JP4758851B2 - Thermosetting resin decorative board - Google Patents

Description

  The present invention relates to a thermosetting resin decorative board.

Conventionally, a melamine resin decorative board that is integrated with heat and pressure using a melamine resin impregnated paper as a decorative layer and a phenol resin impregnated paper in which a kraft paper is impregnated with a phenol resin is known as a core layer. This melamine resin decorative plate has a main thickness of 0.8 to 1.4 mm, and is used for vertical surfaces such as a horizontal surface, a wall surface, a pillar and the like such as a wash counter, a desk and a table because of its excellent physical properties. In recent years, a thick decorative board having a thickness of 3 to 10 mm is also known for the purpose of improving impact resistance. Usually, 15 to 50 phenol resin-impregnated papers are laminated with melamine resin-impregnated papers, It is pressure formed.
JP-A-5-318640 JP-A-9-164645 JP-A-9-254331

  However, since the core layer is thick, there is a disadvantage that the balance with the decorative layer cannot be achieved and the dimensional shrinkage due to the influence of temperature and humidity is large. In addition, when a large amount of inorganic filler with poor reactivity is used in the core layer, the organic resin content becomes non-uniform because there is little organic resin content as a binder, and the resulting decorative board warps in a wave shape. There was a problem that it was easy.

The present invention has been studied to solve the above problems, and polypropylene glycol, and a thermosetting resin as the organic resin component, a slurry with a calcium carbonate as an inorganic filler, inorganic fiber woven fabric or A thermosetting resin decorative board having a core layer of a prepreg impregnated and dried in a nonwoven fabric ,
In the slurry, 5 to 50 parts by weight of the polypropylene glycol is blended with respect to 100 parts by weight of the solid content of the thermosetting resin,
The blending ratio of the thermosetting resin and the calcium carbonate is 1: 2 to 20 in solid content ratio,
The said calcium carbonate is a thermosetting resin decorative board characterized by using together the thing of an average particle diameter of 1-2 micrometers, and an average particle diameter of 4-5 micrometers .

  In the present invention, a woven fabric or a non-woven fabric of inorganic fibers is used as the base material of the core layer instead of the conventional kraft paper, so that the dimensional shrinkage caused by the base material can be suppressed, and the conventional heat is used as the resin impregnating the base material. Since the slurry containing polyether polyol in addition to organic resin and calcium carbonate from curable resin alone can be used, dimensional shrinkage due to the influence of the resin can be suppressed, and the thermosetting resin decorative board integrated with the decorative layer also shrinks in size. Is extremely small. Further, the obtained decorative board does not generate warp caused by temperature and humidity. Hereinafter, the present invention will be described in detail.

The base material for the core layer used in the present invention is a woven or non-woven fabric of inorganic fibers. Examples of the inorganic fibers include glass fibers, rock wool, carbon fibers, and the basis weight of the base material is 10 to 200 g. A range of / m ² is preferable, and it is particularly preferable to use glass fibers that are excellent in impregnation of the slurry.

  The slurry impregnated in the base material is a slurry containing only an organic resin component and calcium carbonate which is a non-hydrated inorganic substance as a filler, and examples of the organic resin include thermosetting properties such as amino-formaldehyde resin and phenol-formaldehyde resin. A phenol-formaldehyde resin that can be suitably used because it is excellent in various physical properties such as heat resistance and dimensional change of the finished product, and particularly excellent in impact resistance is preferable.

  The amino-formaldehyde resin is obtained by reacting an amino compound such as melamine, urea, benzoguanamine, acetoguanamine and formaldehyde.

Phenol-formaldehyde resin is composed of 1 to 3 moles of formaldehyde with respect to 1 mole of phenolic hydroxyl groups of phenols such as phenol, cresol, xylenol, octylphenol, phenylphenol, bisphenol A, bisphenol S, bisphenol F, water, It can be obtained by reacting under a basic catalyst such as sodium oxide or triethylamine.
As the organic resin of the slurry impregnated in the base material, a mixture of 5 to 50 parts by weight of polyol polyether with 100 parts by weight of the solid content of the thermosetting resin is used in the thermosetting resin. If the blending amount is less than the lower limit, the warp suppressing effect cannot be sufficiently obtained. If the blending amount exceeds the upper limit, the viscosity is increased, and the drying property is remarkably lowered, making impregnation difficult.

  The polyether polyol preferably has a number average molecular weight in the range of 300 to 2500, and a hydroxyl value in the range of 50 to 300 mgKOH / g. When the number average molecular weight exceeds the upper limit, the viscosity increases. Decrease in permeability to paper during impregnation and resin adhesion amount are likely to be non-uniform, and if it is less than the lower limit, the curability of the resin tends to be inferior and processability is lowered. Similarly, when the hydroxyl value exceeds the upper limit, the viscosity increases, and the amount of resin adhering at the time of impregnation tends to be non-uniform. When the hydroxyl value is less than the lower limit, the curability of the resin tends to be inferior, and the workability decreases.

  As a preferable thing of a polyether polyol, there exists a polyether polyol shown, for example by Chemical formula 1.

(Where R is a polyhydric alcohol residue; (OR ₁ ) _n is a polyoxyalkylene chain comprising an oxyalkylene group having an alkylene group having 2 to 4 carbon atoms; n is a number indicating the degree of polymerization of the oxyalkylene group. (The number corresponds to a molecular weight of 300 to 3000, preferably 700 to 2000; p is 2 to 6, preferably 2 to 4.)
Preferable examples of the polyhydric alcohol corresponding to R in Chemical Formula 1 include, for example, aliphatic dihydric alcohols (for example, ethylene glycol, propylene glycol, 1,4-butylene glycol, neopentane glycol), and trihydric alcohols (for example: Glycerin, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl- 2,3,4-pentanetriol, pentamethylglycerin, pentaglycerin, 1,2,4-butanetriol, 1, , 4-pentanetriol, trimethylolpropane, etc.), tetrahydric alcohols (eg erythritol, pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1, 2,3,5-pentanetetrol, 1,2,4,5-hexanetetrol, etc.), pentahydric alcohol (eg, adnit, arabit, xylit, etc.), hexahydric alcohol (eg, sorbit, mannit, exit) Etc.).

  The polyhydric alcohol is preferably a divalent to tetravalent alcohol, and propylene glycol, glycerin and the like are particularly preferable. The polyether polyol represented by the above chemical formula 1 can be produced by adding an alkylene oxide having 2 to 4 carbon atoms to such a polyhydric alcohol so as to have a desired molecular weight by a conventional method. Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, and butylene oxide, and it is particularly preferable to use propylene oxide.

  There is no restriction | limiting in particular as calcium carbonate, Heavy calcium carbonate, light calcium carbonate (precipitation calcium carbonate), etc. can be used. Heavy calcium carbonate having an average particle size of 0.05 to 10 μm, more preferably 1 to 5 μm is preferable. If the lower limit is not reached, secondary aggregation tends to occur and agglomeration tends to occur, and impregnation suitability tends to deteriorate. The surface of the decorative resin decorative board is not smooth, resulting in poor appearance. Light calcium carbonate refers to calcium carbonate that is chemically produced by firing limestone, and heavy calcium carbonate refers to finely powdered calcium carbonate prepared by dry or wet pulverization of white crystalline limestone.

The blending ratio of the organic resin and calcium carbonate is preferably 1: 2 to 20 in terms of solid content, and if the calcium carbonate is less than the lower limit, the warp of the decorative board is large. Strength will fall. More preferably, close packing is preferably performed using a plurality of types having different average particle diameters. For example, 80 to 50: 20 to 20 having an average particle diameter of 1 to 2 μm and an average particle diameter of 4 to 5 μm. When used at a ratio of 50, the filling rate is improved, the core layer becomes strong, and the moisture-proof performance is improved. Other than this blending ratio, aggregation occurs between the calcium carbonate particles, and the impregnation property to the inorganic fiber base material is lowered.

  The impregnation rate of the slurry to the base material is preferably 500 to 2000% by the calculation method represented by Equation 1, and if the impregnation rate exceeds the upper limit, the solid content is dropped off and is difficult to handle, and if the lower limit is not reached Delamination easily occurs.

  The content of the organic resin component in the prepreg is desirably 4 to 30% by the calculation method represented by Equation 2, heat resistance is deteriorated when the lower limit is not reached, and strength and adhesion are inferior when the upper limit is exceeded. It becomes easy.

  In addition, a silane coupling agent is blended in the slurry to improve adhesion to the resin-impregnated decorative paper described later, and reacts with the methylol group of amino-formaldehyde resin, the hydroxyl group of phenol-formaldehyde resin, and glass fiber. It is firmly bonded in three dimensions. The blending ratio of the organic resin component and the silane coupling agent is preferably 1: 0.01 to 0.5 in terms of solid content. If the silane coupling agent is less than the lower limit, sufficient adhesion with the surface design layer is achieved. If it exceeds the upper limit, the viscosity is remarkably increased and impregnation becomes difficult.

  Among the silane coupling agents, epoxy silane coupling agents are particularly preferable from the viewpoint of adhesion. For example, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ- Examples thereof include glycidyloxypropylmethyldiethoxysilane and glycidoxypropyltrimethoxysilane.

The thermosetting resin decorative board of the present invention is formed by laminating a plurality of prepregs obtained by impregnating a slurry into a substrate and drying, a resin-impregnated decorative paper as a decorative layer, and a resin-impregnated surface paper as necessary In addition, it is obtained by hot pressing with a flat plate press, a continuous press or the like, and the warpage is greatly reduced. The hot pressure conditions may be a temperature of 120 to 140 ° C. and a pressure of 40 to 70 kgf / cm ² .

The resin-impregnated decorative paper is obtained by impregnating a decorative liquid for decorative board of 80 to 160 g / m ^{2 with} a resin liquid composed of a thermosetting resin and drying it. As the thermosetting resin, the amino-formaldehyde described above is used. Resins are preferably used because of their excellent heat resistance and wear resistance.

The resin-impregnated surface paper is used for the purpose of improving the abrasion resistance when printing paper is used as decorative paper, and is made of a thermosetting resin on the surface paper that becomes transparent after impregnation of 20 to 40 g / m ^2. As the thermosetting resin, an amino-formaldehyde resin is preferably used as in the case of decorative paper.

  EXAMPLES Hereinafter, although an Example is given and demonstrated in detail, this invention is shown more concretely and is not specifically limited. In addition, the part in an Example and a comparative example shows solid content.

  A resol type phenol resin having a molar ratio of formaldehyde to phenol of 1.3 was reacted with a sodium hydroxide catalyst, and methanol was added to obtain an unmodified phenol-formaldehyde resin having a solid content of 50% by weight.

Core layer 100 g / m ² of glass fiber non-woven fabric, 12 parts of the unmodified phenol-formaldehyde resin, Adeka polyether P-1000 (manufactured by Adeka Co., Ltd., polypropylene glycol, average molecular weight 1000, hydroxyl group) 110) (30 parts with respect to 100 parts of phenol resin solid content), 60 parts of calcium carbonate having an average particle diameter of 2 μm, 27.5 parts of calcium carbonate having an average particle diameter of 5 μm, glycidoxypropyltrimethoxy A slurry containing 0.5 part of silane (SH-6040: manufactured by Toray Dow Corning Co., Ltd.) was impregnated so that the impregnation ratio shown in Formula 1 was 1000% to obtain a prepreg.

In this case, the weight of the solid content after slurry impregnation is 1100 g / m ² from Equation ¹ , and the slurry content is 1000 g / m ² by subtracting the weight of the glass fiber nonwoven fabric from 1100 g / m ² .

Furthermore, 1000 g / m ² contains 12 parts of phenol resin, 1.8 parts of polyether polyol, 87.5 parts of calcium carbonate, and 0.5 part of silane coupling agent, so that the organic resin component is 135.5 g / m ² and calcium carbonate are 859.5 g / m ² .

  Therefore, the content (%) of the organic resin component in the prepreg calculated from Equation 2 is 12.3% by 135.5 / (100 + 135.5 + 859.5) × 100.

Decorative layer A plain paper decorative paper having a basis weight of 120 g / m ² was impregnated with a melamine-formaldehyde resin so that the impregnation ratio represented by the formula 1 was 100% to obtain a melamine resin-impregnated decorative paper.

Thermosetting resin decorative board In order from the bottom, 1 sheet of melamine resin impregnated decorative paper, 4 sheets of prepreg, and 1 sheet of melamine resin impregnated decorative paper are laminated at 140 ° C., 100 kg / cm ² , using a flat finish plate. The thermosetting resin decorative board of Example 1 was obtained by hot pressing under the condition of 90 minutes.

Example 2 (when the polyether polyol is P-700)
In Example 1, it replaced with ADEKA polyether P-1000, and it implemented similarly except having used ADEKA polyether P-700 (Adeka Co., Ltd. make, polypropylene glycol, average molecular weight 700, hydroxyl value 130).

Example 3 (when the polyether polyol is P-2000)
In Example 1, it replaced with ADEKA polyether P-1000, and it implemented similarly except having used ADEKA polyether P-2000 (the product made by ADEKA, polypropylene glycol, the average molecular weight 2000, and the hydroxyl value 56).

Example 4 (When the blending ratio of the polyether polyol is close to the lower limit)
In Example 1, it implemented similarly except having made P-1000 into 0.4 part.

Example 5 (When the blending ratio of the polyether polyol is the upper limit)
In Example 1, it implemented similarly except having made P-1000 into 3 parts.

Comparative Example 1 (when the blending ratio of the polyether polyol is less than the lower limit)
In Example 1, it implemented similarly except having made P-1000 into 0.2 part.

Comparative Example 2 (when the blending ratio of the polyether polyol exceeds the upper limit)
In Example 1, it implemented similarly except having made P-1000 into 3.3 parts.

Comparative Example 3 (when no polyol polyether was blended)
In Example 1, it implemented similarly except not having mix | blended ADEKA polyether P-1000.

Comparative Example 4 (when the proportion of calcium carbonate is less than the lower limit)
In Example 1, it carried out similarly except having set it as 20 parts of calcium carbonate with an average particle diameter of 2 micrometers, and 8 parts of calcium carbonate with an average particle diameter of 5 micrometers.

Comparative Example 5 (when the proportion of calcium carbonate exceeds the upper limit)
The same procedure as in Example 1 was performed except that 190 parts of calcium carbonate having an average particle diameter of 2 μm and 80 parts of calcium carbonate having an average particle diameter of 5 μm were used.

Comparative Example 6 (in the case of only calcium carbonate having an average particle diameter of 2 μm)
In Example 1, it implemented similarly except having set it as 87.5 parts of calcium carbonate with an average particle diameter of 2 micrometers.

Comparative Example 7 (in the case of only calcium carbonate having an average particle diameter of 5 μm)
In Example 1, it implemented similarly except having set it as 87.5 parts of calcium carbonate with an average particle diameter of 5 micrometers.

  The evaluation results are shown in Table 1.

The evaluation method was as follows.
Dimensional change rate: Measured based on JIS K 6902; 1998 (Test method for thermosetting resin high-pressure decorative board).
Warpage test 1: The fiber direction of the decorative board is vertical, and the test piece is cut into a size of length × width = 900 mm × 300 mm. The test piece is allowed to stand in an environment of 40 ° C./30% for one week, placed on a horizontal plane, and the warp size at each corner is measured. The average of 4 points of warpage from the horizontal plane was taken as 3 mm or less, and more than that was taken as x.
Warpage test 2: The fiber direction of the decorative board is vertical, and the test piece is cut into a size of length × width = 900 mm × 300 mm. The test piece is allowed to stand in an environment of 40 ° C./90% for one week, placed on a horizontal plane, and the warp size at each corner is measured. The average of 4 points of warpage from the horizontal plane was taken as 3 mm or less, and more than that was taken as x.
Appropriate impregnation: A glass fiber base material that was able to impregnate the slurry for the desired resin ratio was evaluated as “◯”, and a glass fiber base material that was agglomerated and the impregnation amount could not be controlled was evaluated as “X”.

The structure sectional view of the thermosetting resin decorative board of the present invention.

Explanation of symbols

1 resin impregnated decorative paper layer 2 core layer 3 thermosetting resin decorative board

Claims (5)

And polypropylene glycol, and a thermosetting resin as the organic resin component, a slurry with a calcium carbonate as an inorganic filler, impregnated into woven or non-woven inorganic fibers, thermosetting of the dried prepreg as a core layer A resin decorative board,
In the slurry, 5 to 50 parts by weight of the polypropylene glycol is blended with respect to 100 parts by weight of the solid content of the thermosetting resin,
The blending ratio of the thermosetting resin and the calcium carbonate is 1: 2 to 20 in solid content ratio,
The calcium carbonate has a mean particle diameter of 1 to 2 μm and a mean particle diameter of 4 to 5 μm in combination . The thermosetting resin decorative board according to claim 1, wherein a silane coupling agent is blended in the slurry. The thermosetting resin decorative board according to claim 2, wherein a mixing ratio of the thermosetting resin and the silane coupling agent is 1: 0.01 to 0.5 in a solid content ratio. The thermosetting resin decorative board according to claim 1, wherein the polypropylene glycol has a number average molecular weight of 300 to 2500. The thermosetting resin decorative board according to claim 1, wherein the thermosetting resin is a phenol-formaldehyde resin, and the woven or non-woven fabric of inorganic fibers is a glass fiber non-woven fabric.