JPH03215511A - Resin composition for wooden decorative material, decorative material treated therewith, and composite panel made from the material - Google Patents

Abstract

PURPOSE:To prepare the title compsn. which, when applied in producing a wooden decorative material, gives a coating film having improved durability, hardness, and dimensional stability and being easily ground by compounding a specific unsatd. polyester, a polymerizable monomer contg. a specific polymerizable monomer as the essential component, and an org. peroxide. CONSTITUTION:The title compsn. having a viscosity (25 deg.C, Gardner) of 0.3-10P is prepd. by compounding 80-20 pts.wt. unsatd. polyester contg. polybasic acid units comprising unsatd. and satd. polybasic acid units in a molar ratio of the unsatd. to satd. acid units of (1:0)-(0.2:0.8) and having a mol.wt. of 300-5000 and an acid value of 50 or lower, 20-80 pts.wt. polymerizable monomer component contg. 3-50wt.% dicyclopentenyloxyalkyl (meth)acrylate of formula 1 (wherein R is H or methyl; R' is a 2-12C alkylene group or a 4-12C oxyalkylene group wherein at least two 2C or higher alkylene groups are linked through an oxygen atom), the sum of the polyester and the monomer component being 100 pts.wt., and 0.1-10 pts.wt. org. peroxide.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a resin composition for decorative wood materials, and more specifically, a resin composition for wood decorative materials that can be suitably used for architectural finishing materials such as flooring materials, furniture surface materials, etc. Related to resin compositions for decorative materials, treated wood decorative materials, and composite boards. [Prior Art] Wood has been widely used for decorative materials, interior materials, furniture, etc. because it is easy to process and has a beautiful grain. However, wood is porous and prone to wear, damage, fuzzing, etc. It also has the problem of staining, discoloration, and staining in a short period of time.

To solve this problem, a coating film is usually applied to the wood surface, but since the coating thickness needs to be 30μ or more, it spoils the appearance of the material of the wood, and it is also difficult to apply a coating of such thickness. Application of the film requires repeated undercoating and drying steps, which has the disadvantage of reducing productivity. As a remedy for this drawback, a decorative wood material (hereinafter referred to as veneer) is immersed in a mixture of synthetic resin, polymerizable monomer, etc., and the conduit portion of the veneer is impregnated with resin, etc. (hereinafter referred to as veneer). The veneer impregnated with the veneer is called impregnated veneer), and the veneer and synthetic resin are made into a composite by heat compression (wood-plastic combination, hereinafter referred to as W).
A method has been developed to achieve this (abbreviated as PC) (hereinafter referred to as WP).
The treated veneer is obtained by step C).

WPC significantly increases the surface strength of the treated veneer, but in order to use it as a flooring material for stores, etc., it must meet even harsher conditions, including greater durability, surface hardness, stain resistance, and dimensional stability. It is necessary and requires the color and feel of natural wood.

However, with conventional methods, cracks occur on the surface due to repeated heating and cooling, especially at the boundary between the spring wood and fall wood of treated veneers, and the concentration difference between the spring wood and fall wood cannot be maintained. However, it had the disadvantage of discoloration. In order to improve these drawbacks, methods for treating the veneer itself have been developed (Japanese Patent Application Laid-open No. 63-56402, Japanese Patent Application Laid-open No. 63-564).
No. 03) has the disadvantage that painting workability is significantly reduced.

In addition, the treated veneer requires surface grinding, which removes excess resin adhering to the surface, exposes the surface of the treated veneer, and creates the fine grain of natural wood.
It also improves the adhesion of top coat paint. Sandblasting, sandpaper, etc. are used as means for this grinding, but if the resin on the surface has insufficient curing properties or is extremely hard, the grinding process takes a long time and the work efficiency decreases significantly. There was a problem.

[Problem to be solved by the invention]

The object of the present invention is to solve the problems of the prior art described above, and to provide a treated veneer that has excellent durability, hardness, and dimensional stability of the coating film, and that allows easy grinding of the coating film. Resin composition for boards,
Our goal is to provide treated veneers and composite boards.

[Means to solve the problem]

In view of the above-mentioned problems, the present inventors conducted intensive research and found that an unsaturated polyester (A) having specific components, a molecular weight, and an acid value, and a specific polymerizable monomer that imparts excellent physical properties as well as air drying properties. Polymerizable monomer (B) containing as an essential component
The inventors have discovered that a composition containing an organic peroxide (C) can solve the above problems, and have arrived at the present invention.

That is, the present invention contains an unsaturated polyester (A), a polymerizable monomer (B), and an organic peroxide (C), and has a viscosity (25°C, Gardner) of 0. 3 to 10 poise, and the unsaturated polyester (A) contains unsaturated polybasic acid (a) and saturated polybasic acid Φ) as polybasic acid components in a molar ratio (a): (b) = 1-0.2: O ~ 0.8 (7)
The molecular weight is 300 to 5,000, and the acid value is 5.
0 or less, the amount of the polymerizable monomer (B) used is 20 to 80% by weight based on the total amount of (A) and (B), and the polymerizable monomer contains the general formula (1) [In the formula, R is a hydrogen atom or a methyl group, R' is 2 to 12
alkylene group having at least 2 carbon atoms or at least 2 carbon atoms
dicyclopentenyloxyalkyl acrylate and dicyclo It contains 3 to 50% by weight of at least one type of pentenyloxyalkyl methacrylate, and the amount of the organic peroxide (C) used is 0.0% based on the total amount of (A) and (B). The present invention relates to a resin composition for a veneer having a concentration of 1 to IO% by weight, a decorative wood material and a composite board in which the composition is impregnated into a decorative wood material and cured.

The unsaturated polyester (A) used in the present invention is obtained, for example, by a condensation reaction of a polybasic acid component and a polyhydric alcohol component.

The polybasic acid component includes an unsaturated polybasic acid (a) and a saturated polybasic acid (b) in a molar ratio of (a):(b) -1 to 0.2.
:O~0.8, preferably 1~O. 3:O~0.7
used at a rate of The amount of unsaturated polybasic acid (a) is 0.
If the amount is less than 2 moles, the resin composition will not be sufficiently cured and the surface hardness will be insufficient when the impregnated veneer is heated and compression molded to form a treated veneer, and cracks will easily occur when used as a flooring material.
Furthermore, when grinding the surface of the treated veneer, sanding cannot be done sufficiently, resulting in a significant decrease in grinding workability.

As the unsaturated polybasic acid of the unsaturated polyester, for example, maleic anhydride, maleic acid, fumaric acid, itaconic acid, etc. are used. Further, as the saturated polybasic acid, for example, phthalic acid, maleic anhydride, isophthalic acid, tetrahydrophthalic anhydride, hymic acid, trimellitic acid, etc. are used. These may be used alone or in combination of two or more.

Examples of the polyhydric alcohol of unsaturated polyester include ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, hydrogenated bisphenol A1 glycerin, Examples include trimethylolpropane, pentaerythritol, trimethylolethane, etc., and these may be used alone or in combination of two or more.

In addition, as materials other than the above-mentioned components, for example, allyl-containing compounds such as trimethylolpropane diallyl ether, epoxy resins such as Epicote 828 (trade name, manufactured by Shell Chemical Co., Ltd.), petroleum, resins, etc. may be used in combination.

Unsaturated polyester (A) is synthesized by a known method. For example, one or more of each of an unsaturated polybasic acid, a saturated polybasic acid and a polyhydric alcohol used as necessary, and other materials as necessary are charged into a reaction vessel,
The reaction bond water is heated at 0°C to 220°C for 1 to 20 hours while cooling, and the molecular weight and acid value are adjusted to a predetermined molecular weight and acid value. One or more of each of 8 moles or less of a saturated polybasic acid and a polyhydric alcohol were charged into a reaction vessel, and the mixture was heated at 140°C to 220°C for 1 to 1
After heating for 0 hours, add one or more unsaturated polybasic acids of 0.2 mol or more and other materials if necessary, heat again at 140°C to 220°C for 1 to 10 hours, and heat to a predetermined temperature. Adjust so that the characteristics are as follows.

In the present invention, the ratio of polybasic acid and polyhydric alcohol used is not particularly limited and can be any known ratio, but it is preferable to carry out the reaction with the polyhydric alcohol in excess of 5 to 50 mol%. .

Animal and vegetable oil In the present invention, the molecular weight of the unsaturated polyester (A) is adjusted to be in the range of 300 to 5,000.
If the molecular weight is less than 300, the coating film after curing will be brittle and cracks will easily occur on the surface of the treated veneer during thermal cycle tests, etc., and if the molecular weight exceeds 5,000, penetration into the veneer conduit portion will be insufficient. As a result, the resin adheres only to the surface of the veneer, making it impossible to obtain a natural wood color after grinding, and cracks easily occur on the surface of the treated veneer during thermal cycle tests.

Further, the acid value of the unsaturated polyester is adjusted to be 50 or less, preferably 30 or less. If the acid value exceeds 50, the water resistance of the treated veneer will be significantly reduced.

The polymerizable monomer (B) used in the present invention includes dicyclopentenyloxyalkyl acrylate and dicyclopentenyloxyalkyl methacrylate (hereinafter referred to as dicycloacrylate derivatives) represented by the general formula (I). At least one species is present in the polymerizable monomer at a concentration of 3 to 50%.
% by weight, preferably 5 to 30% by weight. If the amount of dicycloacrylate derivative used is less than 3% by weight, toughness and air drying properties cannot be imparted, and if the amount is less than 3% by weight,
If it exceeds 100%, the compatibility with the unsaturated polyester (A) will deteriorate, and the composition will become cloudy or separate.

This dicycloacrylate derivative has α. It has a dicyclopentenyl group that imparts β and an oxyalkylene group (-0-R'-0-) that imparts toughness, so when it is copolymerized with the unsaturated polyester (A), it imparts toughness to the coating film. It can provide air-drying properties, and it also prevents cracking during thermal cycle tests on treated veneers and significantly improves surface grindability.

Dicycloacrylate derivatives are known compounds, such as dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxypyl acrylate, dicyclopentenyloxypyl methacrylate, and the like. These compounds are produced by adding alkylene glycol or oxyalkylene glycol to dicyclopentadiene as shown in Japanese Patent Publication No. 61-43337, and adding the resulting alkylene glycol monodicyclopentenyl ether to acrylic acid or methacrylic acid. It can be produced by condensation reaction with methyl acrylate or ester exchange reaction with methyl acrylate or methyl methacrylate.

It can also be produced by addition-reacting alkylene glycol monoacrylate or alkylene glycol monomethacrylate to dicyclopentadiene as shown in Japanese Patent Publication No. 57-200331.

Other polymerizable monomers (B) used in the present invention include, for example, styrene, vinyltoluene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylic ester, methacrylic ester, glycidyl methacrylate, 2-
Hydroxyethyl methacrylate, 2-hydroxybutylene acrylate and the like can be mentioned. Two or more of these may be used in combination.

The amount of the polymerizable monomer (B) used is 20 to 80% by weight, preferably 30 to 70% by weight based on the total amount of (A) and (B).
Weight%. If the amount of the polymerizable monomer (B) used is less than 20% by weight, the reaction with the unsaturated polyester (8) will not be sufficient and a highly hard coating film will not be obtained, and if it exceeds 80% by weight, the curability will be poor. In addition, the quality of the finish, especially the natural color tone of the wood, is reduced.

Examples of the organic peroxide (C) used in the present invention include ketone peroxides, peroxyketals, hydroperoxides, peroxydicarbonates, and peroxyesters. The amount of the organic peroxide (C) used is 0.1 to 10% by weight, preferably 0.1 to 10% by weight, based on the total amount of the unsaturated polyester (^) and the polymerizable monomer (B). It is 1 to 5.0%. This amount is 0.
If it is less than 1% by weight, the coating film after heat molding will not be sufficiently cured, and the surface hardness, thinner resistance, etc. will decrease, and if it exceeds 10% by weight, the organic peroxide will act as a plasticizer. The cured coating becomes soft.

Viscosity of the resin composition for veneers of the present invention (Gardna, 25°C
) is adjusted to 0.3 to 10 voices. Viscosity is 0. If it is less than 3 voids, impregnation into the veneer becomes easy, but the amount of polymerizable monomer (B) must be greater than 80% by weight, and the coating film after heat forming becomes brittle. Also 1
If it exceeds 0 poise, the impregnability of the veneer will decrease, and a molded product with toughness will not be obtained.

A treated veneer is obtained by impregnating and curing the veneer composition of the present invention in a veneer.

A known method can be used to impregnate the veneer with the resin composition. Generally, the veneer is depressurized (2~
After impregnating the composition with the composition in a state where it is easy for the composition to enter the conduit in the veneer, the pressure is immediately released, and the pressure is released for several hours (usually 30 kg/cJ) under normal pressure or increased pressure (usually 30 kg/cJ).
This is usually done by leaving it for about 10 to 24 hours). The impregnated veneer thus obtained is pressurized and heated (for example, at 80°C to 150°C for 3 to 20 minutes, at a rate of 8 to 20 kg/
c) and hardened to form a treated veneer. The treated veneer may be used by adhering to a base material such as plywood, or the impregnated veneer may be cured by pressurizing and heating at the same time as adhesion. A known adhesive can be used to bond the treated veneer and plywood.

The veneer is not particularly limited, and may include cedar, pine,
It may be a coniferous wood such as Japanese cypress or a broadleaf wood, an evergreen wood such as cedar or oak, or a deciduous wood such as birch, beech, or oak.

Treated veneer is bonded to a base material such as plywood to make a composite board.
The surface of the treated veneer bonded to plywood is ground with sandpaper, plasto sander, puff sander, etc. to remove excess resin adhering to the surface, exposing the surface layer and revealing the fine grain of the wood. At the same time as it is released, it is given adhesion with top coat paint (urethane paint, Lasocar paint, etc.). The treated veneer and composite board obtained using the resin composition of the present invention are easy to grind and have excellent workability.

〔Example〕

The present invention will be explained below with reference to Examples and Comparative Examples. "Parts" and "%" in the following examples mean "parts by weight" and "% by weight" unless otherwise specified.

<Production of unsaturated polyester (A)> (1) Production of unsaturated polyester (A-1) 770 parts (7.26 mol) of diethylene glycol was placed in a 2-liter flask equipped with a stirrer, gas introduction tube, reflux condenser, and thermometer. ,
391 parts (2.36 mol) of isophthalic acid and 0.1 part of hydroquinone were added, and the temperature was raised to 220°C over 4 hours while blowing nitrogen gas.
ag/g). The reaction time required 6 hours. Then, it was cooled to 120°C, and maleic anhydride 3
55 parts (3.62 moles) were added, the temperature was raised again to 220°C, and the esterification reaction proceeded at the same temperature while measuring the acid value of the contents in the kettle. After heating for 10 hours, an unsaturated polyester (A-1) having an acid value of 12.5 was obtained.

The molecular weight was determined by HLC (Hispi-1' Rekind Chromatograph, Hitachi Chromatograph 635, manufactured by Hitachi, Ltd.).
-0200), and the average molecular weight was 1,850 when measured using boristyrene as a standard substance.

(2) Production of unsaturated polyester (A-2) In the same manner as in (1), 2! diethylene glycol 892 in a flask of
parts (8.42 mol), 381 parts (2.30 mol) of isophthalic acid
mole) and hydroquinone 0. Prepare 1 part, 22
The temperature was raised to 0°C, and the reaction was continued at the same temperature until the acid value reached 10. The time required was 4 hours.

It was then cooled to 120°C, and 525 parts of maleic anhydride (
5.36 mol) was added, and the temperature was raised to 220° C. in the same manner as in (1), and the esterification reaction was proceeded while measuring the acid value of the contents in the pot. After heating for 6 hours, an unsaturated polyester (A-2) having an acid value of 18.5 was obtained. When its molecular weight was measured in the same manner as in (1), the average molecular weight was 2,300.

(3) Production of unsaturated polyester (A-3) In the same manner as in (1), add 10 dipropylene glycol to a 2i flask.
26 parts (7.66 mol), adivic acid 186 parts (1.2
7 mol), 212 parts (1.28 mol) of isophthalic acid and 0.7 mol of hydroquinone. 1 part was charged, the temperature was raised to 220''C, and the reaction was carried out at the same temperature until the acid value reached 12.5. The required time was 4.5 hours.

It was then cooled to 120°C, and 375 parts of maleic anhydride (
3.83 mol) and heated to 220°C in the same manner as in (1).
The esterification reaction was carried out while measuring the acid value of the contents in the pot. After heating for 9.5 hours, an unsaturated polyester (A-3) having an acid value of 8.7 was obtained. Its molecular weight (1)
When measured in the same manner as above, the average molecular weight was 1,850. Production of dicyclopentenyloxyethyl methacrylate> 660 parts of dicyclopentadiene, 160 parts of ethylene glycol, and 4 parts of para-toluenesulfonic acid were charged into a 22 flask, heated to 120°C, heated at the same temperature for 4 hours, and then heated to 80°C. The mixture was cooled to 0.degree. C., then 430 parts of methacrylic acid and 4 parts of valatoluenesulfonic acid were added, the temperature was raised to 100.degree. C., and the mixture was heated at the same temperature for 5 hours while removing distilled water. The resulting reaction product was neutralized with magnesium oxide. Furthermore, the reaction product was washed with water, and water was removed by vacuum distillation to obtain dicyclopentenyloxyethyl methacrylate.

Examples 1 to 4 and Comparative Examples 1 to 3 Resin compositions for veneers were prepared with the compositions and blending amounts shown in Table 1, respectively.

<Test example> Thickness l. Put the 5III1 oak veneer into a 4i stainless steel tank, reduce the pressure inside the tank to 4mHg/cd,
After standing for 4 hours, the pressure was released, and each resin composition prepared according to Table 1 was injected, and the pressure inside the tank was reduced to 30 kg pressure/
CD and left in that state for 16 hours, the pressure was released to obtain an impregnated veneer. This impregnated veneer was taken out and cured in a hot press (130°C for 3 minutes, 12 kg pressure/C-) to obtain a treated veneer. Furthermore, this treated veneer was adhered to plywood using an adhesive to obtain a composite board. The grindability, finishability, hardness, and durability (cold/hot cyclic test) of this composite plate were examined as follows, and the results are shown in Table 2.

Grindability: The ease of grinding was compared when the surface of a treated veneer on a composite board was ground using a Belt Sangu made of waterproof paper #240.

◎...The surface can be completely polished after several times of polishing.

○...The surface can be completely ground by polishing twice.

△...The surface can be completely ground by polishing 5 times.

×...The surface can be completely ground by polishing 8 times.

Finishing (visual): ○...The pattern of the spring wood and winter wood of the treated veneer on the composite board is clearly visible.

Δ...The pattern of the spring wood and winter wood of the treated veneer on the composite board appears slightly blurred.

Hardness: Pencil hardness: A Mitsubishi Yuni pencil was pressed firmly against the surface of the treated veneer at an angle of 45 degrees to determine the hardness until no scratches were left.

Barcol hardness: The hardness of the composite board surface was investigated using Barcol 935.

Cold and heat cycling test: The composite board was left in a dryer at 80°C for 2 hours, then immediately placed in a refrigerator at -20°C for 2 hours, and then
The test was repeated as a cycle, and the occurrence of cracks on the surface of the composite board was visually observed. From the results shown in Table 2, the resin composition for veneers of the present invention has excellent grindability, and the treated veneer and composite board obtained is shown to have high hardness and high durability.

〔Effect of the invention〕

According to the resin composition for veneers of the present invention, treated veneers and composite boards with excellent durability, hardness, dimensional stability, and grinding workability can be obtained.

Claims (1)

[Claims] 1. Contains an unsaturated polyester (A), a polymerizable monomer (B) and an organic peroxide (C), and has a viscosity (25°C, Gardner) of 0.3 to 10 poise The unsaturated polyester (A) is a resin composition, and the unsaturated polyester (A) has an unsaturated polybasic acid (a) and a saturated polybasic acid (b) as polybasic acid components in a molar ratio of (a):(b)=1. 0.2:0 to 0.8, the molecular weight is 300 to 5,000, and the acid value is 50 or less, and the amount of the polymerizable monomer (B) used is the same as that of (A). It is 20 to 80% by weight based on the total amount of (B), and the polymerizable monomer has the general formula (I) ▲numeric formula, chemical formula, table, etc.▼(I) [In the formula, R is hydrogen Atom or methyl group, R' is 2-12
alkylene group having at least 2 carbon atoms or at least 2 carbon atoms
dicyclopentenyloxyalkyl acrylate and dicyclo It contains 3 to 50% by weight of at least one type of pentenyloxyalkyl methacrylate, and the amount of the organic peroxide (C) used is 0.1 to 10% by weight based on the total amount of (A) and (B). Resin composition for decorative wood materials. 2. A treated wood decorative material obtained by impregnating and curing the resin composition for wood decorative materials according to claim 1 into a wood decorative material. 3. A composite board formed by adhering the treated wood decorative material according to claim 2 to a base material.