JP6377492B2 - Veneer - Google Patents

Description

The present invention relates to a decorative board.

  Melamine decorative veneer has abundant color patterns, and has excellent features such as impact resistance, bending strength, anti-contamination physical and chemical performance, and maintenance, so furniture and fixtures in public facilities such as stores and medical welfare facilities Is used in a wide range of applications from furniture to residential furniture.

  This decorative melamine board is generally composed of a decorative layer, a core layer, etc., the decorative layer is impregnated with melamine resin in the decorative paper, the dried resin-impregnated patterned paper, and the core layer is impregnated with phenolic resin in the kraft paper. A dried resin-impregnated core paper is used, and a surface protective layer, a balance layer, and an intermediate layer are provided as necessary.

  In recent years, the use of plant-derived raw materials has been studied due to growing environmental awareness, and the cashew oil according to the present invention has been applied to molded products and laminates for electronic use as a raw material when synthesizing phenol resins. I'm starting.

  For example, Patent Document 1 discloses a novolac-type cashew-modified phenol resin obtained by reacting phenols, cashew nut shell oil and aldehydes in the presence of an acid catalyst, and a dry oil-modified phenol for printed boards and electrical insulating boards.・ Technology using formaldehyde resin is disclosed.

  For example, Patent Document 2 discloses a phenol resin molding material containing a phenol resin containing a cashew-modified phenol resin and / or an oil-modified phenol resin and an inorganic filler.

Japanese Patent Laid-Open No. 5-279696 JP 2006-241337 A

  Here, the conventional melamine decorative board has very excellent impact resistance, dimensional stability, bending characteristics and the like, but has a tendency to be inferior in crack resistance and heat resistance. Specifically, cracks and cracks occur in harsh and harsh environments, and scratches and scratches occur in scenes that require a high degree of wear, such as the work table top. It was.

  The present invention provides a decorative board with improved crack resistance, heat resistance, and abrasion resistance while maintaining the excellent physical properties such as impact resistance, dimensional stability and bending characteristics of the conventional melamine decorative board. It is to provide.

The decorative board of the present invention comprises a core layer, which is a prepreg obtained by impregnating a fibrous base material with a resin liquid mainly composed of a plant-derived raw material-modified phenolic resin and dried, and a resin liquid mainly composed of a thermosetting resin. impregnating the decorative paper, and decorative layer composed of a resin-impregnated paper was dried, and then laminated, Ri Na are integrated by heat molding, the plant-derived material modified phenolic resin is Ru cashew nut shell oil modified phenol resin der It is characterized by that.

  The decorative board of the present invention is compatible with applications in more severe environments besides normal furniture and furniture. Moreover, since biomass raw material is used, it corresponds to recent environmental problems. As specific effects, cigarette resistance and crack resistance were improved compared to conventional decorative panels, and surprisingly, wear resistance was improved.

  The synthesis of the plant-derived raw material-modified phenol resin is preferably performed by a two-step reaction. In the first stage reaction, a monomer having a phenolic hydroxyl group, an aldehyde, and a catalyst are charged, heated with stirring, reacted for a predetermined time, and then naturally cooled. Next, in the second stage reaction, an aldehyde and a catalyst are further added, and the mixture is heated with stirring and reacted for a predetermined time. Such a two-stage reaction has the advantage that the unreacted monomer is volatilized and hardly remains in the final product. If a large amount of unreacted monomer remains in the resin, an odor problem occurs or the quality of the resin and the decorative board is not stable.

  Examples of plant-derived materials include cashew nut shell oil and lignin. In the present invention, it is preferable to use cashew nut shell oil.

  (A) Cashew nut shell oil is obtained by extracting an oily liquid from cashew nut shell, and has an advantage that the yield is very large and the supply thereof is not hindered. Cashew nut shell oil contains 70 to 99 mol% of cardanol as a main component, and cardol and the like as other components. Since these have a phenolic hydroxyl group, they can be reacted with aldehydes to synthesize a cashew nut shell oil-modified phenol resin. Cashew nut shell oil may be used as a reaction raw material as it is, but it contains impurities such as dimers and trimers. Therefore, it is better to use purified cashew nut shell oil purified by distillation, solvent extraction, etc. It is preferable because it is stable.

  In the present invention, one or two or more petroleum-derived (b) phenols can be used in combination with cashew nut shell oil. Examples of petroleum-derived phenols include phenol, cresol, resorcin, xylenol, octylphenol, phenylphenol, bisphenol A, bisphenol S, and bisphenol F. By using together plant-derived raw materials and petroleum-derived raw materials in an appropriate ratio, there is an effect that the physical properties of the molded decorative board are dramatically improved.

  The blending ratio of (a) cashew nut shell oil, which is a plant-derived raw material, and (b) phenols, which is a petroleum-derived raw material, is preferably 1: 0.1 to 10 by weight, and is 1: 0.3. ~ 8 is particularly preferred. When the amount of cashew shell oil increases, it tends to be separated when both components are mixed, and the resin tends to be unable to be synthesized.

  For the synthesis of the resin, (c) aldehydes are reacted with these monomers having a phenolic hydroxyl group. (C) Examples of aldehydes include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, paraaldehyde, glyoxal, hexamethylenetetramine, phenylacetaldehyde, o-tolualdehyde, benzaldehyde and the like, and one or more are selected. Use. Among these, it is preferable to use formaldehyde or paraformaldehyde having high reactivity during synthesis.

  As the blending amount of the aldehydes in the first stage, 0.01 to 1 part by weight of (c) aldehydes in solid content with respect to a total of 1 part by weight of (a) cashew nut shell oil and (b) phenols It is preferable to mix | blend and it is especially preferable to mix | blend 0.1-0.5 weight part. (C) When the amount of aldehyde increases, the number of crosslinking points increases, and the impact resistance of the molded decorative board tends to be inferior due to a dense structure in terms of molecular structure. When the amount decreases, the adhesion between the decorative layer, the core layer, and the core layers decreases, so that the boiling resistance tends to be inferior. Also, since puncture tends to occur, the cigarette resistance tends to be inferior.

  Moreover, it is preferable to add (c) aldehydes as a 2nd step after a 1st step. (C) As aldehydes, the same aldehyde as in the first stage can be used. The blending amount is 0.001 to 0.1 part by weight based on a total of 1 part by weight of (a) cashew nut shell oil and (b) phenols to synthesize the resin.

  The resin synthesis reaction is preferably carried out with a basic catalyst in both the first stage and the second stage. Examples of basic catalysts include alkali metals such as sodium and potassium, and oxides and hydroxides of alkaline earth metals such as magnesium and calcium, and amines such as triethylamine, triethanolamine, ethylenediamine and aqueous ammonia. 1 type or 2 types or more are selected and used. The catalyst is preferably used in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the total of (a) cashew nut shell oil and (b) phenols.

  As a method of reducing unreacted (c) aldehydes, a formaldehyde catcher agent may be added. As the catcher agent, urea is preferably used. As the reaction solvent, alcohols such as methanol, ethanol, propanol and butanol, aromatic hydrocarbons such as benzene, toluene and xylene, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone may be used.

  After completion of the reaction, it can be diluted with a solvent. Examples of the solvent include one or a mixture of two or more solvents such as methanol, ethanol, isopropanol, butanol, acetone, and methyl ethyl ketone.

  In addition, various additives such as antioxidants, preservatives, antifungal agents, tackifier resins, plasticizers, antifoaming agents, and wettability adjusting agents may be included during the synthesis of the resin liquid of the present invention.

  In the present invention, in forming the decorative board, at least one prepreg obtained by impregnating and drying a fibrous base material with a resin liquid mainly composed of a plant-derived raw material-modified phenol resin is used for the core layer.

  When the fibrous base material is impregnated with the resin liquid, an acidic catalyst may be blended as a curing agent. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, oxalic acid, p-toluenesulfonic acid, acetic acid, phosphoric acid and the like, or salts thereof, and these can be used alone or in combination of two or more.

  As the fibrous base material, it is preferable because the degree of biomass is improved by using wood pulp fibers, for example, bleached softwood, hardwood, unbleached kraft pulp, sulfite pulp, other wood pulp, etc. alone or mixed Used and made paper. An inorganic fiber base material can also be used, and examples thereof include nonwoven fabrics and woven fabrics made of inorganic fibers such as glass fibers, rock wool, and carbon fibers.

The basis weight of the fibrous base material, when considering the strength and impregnation efficiency veneer, using those 30~300g / ^{m 2,} particularly preferably those of 100 to 250 g / ^{m 2.} The impregnation rate is 20% to 200%, preferably 30% to 150% by the calculation method shown in Equation 1, and the core layer can be produced by drying.

  In the decorative board of the present invention, for example, a resin-impregnated decorative paper (hereinafter referred to as a decorative layer) can be disposed on one side of the core layer. As a result, the productivity, interlayer adhesion, and outermost wear resistance of the decorative board are further improved.

For the decorative layer, a resin liquid mainly composed of a thermosetting resin such as amino-formaldehyde resin, diallyl phthalate resin, or unsaturated polyester resin is used, and a decorative paper of 30 to 300 g / m ² for a thermosetting resin decorative board. Can be produced by impregnation so that the impregnation ratio represented by the formula 1 is 80 to 300%. Among these, amino-formaldehyde resins are more excellent in heat resistance and wear resistance.

  The decorative board of the present invention is obtained by hot pressing with a press such as a flat plate press or continuous press, and a decorative layer is formed on at least one side. When the decorative layer is formed only on one side, for example, a balance paper can be arranged on the other side. When the balance paper is provided, although the bendability is lowered, warping and breakage of the decorative board can be further suppressed.

As the balance paper, a decorative liquid whose basis weight is 18 to 40 g / m ² is a resin liquid mainly composed of a thermosetting resin, for example, melamine resin, urea resin, guanamine resin, diallyl phthalate resin, and acrylic resin. For example, a resin impregnated balance paper impregnated with 260 to 320% by the calculation method shown in Equation 1 and dried is used.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and demonstrated in detail about this invention, a specific example is shown and it does not specifically limit to these.

<Example 1>
(1) Production of plant-derived raw material-modified phenolic resin Purified cashew nut shell oil (Cashew Co., Ltd., product name: CX-1000, purity 98%) 86.8 parts by weight, phenol 128.2 parts by weight, 47% formalin 115.2 parts Part by weight, 2.0 parts by weight of 48% aqueous sodium hydroxide solution are charged into a separable flask equipped with a stirrer, reflux condenser and thermometer, heated to 95 ° C., stopped and allowed to cool naturally. It was. When the temperature dropped to 85 ° C., 13.6 parts by weight of 47% formalin and 0.3 part by weight of 48% aqueous sodium hydroxide solution were further added, and the temperature was raised to 95 ° C. again. In this state, synthesis was performed for 90 minutes while maintaining the temperature at 95 ± 5 ° C. Thereafter, the mixture was naturally cooled again, and when the temperature dropped to 60 ° C., 4.6 parts by weight of solid urea and 149.2 parts by weight of methanol were added and further cooled to room temperature to obtain a plant-derived raw material-modified phenol resin. It was.

(2) Manufacture of core layer As a fibrous base material, using a kraft paper having a basis weight of 198 g / m ² , a plant-derived raw material-modified phenol resin is impregnated with a calculation method defined by Equation 1 with an impregnation rate of 50%. Was impregnated and dried at 120 ° C. for 2 minutes to produce a prepreg.

(3) Production of decorative layer Using a decorative paper for a thermosetting resin decorative board having a basis weight of 140 g / m ² as a fibrous base material, a resin liquid mainly composed of a melamine-formaldehyde resin is expressed by the following equation (1). By the calculation method defined, impregnation was performed so that the impregnation rate was 110%, and dried at 120 ° C. for 2 minutes to produce a melamine resin-impregnated decorative paper.

(4) Manufacture of decorative board In order from the bottom, four prepregs as a core layer and one melamine resin-impregnated decorative paper as a decorative layer are laminated, using a flat finish plate, 132 ° C., 60 kgf / cm ² , A decorative panel was obtained by hot pressing under 60 minutes for integration.

<Examples 2 to 9, Comparative Example 1>
It implemented like Example 1 except having manufactured the plant origin raw material modified phenol resin by the mixing | blending shown in Table 1 and Table 2. FIG.

<Comparative example 2>
In Example 1, although it implemented similarly except having used lignin instead of cashew nut shell oil, the uniform resin liquid was not able to be obtained and the fibrous base material was not able to be impregnated.

The evaluation results are shown in Tables 1 and 2.

<Evaluation of physical properties of resin>
A physical property evaluation test was performed on the plant-derived raw material-modified phenolic resins of each Example and Comparative Example. The evaluation method is shown below.
F. F (unreacted formaldehyde concentration): Measured by the hydroxylammonium chloride method based on JIS K6910.
F. P (unreacted phenol concentration): Calculated from the peak area by an internal standard method using an Apiezon L column.
<Evaluation of physical properties of decorative sheet>
Moreover, the physical-property evaluation test was done about the decorative board of each Example and the comparative example. The evaluation method is shown below.
Cigarette resistance: JIS K6902 Method B Impact resistance: JIS K6902 Method B Abrasion resistance: JIS K6902
Dimensional stability: JIS K6902
Boiling resistance: JIS K6902
Crack resistance: A test piece of 50 mm × 150 mm is prepared, and a concave notch of 5 mm × 15 mm is put in the center in the longitudinal direction. The test piece is cured for 16 hours in a test room at a temperature of 40 ° C. and a humidity of 90%. Then, as shown in FIG. 2, after fixing the four corners of a test piece with an instrument, it is left to dry in 80 degreeC dryer. After drying for 9 hours, the length of the generated cracks was measured. Since one sample contains two cracks, this average value is shown in the table.
<Biomass degree>
The calculation method shown in Equation 2 was used. Here, the “solid content of all components in the first and second stages” corresponding to the denominator is a value obtained by removing impurities such as urea and methanol and water added before the reaction and cashew nut shell oil impurities.

  The decorative board of the examples, good results were obtained in each evaluation item, while maintaining the excellent physical properties such as impact resistance, dimensional stability, bending characteristics of the conventional melamine decorative board, further, heat resistance, Crack resistance and wear resistance were improved. On the other hand, the decorative board of the comparative example was inferior in any evaluation item.

The structure sectional view of the decorative board of the present invention. The perspective view which shows the test method of the crack resistance of the decorative board of this invention.

1 Resin impregnated decorative paper (decorative layer)
5 Resin impregnated core paper (core layer)
9 veneer

Claims (8)

Impregnating a decorative base paper with a core layer, which is a prepreg that has been impregnated and dried in a fibrous base material with a resin liquid mainly composed of plant-derived raw material modified phenolic resin, and then dried. A decorative layer made of resin-impregnated paper and laminated by hot pressing , wherein the plant-derived raw material-modified phenolic resin is a cashew nut shell oil-modified phenolic resin. A decorative board characterized by being . 2. The decorative board according to claim 1, wherein the plant-derived raw material-modified phenolic resin is synthesized by a reaction of (a) cashew nut shell oil- (b) phenols- (c) aldehydes. In the first stage reaction, the plant-derived raw material-modified phenol resin is obtained by reacting (a) cashew nut shell oil- (b) phenols- (c) aldehydes in the presence of a catalyst, and in the second stage, 3. The decorative board according to claim 2 , wherein the decorative board is obtained by adding (c) an aldehyde and reacting in the presence of a catalyst. The decorative board according to claim 2 or 3 , wherein a blending ratio of the (a) cashew nut shell oil and the (b) phenol is 1: 0.1 to 10 by weight. In the reaction of the first stage, 0.01 to 1 part by weight of (c) aldehyde is blended in solid content with respect to a total of 1 part by weight of (a) cashew nut shell oil and (b) phenols. The decorative board according to claim 3 or 4 , characterized by the above. In the reaction of the second stage, the amount of (c) aldehydes to be added is 0.001 in solids with respect to a total of 1 part by weight of (a) cashew nut shell oil and (b) phenols. The decorative board according to any one of claims 3 to 5, wherein ~ 0.1 part by weight is added. The decorative board according to any one of claims 1 to 6, wherein the cashew nut shell oil is a purified cashew nut shell oil. The decorative board according to any one of claims 2 to 7, wherein the reaction is performed with a basic catalyst.

Images