HK1138865B

HK1138865B - Composition, transfer sheet, melamine decorative board, and method for producing melamine decorative board

Info

Publication number: HK1138865B
Application number: HK10105559.0A
Authority: HK
Inventors: 谷本尚志; 山本智弘; 伊藤贵春; 本间胜己
Original assignee: 爱克工业株式会社
Priority date: 2007-07-10
Filing date: 2008-05-23
Publication date: 2013-11-01

Description

Composition, transfer sheet, melamine decorative board, and method for producing melamine decorative board

Technical Field

The invention relates to a composition, a transfer sheet, a melamine decorative board, and a method for manufacturing the melamine decorative board.

Background

Melamine decorative boards are used as horizontal surfaces for counters, tables, etc. because of their excellent properties in terms of surface hardness, heat resistance, abrasion resistance, etc. Melamine decorative boards are generally obtained by: a melamine resin-impregnated form paper (pattern paper) obtained by laminating a melamine resin-impregnated form paper and a phenol resin-impregnated core paper and then applying heat and pressure to the laminated paper with a flat press (see patent documents 1 to 3) is as follows: impregnating a model base paper for a decorative sheet with a resin liquid composed of a melamine-formaldehyde resin as a main component, and drying the impregnated model base paper; the phenolic resin impregnated core paper is obtained by: kraft paper is impregnated with a phenol resin solution composed of a phenol-formaldehyde resin as a main component, and the impregnated kraft paper is dried.

Patent document 1: unexamined Japanese patent publication No. H06-199528

Patent document 2: unexamined Japanese patent publication No.2005-199495

Patent document 3: unexamined Japanese patent publication No.2005-146272

Disclosure of Invention

Problems to be solved by the invention

The melamine decorative board has excellent surface hardness, heat resistance, abrasion resistance, and the like due to the characteristics of the resin used therein. On the other hand, the melamine decorative laminated board is disadvantageous in that a sebum film (hereinafter referred to as fingerprint) such as a fingerprint is easily noticeable due to grease dirt adhering to the surface of the melamine decorative laminated board. A further disadvantage is that the pattern on the printed paper cannot be clearly shown due to light reflection and white spots (blu) on the melamine resin layer.

The present invention has been made to overcome these conventional disadvantages. An object of the present invention is to provide a composition useful for producing a melamine decorative laminated board on which fingerprints and the like are less noticeable and a pattern on printed paper can be clearly displayed; a transfer sheet usable for manufacturing the melamine decorative laminated sheet; melamine decorative boards; and a method for manufacturing the melamine decorative board.

Means for solving the problems

The composition of the present invention comprises (a) a silicone sol; and (b1) a silicone-grafted polymer obtained by compounding a fluororesin or an acrylic resin with silicone and/or (b2) a room temperature glass coating agent (room temperature ガラスコ - テイング strain coating agent).

In other words, there are three different types of compositions in the present invention, namely, a composition comprising component (a) and component (b1), a composition comprising component (a) and component (b2), and a composition comprising component (a), component (b1), and component (b 2).

The composition of the present invention can be used, for example, to form a low refractive index layer comprising a cured product of the composition of the present invention on the surface of a melamine decorative sheet. In the melamine decorative board having formed on the surface thereof the low refractive index layer comprising the cured product of the composition of the present invention, fingerprints adhering to the surface are less noticeable. This is because the low refractive index layer has a lower refractive index than the melamine resin layer, and therefore the refractive index difference between the adhesion fingerprint and the low refractive index layer is smaller than the refractive index difference between the adhesion fingerprint and the melamine resin layer. Also, the low refractive index layer has low reflectance and a low refractive index, thereby reducing light reflection and white spots. As a result, the pattern on the printed paper for the melamine decorative board can be clearly displayed to provide the melamine decorative board with high design quality.

In the decorative sheet of the present invention, since a low refractive index layer containing a cured product of the above composition is formed on a surface, fingerprints adhering to the surface are less noticeable, and patterns on printed paper are clearly displayed, thereby achieving high design quality. The low refractive index layer preferably has a refractive index of 1.5 or less. By setting the refractive index to 1.5 or less, the fingerprint becomes less noticeable and the pattern on the printed paper is more clearly displayed.

The transfer sheet of the present invention comprises a base material and the above-mentioned composition provided on the base material. The transfer sheet can be used for forming a low refractive index layer on the surface of a melamine decorative sheet. The transfer sheet makes it easy to form a low refractive index layer.

The manufacturing method of the melamine decorative board comprises the following steps: stacking the above transfer sheet, melamine resin-impregnated paper and core material, applying heat and pressure thereto to perform hot press forming, and removing the base material of the transfer sheet. According to this method, a melamine decorative board having a low refractive index layer on the surface can be easily produced. In the hot press forming by applying heat and pressure, the temperature is preferably in the range of 110-180 ℃ and the pressure is preferably in the range of 5-10 MPa.

Drawings

Fig. 1 is an explanatory view showing a manufacturing method of a melamine decorative board.

Fig. 2 is a sectional side view showing the structure of the melamine decorative panel.

Fig. 3 is a photograph showing the clarity on the surface of the melamine decorative laminated board, the right half corresponding to the melamine decorative laminated board of example 1, and the left half corresponding to the melamine decorative laminated board of comparative example 1.

Fig. 4 is a photograph showing how much fingerprints are adhered to the surface of the melamine decorative laminated board, the right half corresponding to the melamine decorative laminated board of example 1, and the left half corresponding to the melamine decorative laminated board of comparative example 1.

Description of the figures

1, 11.. transfer sheet, 1a.. OPP film, 1b.. dry film, 2.. melamine resin impregnated backer (overlay) paper, 3.. melamine resin impregnated decorative paper, 4.. phenolic resin impregnated core paper, 5.. melamine decorative board, 6.. low refractive index layer

Detailed Description

Hereinafter, the present invention will be described in detail. The silicone graft type polymer (component (b1)) used in the composition of the present invention is obtained by compounding a fluororesin or an acrylic resin with silicone. Specifically, the silicone graft type polymer can be obtained by copolymerizing: (A)2 to 70% by weight of an organic solvent-soluble fluororesin having an unsaturated bond radically polymerizable via a urethane bond; (B)4 to 40% by weight of a polysiloxane free-radically polymerizable at one terminal end represented by the following formula 1 (wherein R is¹Represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; r²、R³、R⁴、R⁵And R⁶May be the same as or different from each other, represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; and n represents an integer of 2 or more), and/or a polysiloxane (wherein R is represented by the following formula 2) which is radically polymerizable at one terminal(s)⁷Represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; r⁸、R⁹、R¹⁰、R¹¹And R¹²May be the same as or different from each other, represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; p represents an integer of 0 to 10; and q represents an integer of 2 or more); and (C)15 to 94% by weight of a radically polymerizable monomer which undergoes radical polymerizationUnder conditions which are unreactive toward component (A), except for polymerization with double bonds.

[ chemical formula 1]

[ chemical formula 2]

Another example of the silicone graft type polymer obtained by compounding a fluororesin or an acrylic resin with silicone includes a polymer obtained by copolymerizing: (A)2 to 70% by weight of an organic solvent-soluble fluororesin having an unsaturated bond radically polymerizable via a urethane bond; (B)5 to 55% by weight of a polysiloxane free-radically polymerizable at one terminal end represented by the above formula 1, and/or a polysiloxane free-radically polymerizable at one terminal end represented by the above formula 2; and (C)5 to 55% by weight of a monomer having an alkoxysilyl group; (D)15-50 wt% of a monomer having a hydroxyl group; and (E)0 to 73% by weight of a monomer having a functional group which is unreactive to the above components (A) to (D) other than radical polymerization.

Still another example of the silicone graft-type polymer obtained by compounding the fluororesin or the acrylic resin with silicone includes a polymer in which component (a) is replaced with an acrylic (co) polymer containing a curable group, having an unsaturated bond radically polymerizable via a urethane bond, and also being soluble in an organic solvent in each of the above-described silicone graft-type polymers.

Commercially available silicone graft type polymers obtained by compounding a fluororesin or an acrylic resin with silicone include ZX-007C, ZX-001, ZX-022H, ZX-028R, ZX-036 (both manufactured by Fuji Kasei Kogyo Co., Ltd.), and the like.

The ordinary temperature glass coating agent (component (b2)) used in the composition of the present invention includes a coating agent obtained by: an alcohol-soluble organosilicon compound is ionized in a solution composed of water and an organic solvent or the like, and halogen and boron are added thereto as a catalyst.

B³⁺The effect of the ions is to inhibit SiF by reacting with F-ions₆Generation and volatilization of₂A reduction in the amount of (c). B is³⁺Ions with F^-Ion reaction to produce BF₄ ^-Complex ion, and in BF₄ ^-B in complex ion is very easy to Si (OR)_nSi in (b) to obtain SiF^- _n+1Complexing ions. Hydrolysis and dehydration condensation represented by the following formula are promoted, and as a result, a metal oxide glass is obtained in a normal temperature range. The rest of B³⁺Ion due to methanol (CH)₃ ⁺) In the presence of B (OCH)₃)₃Form of (1) volatilizes and disappears, F^-Ion passage with OH contained in the base material or the like^-The catalytic reaction of radicals and the like volatilizes and disappears in the form of HF. Here, R represents an alkyl group, M represents a metal, and X represents a halogen.

B³⁺+4X^-→BX₄ ^-

M(OR)_n+BX₄ ^-+n/2H₂O→MX^- _n+1+nROH+B³⁺

MX^- _m+1+nH₂O→M(OH)_n+(n+1)X^-

M(OH)_n→ metal oxide glass + H₂O

Releasing boron ions B³⁺Examples of the compounds of (1) include, for example, trialkoxyboranes B (OR)₃Among them, triethoxyborane B (OEt)₃. In the reaction solution B³⁺The concentration of the ions is preferably in the range of 1.0 to 10.0 mol/l. The halogen ion is preferably F^-、Cl^-Or F^-And Cl^-A mixture of (a). The compound used as the halide ion source may be a compound that generates F in a reaction solution^-Ions or Cl^-Any compound of an ion. As F^-Ion source, e.g. preferably ammonium bifluoride NH₄F, HF, sodium fluoride NaF, and the like. As Cl^-Ion source, e.g. preferably ammonium chloride NH₄Cl, and the like.

Commercially available room temperature glass coating agents include Siragusital A6200, Siragusital B4373(BN) (both manufactured by Bokuto Kasei Kogyo Co., Ltd.), and the like.

The silicone sol used in the composition of the present invention includes, for example, a colloidal solution comprising colloidal silica having a particle size of 1 to 40nm (more preferably, 7 to 30nm) stably dispersed in an organic solution. The silica concentration is preferably 1 to 50% by weight, more preferably 40% by weight or less, to suppress gelation.

Commercially available organosilicones include IPA-ST, IPA-ST-ZL, MeOH-silica sol, NPC-ST-30, EG-ST, DMAC-ST, and the like manufactured by Nissan Chemical Industries, Ltd; OSCAL manufactured by Shokubai Kasei Kogyo co, ltd; quartron (registered trademark) manufactured by Fuso Chemical co., ltd.; highlink (registered trademark) OG Silica Organosol manufactured by Clariant Japan k.k.

In the composition of the present invention, it is preferable to use an organic silica sol obtained by replacing an aqueous silica sol with a hydrophilic solvent such as alcohol or the like. In the organic silica sol obtained from the aqueous silica sol as a raw material, the amount of hydroxyl groups on the silica surface becomes sufficient. Therefore, when the low refractive index layer of the melamine decorative board is formed using the composition of the present invention, adhesion between the low refractive index layer and the melamine layer is promoted, thereby improving the surface durability of the melamine decorative board. When the silicone sol is dispersed in the hydrophobic solvent, the surface of the silicone sol is hydrophobized to stabilize the silicone sol. In this silicone sol, silica does not have a sufficient amount of hydroxyl groups on its surface, and adhesion between the low refractive index layer and the melamine layer may be poor.

Here, the hydrophilic (polar) solvent refers to a solvent having an affinity with water. Examples thereof are hydrophilic organic solvents including hydrophilic groups such as hydroxyl groups, carboxyl groups, carbonyl groups, and the like in their molecules. Examples of the hydrophilic (polar) solvent include a protic polar solvent and an aprotic polar solvent. Specific examples of the protic polar solvent include: alcohol-based solvents such as methanol, ethanol, isopropanol, ethylene glycol, propanol, and the like; and cellosolve-based solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, n-propyl cellosolve, and the like. Specific examples of the aprotic polar solvent include acetone, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), pyridine, and the like.

In the composition of the present invention, the mixing ratio between component (a) and component (b1) is preferably set so that the amount of component (a) is 4 to 18 parts by weight (in terms of converted solid amount) per part by weight of component (b1) (in terms of converted solid amount). By setting the amount of component (a) to 4 parts by weight or more, the amount of hydroxyl groups on the silica surface becomes sufficient, and therefore, close adhesion between the low refractive index layer and the melamine layer is promoted, thereby improving the surface durability of the melamine decorative board. Further, by setting the amount of component (a) to 18 parts by weight or less, the amount of component (b1) does not become too small. As a result, fingerprints become less noticeable on the surface of the melamine decorative board, and the pattern on the printed paper becomes clearer.

In the composition of the present invention, the mixing ratio between component (a) and component (b2) is preferably set so that the amount of component (a) is 4 to 18 parts by weight (in terms of converted solid amount) per part by weight of component (b2) (in terms of converted solid amount). By setting the amount of component (a) to 4 parts by weight or more, the amount of hydroxyl groups on the silica surface becomes sufficient. Therefore, close adhesion between the low refractive index layer and the melamine layer is promoted, thereby improving the surface durability of the melamine decorative board. Further, by setting the amount of component (a) to 18 parts by weight or less, the amount of component (b2) does not become too small. As a result, fingerprints become less noticeable on the surface of the melamine decorative board, and the pattern on the printed paper becomes clearer.

Examples of the base material used as the transfer sheet of the present invention include plastic films and metal foils. As the plastic film, for example, a polyester film, a polyethylene film, a polypropylene film, cellophane, a cellulose diacetate film, a cellulose triacetate film, a cellulose acetate butyrate film, a polyvinyl chloride film, a polyvinylidene chloride film, a polyvinyl alcohol film, an ethylene-vinyl alcohol film, a polystyrene film, a polycarbonate film, a polymethylpentene film, a polysulfone film, a polyether ketone film, a polyether sulfone film, a polyether imide film, a polyimide film, a fluororesin film, a nylon film, an acrylic film, or the like can be used.

As the metal foil, for example, gold foil, silver foil, copper foil, zinc foil, indium foil, aluminum foil, tin foil, iron foil (including stainless steel (SUS) foil), titanium foil, or the like can be used.

The transfer sheet of the present invention can be produced, for example, by coating the combination onto the base material. As the coating method, known methods such as a spray coating method, a gravure coating method, a bar coating method, a blade coating method, a roll coating method, a blade coating method, a die coating method, a curtain coating method, a reverse coating method, a Comma coating (Comma Coat, コンマ - ト) method, and the like can be used. The transfer sheet obtained by these methods is stacked on melamine resin-impregnated paper (for example, melamine resin-impregnated model paper and melamine resin-impregnated coating paper) such that the surface of the coating composition is in contact with the melamine resin-impregnated paper, and then, heat and pressure are applied to the stacked transfer sheet and the melamine resin-impregnated paper together with the core material to perform hot press molding.

When the composition comprises component (a) and component (b1), the thickness (after drying) of the low refractive index layer formed using the composition of the present invention is preferably in the range of 0.5 to 15 μm. By setting the thickness within this range, the refractive index of the low refractive index layer is easily made 1.5 or less. In addition, by setting the film thickness to 0.5 μm or more, fingerprints become less noticeable on the surface of the melamine decorative laminated board, and the pattern on the printed paper becomes clearer. Further, by setting the film thickness to 15 μm or less, whitening of the low refractive index layer is less likely to occur, and the appearance of the melamine decorative board becomes excellent.

When the composition comprises component (a) and component (b2), the thickness (after drying) of the low refractive index layer formed using the composition of the present invention is preferably in the range of 0.5 to 15 μm. By setting the thickness within this range, the refractive index of the low refractive index layer is easily made 1.5 or less. In addition, by setting the film thickness to 0.5 μm or more, fingerprints become less noticeable on the surface of the melamine decorative laminated board, and the pattern on the printed paper becomes clearer. Further, by setting the film thickness to 15 μm or less, whitening of the low refractive index layer is less likely to occur, and the appearance of the melamine decorative board becomes excellent.

In the melamine decorative laminated board of the present invention and the method for manufacturing the melamine decorative laminated board of the present invention, as the decorative paper for decorative laminated boards, for example, a melamine resin-impregnated paper (melamine resin-impregnated pattern paper) obtained by, for example, the following method can be used: a decorative paper for a decorative sheet is impregnated with a resin liquid composed of a melamine-formaldehyde resin as a main component, and the impregnated decorative paper is dried. The weight per unit area (tare weight) of the decorative paper for decorative boards is preferably, for example, in the range of about 80 to 140g/m²The range of (1). The degree of impregnation of the resin solution defined by the following numerical formula 1 is, for example, preferably in the range of 70 to 160%.

[ mathematical formula 1]

In the melamine decorative laminated board of the invention and the method for manufacturing the melamine decorative laminated board of the invention, in order to improve abrasion resistance on the surface of the melamine decorative laminated board, melamine resin-impregnated coated paper, which is base paper for a base paper, is stacked as the uppermost layer (excluding the low refractive index layer), and heat and pressure are applied to the stacked body to perform hot press moldingObtained by impregnating a resin solution containing a melamine-formaldehyde resin as a main component. The melamine resin impregnated paperboard has an impregnation rate of 200-400% and an impregnation weight of about 20-60g/m²And drying the impregnated coating base paper.

In the melamine decorative laminated board of the invention and the method for manufacturing the melamine decorative laminated board of the invention, a core material may be used. The core material is obtained as follows: for example, by impregnating kraft paper with a resin liquid composed of a phenol-formaldehyde resin as a main component and drying the impregnated kraft paper. The kraft paper preferably has a weight per unit area of, for example, about 150-300g/m²The range of (1). The impregnation rate of the resin solution defined by the above equation 1 is preferably in the range of 30 to 80%, for example.

The invention will be described hereinafter by way of examples, experimental examples and comparative examples, which do not limit the invention in any way.

Example 1

1. Preparation of the composition

1 part by weight (in terms of solid amount) of the siloxane graft type polymer was mixed with 10 parts by weight (in terms of solid amount) of the silicone sol. As the silicone graft type polymer, ZX-022H (hydroxyl value: 120, acid value: 0, solvent type: xylene/butyl acetate/isopropyl alcohol, manufactured by Fuji Kasei Kogyo Co., Ltd.) obtained by compounding a fluororesin and silicone was used. As the organic silica sol, IPA-ST (isopropyl alcohol-dispersed silica sol, average particle diameter: 10-20nm, SiO)₂: 30 wt%, manufactured by Nissan Chemical Industries, ltd). Further, IPA-ST is an organic silica sol using a hydrophilic solvent (isopropyl alcohol).

The above mixture was diluted with isopropyl alcohol so that the total solid content became 20% by weight, and a composition was obtained.

2. Preparation of transfer sheet

The above composition was uniformly coated on an OPP film having a thickness of 30 μm by a bar coating method so that the film thickness of the composition after drying was 3 μm. The OPP film was dried to obtain a transfer sheet 1. In the transfer sheet 1, a layer containing a dried product of the above composition is formed on the OPP film.

3. Preparation of melamine decorative board

For a weight per unit area for decorative panels of 40g/m²The coated paper of (2) is impregnated with a resin solution composed of a melamine-formaldehyde resin as a main component. The immersion rate of the resin solution was set to 300% according to the calculation method defined by the above equation 1. The impregnated coated paper was dried to obtain a melamine resin impregnated liner paper 2.

For a weight per unit area for decorative panels of 100g/m²The black decorative paper of (2) is impregnated with a resin solution composed of a melamine-formaldehyde resin as a main component, and the impregnation rate of the resin solution is set to 100% by the calculation method defined by the above numerical formula 1. The impregnated decor paper is dried to obtain a melamine resin impregnated decor paper 3.

The weight per unit area is 200g/m²The kraft paper of (1) is impregnated with a resin solution containing a phenol-formaldehyde resin as a main component, and the impregnation rate of the resin solution is set to 50% by the calculation method defined by the above equation 1. The impregnated kraft paper is dried to obtain a phenolic resin impregnated core paper 4.

As shown in fig. 1, five sheets of phenol resin-impregnated core paper 4, one sheet of melamine resin-impregnated decorative paper 3, one sheet of melamine resin-impregnated liner paper 2, and one sheet of the transfer sheet 1 are stacked in this order. A transfer sheet 1 comprising an OPP film 1a and a dry film 1b of the composition is stacked with the transfer sheet 1 oriented so that the dry film 1b is in contact with a melamine resin impregnated liner paper 2. The hot press molding was performed by applying heat and pressure to the stacked body at a temperature of 135 ℃ and a pressure of 8MPa for 80 minutes. Then, the OPP film 1a is removed as shown in fig. 2 to obtain a melamine decorative laminated board 5. A low refractive index layer 6 comprising a cured product of the composition is formed on the surface of the melamine decorative sheet 5. The low refractive index layer 6 is a layer resulting from a dried film 1b of the composition.

Example 2

A transfer sheet was prepared in the same manner as in example 1, except that the film thickness of the composition after drying (thickness of the low refractive index layer) on the transfer sheet was set to 0.5 μm. Further, a melamine decorative laminated sheet having a low refractive index layer formed on the surface thereof was prepared in the same manner as in example 1, except that the above transfer sheet was used.

Example 3

A transfer sheet was prepared in the same manner as in example 1, except that the film thickness of the composition after drying (thickness of the low refractive index layer) on the transfer sheet was set to 15 μm. Further, a melamine decorative board having a low refractive index layer formed on the surface thereof was prepared in the same manner as in example 1, except that the transfer sheet was used.

Example 4

A composition was prepared in the same manner as in example 1 except that the mixing ratio between the silicone graft type polymer and the silicone sol was set as follows:

siloxane graft type polymer: 1 part by weight (in terms of solid content)

Organic silicon sol: 4 parts by weight (in terms of converted solids).

Further, a transfer sheet and a melamine decorative sheet having a low refractive index layer formed on the surface thereof were prepared in the same manner as in example 1, except that the composition was used.

Example 5

siloxane graft type polymer: 1 part by weight (in terms of solid content)

Organic silicon sol: 6 parts by weight (in terms of converted solids).

Example 6

siloxane graft type polymer: 1 part by weight (in terms of solid content)

Organic silicon sol: 14 parts by weight (in terms of converted solids).

Example 7

siloxane graft type polymer: 1 part by weight (in terms of solid content)

Organic silicon sol: 18 parts by weight (in terms of converted solids).

Example 8

A composition was prepared in the same manner as in example 1, except that the same amount of methanol-dispersed silica sol (methanol-dispersed silica sol, average particle diameter: 10 to 20nm, Si)O₂: 30 wt%, manufactured by Nissan Chemical Industries, ltd.) instead of IPA-ST as the organic silica sol. Further, the methanol silica sol is an organic silica sol using a hydrophilic solvent (methanol).

Example 9

A composition was prepared in the same manner as in example 1, except that the same amount of NPC-ST-30 (average particle diameter: 10-20nm, n-propylcellosolve-dispersed silica sol, SiO) was used₂: 30 wt%, manufactured by Nissan Chemical Industries, ltd.) instead of IPA-ST as the organic silica sol. Further, NPC-ST-30 is an organic silica sol using a hydrophilic solvent (n-propylcellosolve).

Example 10

A composition was prepared in the same manner as in example 1 except that the same amount of silicone graft type polymer ZX-007C (hydroxyl value: 58, acid value: 5, solvent type: xylene/butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) obtained by compounding a fluororesin and silicone was used instead of ZX-022H as the silicone graft type polymer. Further, a transfer sheet and a melamine decorative sheet having a low refractive index layer formed on the surface thereof were prepared in the same manner as in example 1, except that the composition was used.

Example 11

A composition was prepared in the same manner as in example 1 except that the same amount of silicone graft type polymer ZX-001 (hydroxyl value: 94, acid value: 0, solvent species: xylene/isobutanol, manufactured by Fuji Kasei Kogyo Co., Ltd.) obtained by compounding a fluororesin and silicone was used instead of ZX-022H as the silicone graft type polymer. Further, a transfer sheet and a melamine decorative sheet having a low refractive index layer formed on the surface thereof were prepared in the same manner as in example 1, except that the composition was used.

Example 12

A composition was prepared in the same manner as in example 1 except that the same amount of silicone graft type polymer ZX-022 (hydroxyl value: 120, acid value: 5, solvent species: xylene/butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) obtained by compounding a fluororesin and silicone was used instead of ZX-022H as the silicone graft type polymer. Further, a transfer sheet and a melamine decorative sheet having a low refractive index layer formed on the surface thereof were prepared in the same manner as in example 1, except that the composition was used.

Example 13

A composition was prepared in the same manner as in example 1 except that the same amount of silicone graft type polymer ZX-028-R (hydroxyl value: 100, acid value: 5, solvent type: butyl acetate, manufactured by FujiKasei Kogyo Co., Ltd.) obtained by compounding an acrylic resin and silicone was used instead of ZX-022H as the silicone graft type polymer. Further, a transfer sheet and a melamine decorative sheet having a low refractive index layer formed on the surface thereof were prepared in the same manner as in example 1, except that the composition was used.

Example 14

A composition was prepared in the same manner as in example 1 except that the same amount of silicone graft type polymer ZX-036 (hydroxyl value: 119, solvent species: butyl acetate/2-propanol, manufactured by Fuji Kasei Kogyo Co., Ltd.) obtained by compounding an acrylic resin and silicone was used instead of ZX-022H as the silicone graft type polymer. Further, a transfer sheet and a melamine decorative sheet having a low refractive index layer formed on the surface thereof were prepared in the same manner as in example 1, except that the composition was used.

Example 15

1. Preparation of the composition

1 part by weight (in terms of solid content) of the room-temperature glass coating agent was mixed with 10 parts by weight (in terms of solid content) of the organic silica sol. As the ordinary temperature glass coating agent, a one-pack type coating agent (commercial name: Siragusital A6200, manufactured by Bokuto Kasei Kogyo Co., Ltd.) was used. The room temperature glass coating agent is obtained by: mixing an alcohol-soluble organosilicon compound (Si (OR))₄) Mixing with alcohol (isopropanol), etc., and adding boron ion B³⁺And a halogen ion F^-As a catalyst to adjust the pH to 4.5-5.0. As the organic silica sol, IPA-ST (isopropyl alcohol-dispersed silica sol, average particle diameter: 10-20nm, SiO)₂: 30 wt%, manufactured by Nissan Chemical Industries, ltd).

2. Preparation of transfer sheet

The above composition was uniformly coated on an OPP film having a thickness of 30 μm by a bar coating method so that the film thickness of the composition after drying was 3 μm. The OPP film was dried to obtain the transfer sheet 11.

3. Preparation of melamine decorative board

Using the above transfer sheet 11, a melamine decorative sheet having a low refractive index layer formed on the surface thereof was prepared in the same manner as in example 1 (see fig. 1).

Example 16

A transfer sheet was produced in the same manner as in example 15, except that the film thickness of the composition after drying (thickness of the low refractive index layer) on the transfer sheet was set to 0.5 μm. Further, a melamine decorative board having a low refractive index layer formed on the surface thereof was prepared in the same manner as in example 15, except that the transfer sheet was used.

Example 17

A transfer sheet was prepared in the same manner as in example 15, except that the film thickness of the composition after drying (thickness of the low refractive index layer) on the transfer sheet was set to 15 μm. Further, a melamine decorative board having a low refractive index layer formed on the surface thereof was prepared in the same manner as in example 15, except that the transfer sheet was used.

Example 18

A composition was prepared in the same manner as in example 15, except that the mixing ratio between the ordinary temperature glass-coating agent and the silicone sol was set as follows:

normal temperature glass coating agent: 1 part by weight (in terms of solid content)

Organic silicon sol: 4 parts by weight (in terms of converted solids).

Further, a transfer sheet and a melamine decorative sheet having a low refractive index layer formed on the surface thereof were prepared in the same manner as in example 15, except that the composition was used.

Example 19

Organic silicon sol: 6 parts by weight (in terms of converted solids).

Example 20

Organic silicon sol: 14 parts by weight (in terms of converted solids).

Example 21

A composition was prepared in the same manner as in example 15, except that the mixing ratio between the ordinary temperature glass-coating agent and the organic silica sol was set as follows:

Organic silicon sol: 18 parts by weight (in terms of converted solids).

Example 22

A composition was prepared in the same manner as in example 15, except that the same amount of methanol silica sol (methanol dispersed silica sol, manufactured by Nissan chemical industries, ltd.) was used instead of IPA-ST as the silicone sol. Further, a transfer sheet and a melamine decorative sheet having a low refractive index layer formed on the surface thereof were prepared in the same manner as in example 15, except that the composition was used.

Example 23

A composition was prepared in the same manner as in example 15, except that the same amount of NPC-ST-30 (n-propylcellosolve dispersed silica sol, manufactured by Nissan chemical Industries, Ltd.) was used instead of IPA-ST as the organosilicon sol. Further, a transfer sheet and a melamine decorative sheet having a low refractive index layer formed on the surface thereof were prepared in the same manner as in example 15, except that the composition was used.

Example 24

A composition was prepared in the same manner as in example 15, except that the same amount of Siragusital B4372(BN) (manufactured by Bokuto Kasei Kogyo co., ltd.) was used instead of Siragusital a6200 as an ordinary temperature glass coating agent. The Siragusital B4372(BN) is a mixture comprising an alcohol-soluble organosilicon compound (Si (OR)₄) As a main agent compound and contains boron ions B³⁺And a halide ion X^-Two-component coating agents as catalysts. The main agent compound and the catalyst, the main agent compound: 10 parts by weight of catalyst: 1 part by weight, and used after being diluted with a diluting solvent to an arbitrary concentration.

(Experimental example 1)

siloxane graft type polymer: 1 part by weight (in terms of solid content)

Organic silicon sol: 3 parts by weight (in terms of converted solids).

Further, a transfer sheet and a melamine decorative sheet having a low refractive index layer formed on the surface thereof were prepared in the same manner as in example 1 except that the composition was used.

(Experimental example 2)

siloxane graft type polymer: 1 part by weight (in terms of solid content)

Organic silicon sol: 20 parts by weight (in terms of converted solids).

(Experimental example 3)

A composition was prepared in the same manner as in example 1, except that the same amount of nBAC-ST (butyl acetate dispersed silica sol, manufactured by Nissan chemical industries, Ltd.) was used instead of IPA-ST as the silica sol. The nBAC-ST is an organic silica sol of which the solvent species is hydrophobic.

(Experimental example 4)

Organic silicon sol: 3 parts by weight (in terms of converted solids).

(Experimental example 5)

Organic silicon sol: 20 parts by weight (in terms of converted solids).

(Experimental example 6)

A composition was prepared in the same manner as in example 15, except that the same amount of nBAC-ST (butyl acetate dispersed silica sol, manufactured by Nissan chemical industries, Ltd.) was used instead of IPA-ST as the silicone sol. The nBAC-ST is an organic silica sol of which the solvent type is hydrophobic.

Comparative example 1

Five sheets of phenolic resin-impregnated core paper, one sheet of melamine resin-impregnated decorative paper, and one sheet of melamine resin-impregnated liner paper were stacked, and hot press-molded at a temperature of 135 ℃ and a pressure of 8MPa under heat and pressure for 80 minutes to obtain a melamine decorative board. The phenolic resin impregnated core paper, melamine resin impregnated decorative paper, and melamine resin impregnated liner paper were each the same as in example 1.

Then, the melamine decorative laminated boards prepared in examples 1 to 24, experimental examples 1 to 6 and comparative example 1 were evaluated.

(evaluation method)

(i) Evaluation of anti-fingerprint Performance Using actual fingerprints

Actual fingerprints were attached to the surface of each melamine decorative board, and it was visually evaluated how noticeable the fingerprints were. The evaluation criteria are as follows:

o: fingerprints are inconspicuous

And (delta): fingerprints are somewhat noticeable

X: fingerprints are noticeable

(ii) Definition of

The clarity of the decorative paper of the melamine decorative board was visually observed under oblique illumination. The evaluation criteria are as follows:

o: the decorative paper can be clearly observed

And (delta): light reflection and white spots were slightly observed

(iii) Surface durability (1)

At about 300g/cm²The surface of each melamine decorative board was wiped back and forth 100 times by the dried crushed cotton yarn under the load of (1) and the change in the gloss on the surface was visually evaluated. The evaluation criteria are as follows:

o: no change in gloss was observed

And (delta): slight changes in gloss were observed

X: changes in gloss were observed

(iv) Surface durability (2)

At about 1kg/cm²The surface of each melamine decorative board was wiped back and forth under a load of (1) by a dry crushed cotton yarn, and the change in the gloss on the surface was visually evaluated. The evaluation criteria are as follows:

5: no change in gloss was observed when or before wiping the surface back and forth 500 times

4: the change in gloss was observed when or before wiping the surface back and forth 400 times

3: the change in gloss was observed when or before wiping the surface back and forth 300 times

2: the change in gloss was observed when or before wiping the surface back and forth 200 times

1: the change in gloss was observed when or before wiping the surface back and forth 100 times

(v) Refractive index

The refractive index on the surface of each melamine decorative board was measured with a multi-wavelength Abbe (Abbe) refractometer (DR-M2, manufactured by agago co., ltd.). The refractive index was measured at a wavelength of 589 nm.

(vi) Surface hardness

According to JIS K5600; 1999 (general test method for coating) the surface hardness of each melamine decorative board was measured under a load of 1 kg.

(vii) Wear resistance

According to JIS K6902; 1998 (test method for laminated thermosetting high-pressure decorative sheet) the abrasion resistance of the surface of each melamine decorative sheet was measured.

(evaluation results)

Tables 1 and 2 show the evaluation results. In Table 1, "(b 1): (a)" represents the weight ratio (in converted solids) between the silicone-grafted polymer (b1) and the silicone sol (a). In table 2, "(b 2): (a)" represents the weight ratio (in converted solids) between the room-temperature glass coating agent (b2) and the silicone sol (a).

[ Table 1]

[ Table 2]

As shown in tables 1 and 2, in the melamine decorative laminated boards of examples 1 to 24, fingerprints were less noticeable, and the printed patterns had high definition. Further, the melamine decorative laminated boards of examples 1 to 24 exhibited high surface durability, high surface hardness, and high abrasion resistance. In contrast, in the melamine decorative laminated board of comparative example 1, fingerprints were noticeable, and the printed pattern had low definition.

Fig. 3 is a photograph showing the surface conditions of the melamine decorative laminated boards of example 1 and comparative example. The right half of the photograph corresponds to the melamine decorative board of example 1, and the left half corresponds to the melamine decorative board of comparative example 1. As is clear from the photograph, in the melamine decorative laminated board of example 1, the decorative paper had high definition, whereas the melamine decorative laminated board of comparative example 1 was whitish and the decorative paper had low definition.

Fig. 4 is a photograph showing fingerprints attached on the surfaces of each of the melamine decorative boards of example 1 and comparative example 1 when the anti-fingerprint performance was evaluated using actual fingerprints. The right half of the photograph corresponds to the melamine decorative board of example 1, and the left half corresponds to the melamine decorative board of comparative example 1. As is clear from the photograph, in the melamine decorative laminated board of example 1, the fingerprint on the surface thereof was far less noticeable than that of the melamine decorative laminated board of comparative example 1. This is attributed to the fact that the melamine decorative laminated board of example 1 includes the low refractive index layer 6.

The evaluation results of each of the melamine decorative boards of experimental examples 1 and 3 were slightly inferior to those of each of examples 1 to 24 in surface durability.

The evaluation results of the melamine decorative laminated board of experimental example 2 were slightly inferior to the results of each of examples 1 to 24 in anti-fingerprint property and clarity.

The evaluation results of each of the melamine decorative boards of experimental examples 4 and 6 were slightly inferior to those of each of examples 1 to 24 in surface durability and surface hardness.

The evaluation results of the melamine decorative laminated board of experimental example 5 were slightly inferior to the results of each of examples 1 to 24 in anti-fingerprint property and clarity.

Claims

1. A composition, comprising:

(a) an organic silica sol; and

(b1) a silicone graft polymer obtained by compounding a fluororesin or an acrylic resin with silicone or (b2) a room temperature glass coating agent,

said (b1) is selected from the following:

(1) a silicone graft type polymer obtained by copolymerizing:

(A)2 to 70% by weight of an organic solvent-soluble fluororesin having an unsaturated bond radically polymerizable via a urethane bond;

(B)4 to 40% by weight of a polysiloxane radically polymerizable at one terminal represented by the following formula 1 and/or a polysiloxane radically polymerizable at one terminal represented by the following formula 2,

[ chemical formula 1]

Wherein R is¹Represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; r²、R³、R⁴、R⁵And R⁶May be the same as or different from each other, represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; n represents an integer of 2 or more,

[ chemical formula 2]

Wherein R is⁷Represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; r⁸、R⁹、R¹⁰、R¹¹And R¹²May be the same as or different from each other, represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; p represents an integer of 0 to 10; q represents an integer of 2 or more; and

(C)15 to 94% by weight of free-radically polymerizable monomers which are unreactive toward component (A) under free-radical polymerization conditions, except for polymerization with double bonds;

(2) a polymer obtained by copolymerizing the following components:

(B)5 to 55% by weight of a polysiloxane free-radically polymerizable at one terminal end represented by the above formula 1, and/or a polysiloxane free-radically polymerizable at one terminal end represented by the above formula 2; and

(C)5 to 55 weight percent of a monomer having an alkoxysilyl group;

(D)15-50 wt% of a monomer having a hydroxyl group; and

(E)0 to 73% by weight of a monomer having a functional group which is not reactive to the above components (A) to (D) except for radical polymerization;

(3) among the silicone graft-type polymers of (1) or (2), silicone graft-type polymers each obtained by replacing the polymer of component (A) with an acrylic-type polymer containing a curable group, having an unsaturated bond radically polymerizable via a urethane bond, and also being soluble in an organic solvent,

said (b2) is selected from the following:

a room temperature glass coating agent obtained by ionizing an alcohol-soluble organic silicon compound in a solution composed of water and an organic solvent and adding thereto a halogen and boron as a catalyst,

and the mixing ratio of the component (a) to the component (b1) or the component (b2) is as follows:

the amount of the component (a) is 4 to 18 parts by weight per part by weight of the component (b1) or (b2) in terms of solid amount.

2. A transfer sheet, comprising:

a base material; and

the composition of claim 1 disposed on the substrate material.

3. A melamine decorative board having a low refractive index layer formed on a surface thereof, the low refractive index layer comprising a cured product of the composition of claim 1.

4. The melamine decorative laminated sheet of claim 3, wherein the low refractive index layer has a refractive index of 1.5 or less.

5. A method of manufacturing a melamine decorative panel, the method comprising the steps of:

stacking the transfer sheet of claim 2, melamine resin-impregnated paper, and a core material;

and applying heat and pressure to the stacked body to perform hot press molding; and

removing the matrix material.