes it possible to impart various properties such as resistance to repeated cellophane tape peeling and excellent water repellency and chemical resistance. .

[Brief description of the drawings]

FIG. 1 shows a schematic cross-sectional view of a layer configuration of a surface-reinforced decorative paper of the present invention.

[Description of Signs] a: Decorative paper base material b: Top coat resin layer c: Internally crosslinked silicone particles

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takao Taguchi 1-5-1, Taito, Taito-ku, Tokyo Letterpress Printing Co., Ltd.

Claims (2)

[Claims] 1. A surface-reinforced paper for decorative board laminated on a decorative substrate, wherein internally cured silicone particles are contained in a thermosetting or active energy ray-curable topcoat resin applied on the decorative substrate. Surface-enhanced decorative paper characterized in that: 2. The particle size of the internally crosslinked silicone particles is 0.05.
The surface-reinforced decorative paper according to claim 1, which has a thickness of from 50 m to 50 m.