JP6967977B2 - Non-combustible decorative panel - Google Patents

Description

The present invention relates to a non-combustible decorative panel.

For the inner wall panel of the tunnel, for example, a non-combustible base material such as a flexible board coated with paint, a tile attached, and an enamel attached are used.

Japanese Unexamined Patent Publication No. 10-8895

Conventionally, painted panels, tile panels, and enamel panels have been used for the inner wall panels of tunnels, and there is a problem that a pattern cannot be applied. Further, conventionally, when a non-combustible base material (flexible board) and a melamine decorative impregnated paper are hot-press molded, there is a problem that both non-combustibility and adhesiveness cannot be achieved.

The present invention has been studied in view of this situation, and includes a decorative layer, an intermediate layer, a primer layer, and an inorganic base material. The intermediate layer uses a heat-resistant fibrous sheet as a base material, and a diallyl phthalate resin and vinyl. It is a non-combustible decorative panel characterized by containing an ester.

It is a non-combustible decorative panel with impact resistance, bending strength, and non-combustibility, and has both designability by printing and hardness of melamine resin, and is suitably used for the inner wall of a tunnel.

The structural sectional view of the non-combustible decorative panel of this invention.

For the decorative layer according to the present invention, a resin solution containing a thermosetting resin such as an amino-formaldehyde resin, a diallyl phthalate resin, an unsaturated polyester resin, or a mixed resin thereof as a main component is used for a thermosetting resin decorative board. 30 to 140 g / m ² of the decorative paper is impregnated so that the impregnation rate shown in Equation 1 is 80 to 300%, and a dried resin-impregnated decorative paper is used. Among the resins, amino-formaldehyde resin having excellent heat resistance and abrasion resistance is particularly preferable, and melamine having excellent water resistance, heat resistance, abrasion resistance, chemical resistance and stain resistance is particularly preferable. -Formaldehyde resin.

In the intermediate layer according to the present invention, as a fibrous sheet having heat resistance, a slurry containing pulp and a silicate compound having bound water as main components, and a coagulation binder, a chemical, an organic fiber, an inorganic fiber, a fixing agent and the like is added. Is made with a round net paper machine, a long net multi-cylinder paper machine, a long net-circle net combination paper machine, an inclined paper machine, etc., and dehydrated and dried 60 to 200 g / m ² silicate compound mixed paper is used. The mixed paper obtained in this way has self-extinguishing properties and can suppress the spread of flames. Examples of pulp include natural pulp such as wood pulp, cotton pulp, and vegetable fiber pulp. In particular, chemical pulp obtained by chemically treating wood pulp having a short fiber length such as broadleaf bleached kraft pulp and coniferous kraft pulp is used. It is strong, has excellent impregnation suitability, and is preferable. Hardwood bleached kraft pulp and softwood kraft pulp may be used in combination, and may be bleached or unbleached.

Examples of the silicate compound having bound water include hydrous magnesium silicate and hydrous magnesium aluminum silicate. The mixed extract ratio of the silicic acid compound having bound water and the pulp is preferably 40 to 95% by weight, more preferably 55 to 85% by weight. If it is less than 40% by weight, the noncombustible performance tends to decrease, and if it exceeds 95% by weight, the paper strength tends to decrease.

The heat-resistant fibrous sheet is impregnated with a resin solution containing a diallyl phthalate resin and a vinyl ester, and dried. Although these resins are radical polymerization type thermosetting resins, they have the advantage that the curing shrinkage is smaller than that of the polycondensation type thermosetting resin, and the warpage and cracks due to the dimensional change of the panel are not small.

The diallyl phthalate resin contains a diallyl phthalate prepolymer and an unsaturated polyester resin, and also contains a filler, a curing agent, a polymerization inhibitor, a mold release material, and an organic solvent. The mixing ratio of the diallyl phthalate prepolymer and the unsaturated polyester resin is preferably 3: 7 to 7: 3 in terms of solid content, and if it is in this range, the elasticity is excellent and the impregnated mixed papers do not adhere to each other, which is preferable.

The vinyl ester resin is also called an epoxy (meth) acrylate, and is obtained by reacting an epoxy resin with an unsaturated monobasic acid using an esterification catalyst. Examples of the epoxy resin include bisphenol A-based epoxy resin, halogenated bisphenol A-based epoxy resin, diglycidyl ether as an adduct of bisphenol A and an alkylene oxide such as ethylene oxide or propylene oxide, bisphenol F-based epoxy resin, and novolak-based epoxy resin. , Cresol novolak type epoxy resin and the like.

Examples of the monobasic acid include acrylic acid, methacrylic acid, crotonic acid, monomethylmalate, monopropylmalate, sorbic acid or mono (2-ethylhexyl) malate, and polybases used in combination with unsaturated monobasic acid. Examples of the acid include crotonic acid, maleic acid, fumaric acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, adipic acid, azelaic acid, 1,12-dodecanedioic acid and dimeric acid.

Examples of the esterification catalyst include tertiary amines such as dimethylbenzylamine and tributylamine; quaternary ammonium salts such as trimethylbenzylammonium chloride; inorganic salts such as lithium chloride and chromium chloride; 2-ethyl-4-. Imidazole compounds such as methylimidazole; tetramethylphosphonium chloride, diethylphenylpropylphosphonium chloride, triethylphenylphosphonium chloride, benzyltriethylphenylphosphonium chloride, dibenzylethylmethylphosphonium chloride, benzylmethyldiphenylphos Phosphonium salts such as phonium chloride and tetraphenylphosphonium bromide; secondary amines; tetrabutylurea; triphenylphosphine; tritrilphosphine; triphenylstibin and the like can be mentioned.

The mixing ratio of the diallyl phthalate resin and the vinyl ester resin is preferably 3: 7 to 7: 3 in terms of solid content, and within this range, the heat resistance is excellent and the adhesion to the decorative layer is also good.

The impregnation rate of the resin liquid to the heat-resistant fibrous sheet is 35 to 60% at the value calculated by Equation 1, and the resin solution is dried.

Examples of the inorganic base material related to the present invention include cement boards, fiber-reinforced cement boards, volcanic vitreous multi-layer boards, calcium silicate boards, magnesium silicate boards, flexible boards, etc., and these base materials have flame-retardant performance. Is high and has excellent strength. In particular, the flexible board has excellent fire resistance, high strength and toughness. The thickness of the inorganic base material is preferably 3 mm to 100 mm from the viewpoint of strength and ease of handling. The density is preferably 0.5 to 2.0 g / cm ^3. If the density is less than the lower limit, the underlying layer is likely to be sucked in, and if it exceeds the upper limit, it becomes heavy and tends to be inferior in handleability.

After surface grinding the inorganic substrate by sandblasting, shotblasting, dialol, sandpaper, etc., a primer layer is provided to improve the smoothness of the substrate surface and prevent the elution of alkaline components. A urethane-based primer having excellent water resistance and heat resistance is preferable for the primer layer. Examples of the urethane-based primer include a polyfunctional polyisocyanate compound having an isocyanate group at the terminal, a polyether polyol, a two-component urethane-based primer containing a polyol such as a polycarbonate polyol as a main component, and a polyfunctional polyisocyanate. Examples thereof include a one-component urethane-based primer as a main component. As the polyisocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate and the like can be used.

Examples of the aromatic polyisocyanate include 1,3-phenylenediocyanate, 1,4-phenylenediocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), and 2 , 6-Tolylene diisocyanate ("2,6-TDI), 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanatebenzene, dianisidine diisocyanate, 4,4 '-Diphenyl ether diisocyanate, 4,4', 4 "-triphenylmethane triisocyanate and the like can be mentioned.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 1,5-pentamethylene diisocyanate (1,5-PDI), 1,2-propylene diisocyanate, and 2,3-propylene diisocyanate. Examples thereof include butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexylisocyanate (PDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, and 1,4-cyclohexanediisocyanate. Methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane , Isophorone diisocyanate (IPDI) and the like. Further, it may be a trimethylolpropane adduct-type modified product of the above-mentioned polyisocyanate compound, a biuret-type modified product reacted with water, or an isocyanurate-type modified product containing an isocyanurate ring.

Among the above-mentioned polyisocyanate compounds, one or more selected from HDI, IPDI, MDI, 2,4-TDI, 2,6-TDI and modified products thereof are preferable. When weather resistance is important, one or more selected from HDI, IPDI and their variants are particularly preferable.

The amount of the primer applied ^{may be about 25 to 70 g / m 2} in terms of solid content, and is carried out by a known roll coater, flow coater, spray coating or the like. If the coating amount does not reach the lower limit, the adhesion to the pattern layer tends to be poor, and if it exceeds the upper limit, the nonflammability is impaired. After forming the primer layer, the intermediate layer and the decorative layer are sequentially laminated, and hot-press molded at a temperature of about 130 to 145 ° C. and a pressure of 60 to 80 kgf / cm ² .

(A) Decorative layer (melamine resin impregnated decorative paper)
A single-color printed decorative paper with a basis weight of 100 g / m ² is impregnated with a resin solution containing melamine-formaldehyde resin as the main component by the calculation method defined by Equation 1 so that the impregnation rate is 130%, and then dried. To produce a melamine resin-impregnated decorative paper.

(B) Intermediate layer 180 g / m ² magnesium silicate mixed paper (trade name: GP-18, manufactured by Tigalex Co., Ltd., hydrous magnesium silicate 80% by weight, pulp 10% by weight, glass fiber 5% by weight, and organic Binder 5% by weight) was used to prepare a resin solution consisting of a mixed resin containing 25 parts by weight of vinyl ester resin with respect to 25 parts by weight of diallyl phthalate resin containing a diallyl phthalate prepolymer and an unsaturated polyester resin in a ratio of 6: 4. The resin-impregnated magnesium silicate mixed paper was produced by impregnating and drying the resin so that the impregnation rate was 50% (36 g / m ^{2 per unit area) by the calculation method defined by Equation 1.}

(C) Primer layer A urethane prepolymer containing MDI (TN-100, manufactured by Sink Chemical Industry Co., Ltd.) was used.

(D) Inorganic base material layer As the inorganic base material layer, a flexible board having a thickness of 6 mm is ground with dialol and sandpaper, and the above primer is applied by spraying so that the ^{amount of the solid content is 40 g / m 2.} After drying at 100 ° C. for 10 minutes, it was dried at 150 ° C. for 10 minutes.

Manufacture of non-combustible decorative panel Resin-impregnated magnesium silicate mixed paper and melamine resin-impregnated decorative paper are sequentially laminated on the primer-coated surface of the flexible board, ^{and heat-pressure integrated at a temperature of 130 ° C., a pressure of 70 kgf / cm 2} , and a time of 90 minutes. bottom.

In Example 1, the same procedure was carried out except that the vinyl ester resin was made up to 10 parts by weight.

In Example 1, the same procedure was carried out except that the vinyl ester resin was 35 parts by weight.

In Example 1, the same procedure was carried out except that the diallyl phthalate prepolymer and the unsaturated polyester resin were set to 3: 7.

In Example 1, the same procedure was carried out except that the diallyl phthalate prepolymer and the unsaturated polyester resin were set to 7: 3.

In Example 1, the same procedure was carried out except that the diallyl phthalate resin was made up to 15 parts by weight.

In Example 1, the same procedure was carried out except that the diallyl phthalate resin was made up to 35 parts by weight.

In Example 1, the same procedure was carried out except that the diallyl phthalate resin was 15 parts by weight and the vinyl ester resin was 35 parts by weight.

In Example 1, the same procedure was carried out except that the urethane primer was set to 30 g / m ^2.

In Example 1, the same procedure was carried out except that the urethane primer was set to 60 g / m ^2.

In Example 1, the same procedure was carried out except that the urethane primer was an HDI prepolymer.

Comparative Example 1
In Example 1, it was carried out in the same manner except for using the kraft paper 180 g / ^{m 2} in place of the 180 g / ^{m 2} of magnesium silicate mixed paper.

Comparative Example 2
In Example 1, the same procedure was carried out except that the melamine resin was used instead of the mixed resin.

Comparative Example 3
In Example 1, the same procedure was carried out except that a phenol resin was used instead of the mixed resin.

Comparative Example 4
In Example 1, the same procedure was carried out except that only the diallyl phthalate resin was used instead of the mixed resin.

The evaluation results are shown in Tables 1 and 2.

The evaluation method was as follows.
1. 1. Non-combustible (1) Total calorific value A non-combustible decorative panel was used as a test body for the test. Each test piece was subjected to a heat generation test of a 20-minute test using an ISO5660-compliant cone calorimeter. A total calorific value of 7.2 MJ / m ² or less was marked with ◯, and a total calorific value of 7.2 MJ / m 2 or less was marked with x.
2. 2. Boil resistance It was carried out based on the boiling resistance of JIS K 6902. No peeling between layers or layers was marked with ◯, and with or without peeling was marked with x.
3. 3. It was cured for 12 hours in a constant temperature bath having a heat resistance of 80 ° C. No peeling between layers or layers was marked with ◯, and with or without peeling was marked with x.

1 Decorative layer 3 Intermediate layer 4 Primer layer 9 Inorganic base material layer 10 Non-combustible decorative panel

Claims (4)

A non-combustible decorative panel comprising a decorative layer, an intermediate layer, a primer layer, and an inorganic base material, the intermediate layer using a heat-resistant fibrous sheet as a base material, and containing a diallyl phthalate resin and a vinyl ester resin. The non-combustible decorative panel according to claim 1, wherein the diallyl phthalate resin contains a diallyl phthalate prepolymer and an unsaturated polyester resin. The non-combustible decorative panel according to claim 2, wherein the compounding ratio of the diallyl phthalate prepolymer and the unsaturated polyester resin is 3: 7 to 7: 3 in terms of solid content. The non-combustible decorative panel according to claim 1, wherein the compounding ratio of the diallyl phthalate resin and the vinyl ester resin is 3: 7 to 7: 3 in terms of solid content.

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