JPH07100727B2 - Resin composition for wood decorative material, treated wood decorative material and composite board - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a resin composition for wood decorative materials, more specifically a wood decorative material that can be suitably used as a finishing material for construction such as flooring materials and furniture surface materials. TECHNICAL FIELD The present invention relates to a resin composition for wood, a treated wood decorative material, and a composite board.

[Conventional technology]

Conventionally, wood is widely used as a decorative material, an interior material, furniture, etc. because it is easy to process and has a beautiful grain.

However, since wood is porous, there is a problem that abrasion, damage, feathering and the like are likely to occur, and that contamination and discoloration occur and stain in a short time.

In order to solve this purpose, a coating film is usually applied on the surface of wood. However, the coating film thickness needs to be 30 μm or more, which impairs the view of the material of the wood and the coating of such thickness. In order to apply a film, the undercoating and drying steps must be repeated, which has the drawback of reducing productivity.

As a remedy for this drawback, a wooden decorative material (hereinafter referred to as a veneer) is dipped in a mixture of synthetic resin, polymerizable monomer, etc.,
The conduit portion of the veneer is impregnated with resin (hereinafter, the veneer impregnated with the mixture is referred to as the impregnated veneer), and heated and compressed to form a composite of veneer and synthetic resin (wood, plastic combination, hereinafter, WPC). A method for achieving this is being developed (hereinafter, the one obtained by WPC is referred to as a treated veneer). This WPC significantly increases the strength of the treated veneer surface, but to use it as a flooring material for stores, etc., it has the color tone and feel of natural wood, as well as durability, surface hardness, and resistance to harsh conditions. It is required to have both stain resistance and dimensional stability.

However, the treated veneer obtained by the conventional method, especially the treated veneer using pine wood as a veneer, is affected by the tar and the like contained in the pine wood, and the color tone and feel peculiar to wood are impaired, and The boundary between the lumber part and the autumnal part has cracks on the surface due to repeated heat and cooling, and the concentration difference between the spring part and the autumnal part cannot be maintained as it is, and there is a drawback that the discoloration occurs. In order to improve these drawbacks, a method of treating the veneer itself has been developed (Japanese Patent Laid-Open Nos. 63-56402 and 6-62).
No. 3-56403), the workability of painting is significantly reduced.

The treated veneer requires surface grinding, which removes excess resin adhering to the surface and exposes the surface of the treated veneer to give a fine grained natural wood finish and topcoat. Improves paint adhesion. As the grinding means, sandblasting, sandpaper, etc. are used, but the curability of the resin on the surface is insufficient,
When it is extremely hard, there is a problem that the grinding process takes a long time and work efficiency is significantly reduced.

[Problems to be Solved by the Invention]

The object of the present invention is to solve the above-mentioned problems of the prior art and to greatly improve the finishability (grain pattern) of the treated veneer even when pine wood is used for the veneer, and at the same time the durability of the coating film. Another object of the present invention is to provide a resin composition for woody decorative material, a treated woody decorative material and a composite board, which can improve hardness and dimensional stability and can easily grind a coating film.

[Means for Solving the Problems]

The present inventors, in view of the above problems, as a result of earnest research, consisting of a specific acid component and a polyhydric alcohol component, an unsaturated polyester having a specific molecular weight and acid value, styrene as a polymerizable monomer, and organic T-as peroxide
The inventors have found that a composition containing butylperoxyisopropyl carbonate can solve the above-mentioned problems and have reached the present invention.

That is, the present invention provides (A) (a) the general formula (I) (In the formula, R ₁ , R ₂ and R ₃ are each independently a carbon number of 1 to 1.
(Meaning 15 alkyl groups), (b) diethylene glycol, (c) isophthalic acid and (d) maleic anhydride in a molar ratio of (a):
(B): (c): (d) = 0.03-0.30: 1.47-0.70: 0.20
Unsaturated polyester having a molecular weight of 300 to 5000 and an acid value of 50 or less obtained by reacting at a composition ratio of 0.80: 0.80 to 0.20, (B) styrene to 20 to the total amount of (A) and (B). 80% by weight and (C) t-butylperoxyisopropyl carbonate in an amount of 0.1-10.0% by weight based on the total amount of (A) and (B), and a viscosity (25 ° C, Gardner) of 100-500 centipoise. Board resin composition,
The present invention relates to a treated wood decorative material obtained by impregnating a wood decorative material with the resin composition for a single plate and curing the same, and a composite plate obtained by adhering the treated wood decorative material as a base material.

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

As the polyhydric alcohol component, the glycidyl ester (a) and diethylene glycol (b) represented by the general formula (I) are used. These are used in a molar ratio of (a) :( b) = 0.03 to 0.3: 1.47 to 0.70, preferably 0.1.
05-0.25: 1.14-0.65.

The glycidyl ester (a) improves the chemical resistance of the treated veneer, prevents the occurrence of cracks due to repeated cold and heat, and imparts dimensional stability. Diethylene glycol (b) is
When the pine wood is used as the veneer, the finish (grain pattern) of the treated veneer is significantly improved, and the combination with the above-mentioned component (a) prevents the occurrence of cracks during repeated heat and cold.

If the amount of glycidyl ester (a) used is less than 0.03 mol, cracks will occur on the surface of the treated veneer due to repeated cold and heat, and if it exceeds 0.30 mol, the hardness of the treated veneer will be insufficient and grinding workability will be remarkably increased. Lower. When the amount of diethylene glycol (b) used exceeds 1.47 mol, the molecular weight of unsaturated polyester (A) becomes small, the surface hardness of the treated veneer is insufficient, and cracks occur when it is used as a flooring material, and less than 0.70 mol. In the case of using a pine wood as the veneer, the finishability of the treated veneer is significantly reduced.

Examples of the glycidyl ester (a) represented by the above general formula (I) include Kajura E manufactured by Shell Chemical Co., Ltd.

As the polyhydric alcohol component, a polyhydric alcohol component other than the above-mentioned components (a) and (b) is used in a range that does not affect the crack resistance and finishability of the treated veneer by repeated cold and heat, specifically (a). ) And (b) relative to the total amount of components
It can be used in the range of 0.5 mol% or less. As this polyhydric alcohol component, for example, ethylene glycol,
Propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, hydrogenated bisphenol A, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, etc. Is mentioned. You may use these 1 type or in mixture of 2 or more types.

As the polybasic acid component, isophthalic acid (c) and maleic anhydride (d) are used, and the use ratio thereof is (c) :( d) = 0.20 to 0.8: 0.80 to 0.20, preferably 0. .
25 to 0.60: 0.75 to 0.40. These components, in combination with the above components (a) and (b), remarkably improve the finishability of the treated veneer particularly when pine wood is used as the veneer. For example, when phthalic anhydride or maleic anhydride is used, when the veneer made of pine wood is used as a treated veneer, the grain pattern is blurred and the intended finish cannot be obtained. The reason for this is not clear, but it is presumed that the cured product of the resin composition using the components (c) and (d) has a refractive index close to that of pinewood.

If the amount of the isophthalic acid (c) used is less than 0.20 mol, the finish of the treated veneer made of pine wood is not sufficient, and 0.80
If it exceeds the mol, the resin composition is insufficiently cured when the impregnated veneer is subjected to heat compression molding to form a treated veneer, and the surface hardness is poor.

As the polybasic acid, a polybasic acid other than the above-mentioned components (c) and (d) is used within a range that does not affect the finishability and curability of the treated veneer, specifically, the components (c) and (d). It can be used in an amount of 0.3 mol% or less based on the total amount. Examples of the polybasic acid include unsaturated polybasic acids such as fumaric acid and itaconic acid, and saturated polybasic acids such as phthalic anhydride, adipic acid, tetrahydrophthalic anhydride, hymic acid and trimellitic acid. You may use these 1 type or in mixture of 2 or more types.

The unsaturated polyester (A) is synthesized by a known method. For example, diethylene glycol, glycidyl ester and isophthalic acid are charged into a reaction kettle, heated at 180 to 230 ° C for 2 to 10 hours while removing reaction water, reacted until a predetermined acid value is reached, and then cooled to 120 ° C. Then, maleic anhydride is charged, and the mixture is heated again at 180 to 230 ° C. for 3 to 10 hours and adjusted to have a predetermined molecular weight and acid value. In the present invention, the polyhydric alcohol component is allowed to react in an excess of equimolar or more with respect to the polybasic acid component, so that the molecular weight and acid value of the unsaturated polyester (A) can be easily adjusted.

The molecular weight of the unsaturated polyester (A) is adjusted to be in the range of 300 to 5000, preferably 700 to 3000. If the molecular weight is less than 300, the coating film after curing is brittle, and the crack resistance of the treated veneer after repeated cold and heat is poor, and if it exceeds 5000, the penetration into the conduit part of the veneer is insufficient and only the veneer surface is present. The resin adheres to and the natural woody color tone cannot be obtained after grinding, and the crack resistance of the treated veneer after repeated cold and heat is poor.

The acid value of the unsaturated polyester (A) is 50 or less, preferably
Adjusted to be 30 or less. If the acid value exceeds 50, the water resistance and chemical resistance of the treated veneer will be significantly reduced.

The amount of styrene (polymerizable monomer) (B) used in the present invention is 20 to 80% by weight, preferably 30 to 70% by weight, based on the total amount of (A) and (B). If the amount used is less than 20% by weight, the reaction with the unsaturated polyester (A) is insufficient and a coating film having high hardness cannot be obtained. On the other hand, if the amount exceeds 80% by weight, the curability is deteriorated and the finishability, especially The color tone of natural wood deteriorates. Styrene (B), in combination with the unsaturated polyester (A), remarkably improves the finishability of a treated veneer using pine wood. For example, when styrene is replaced with another polymerizable monomer such as methyl methacrylate or vinyltoluene, the desired finish of the treated veneer using pinewood cannot be obtained. The reason for this is not clear, but it is presumed that it is due to the relationship between the refractive indexes of the pine wood and the cured product, as described above.

As the polymerizable monomer, a polymerizable monomer other than styrene,
It can be used in a range that does not affect the finish of the treated veneer, specifically, in a range of 30% by weight or less based on the total amount of styrene. Examples of the polymerizable monomer include vinyltoluene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2 −
Examples thereof include hydroxy (meth) propyl acrylate. You may use these 1 type or in mixture of 2 or more types.

The amount of t-butylperoxyisopropyl carbonate (organic peroxide) (C) used in the present invention is 0.1 to 10.0% by weight, preferably 0.1 to 10.0% by weight, based on the total amount of the unsaturated polyester (A) and styrene (B). Is 0.1 to 5.0% by weight. If this amount is less than 0.1% by weight, the curing of the coating film after heat molding will be insufficient, and the surface hardness, thinner resistance, chemical resistance, etc. will decrease, and if it exceeds 10% by weight, organic peroxides will The plasticizer acts to make the coating film soft after heat molding. t
-Butyl peroxyisopropyl carbonate (C)
The combination of the unsaturated polyester (A) and styrene (B) remarkably improves the finishability of a treated veneer made of pine wood. For example, when benzole peroxide, t-butylperoxybenzoate, or the like is used instead of t-butylperoxyisopropylcarbonate, the pine wood grain pattern does not appear three-dimensionally even when the pine wood is used as a treated veneer. Finished in a lean form.

As the organic peroxide, an organic peroxide other than t-butylperoxyisopropyl carbonate is used in a range that does not affect the finish of the treated veneer, specifically, with respect to the total amount of t-butylperoxyisopropyl carbonate (C). 0.5
It can be used in the range of not more than wt%. Examples of the organic peroxide include benzol peroxide, dicumyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and cumene hydroperoxide.

The viscosity of the resin composition for a single plate of the present invention is adjusted to be 100 to 500 centipoise (Gardner, 25 ° C.). If the viscosity is less than 100 centipoise, the veneer can be easily impregnated with the composition, but it is necessary to use more than 80% by weight of styrene (B), and the coating film after heat molding becomes brittle. On the other hand, when it exceeds 500 centipoise, the impregnating property of the composition into a single plate is deteriorated and a tough molded product cannot be obtained.

A treated veneer is obtained by impregnating a veneer with the resin composition for veneers of the present invention and curing. The veneer is not particularly limited to pine, and may be coniferous wood such as cedar and cypress, hardwood, or single green wood such as oak, Deciduous wood materials such as beech, birch and oak may be used.

As a method of impregnating the single plate with the resin composition, a known method can be adopted. Generally, decompress the veneer (2
~ 5 mmHg / cm ² ), and impregnating the composition so that the composition easily enters the conduit in the veneer, then immediately decompressing,
At normal pressure or pressure (usually 30 kg / cm ² ) for several hours (usually
It is performed by leaving it for about 10 to 24 hours. The impregnated veneer thus obtained is pressed and heated (for example, 80 to 15
The resin composition is cured at 0 ° C. for 3 to 20 minutes at 8 to 20 kg / cm ² ) to obtain a treated veneer.

The treated veneer is bonded to a base material such as plywood to form a composite plate.
A known adhesive can be used to bond the treated veneer and the plywood. In addition, the impregnated single plate may be adhered to the substrate when being pressed and heated to be cured. The treated veneer bonded to plywood is
The surface is ground with sandpaper, blast sander, buff sander, etc. to remove the excess resin adhering to the surface, the surface layer is exposed, and the fine grain of the original wood is revealed, and the top coat paint (urethane paint, urethane paint, Adhesiveness with lacquer paint etc. is given.

The resin composition for a veneer of the present invention is particularly effective for pine wood, which has the most difficult finish after impregnation and heat molding, but can also be used for veneers made of other various types of wood. Further, the treated veneer and composite plate obtained by using the veneer resin composition of the present invention are easy to grind and have excellent workability.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to Examples. "Parts" and "%" in the following examples mean "parts by weight" and "% by weight" unless otherwise specified.

<Manufacture of Unsaturated Polyester> (1) Manufacture of Unsaturated Polyester (A-1) In a flask 2 equipped with a stirrer, a gas introduction tube, a reflux condenser and a thermometer, Cardura E (manufactured by Shell Chemical Co., general formula In (I), R ₁ and R ₃ are methyl groups, and R ₂ has 12 to 12 carbon atoms.
Is an alkyl group of 14 and has a molecular weight of 250 and is an acrylglycidyl ester] 170 parts (0.68 mol), diethylene glycol 1011 parts (9.54 mol), isophthalic acid 339 parts (2.0
4 mol) and 0.1 part of hydroquinone are added, the temperature is raised to 220 ° C. in 4 hours while blowing nitrogen gas, and the acid value becomes 1 at the same temperature.
The reaction was allowed to proceed to 2 (KOH mg / g). The reaction time required 3 hours. Then cool to 120 ° C and maleic anhydride 467.
Parts (4.77 mol) and 50 parts of xylol as a circulating solvent were charged, the temperature was again raised to 220 ° C. in 4 hours, and the esterification reaction was allowed to proceed while measuring the acid value of the contents in the kettle at the same temperature. After heating for 6 hours, the acid value was 15.8, the temperature was cooled to 200 ° C., and the amount of nitrogen gas was increased to remove the xylol in the kettle to proceed the reaction. The mixture was heated at the same temperature for 2 hours to obtain an unsaturated polyester (A-1) having an acid value of 10.8. This molecular weight is HLC
(High speed liquid kit chromatograph, manufactured by Hitachi, Ltd., Hitachi chromatograph 635-0200) using polystyrene as a standard substance, the average molecular weight was 99.
It was 0.

(2) Production of Unsaturated Polyester (A-2) In the same manner as in (1), 631 parts (5.95 mol) of diethylene glycol, 438 parts (1.75 mol) of Cardura E, and 581 parts (3.50 mol) of isophthalic acid were added to the flask. Then, 0.1 part of hydroxone was charged, the temperature was raised to 220 ° C., and the reaction was carried out at the same temperature until the acid value became 6. It took 6 hours.
Then, the mixture was cooled to 120 ° C., charged with 343 parts (3.50 mol) of maleic anhydride and 50 parts of xylol, and charged in the same manner as in (1).
The temperature was raised to 0 ° C., and the esterification reaction proceeded while measuring the acid value of the contents in the kettle. After heating for 4 hours, when the acid value showed 16.8, the mixture was cooled to 200 ° C., the amount of nitrogen gas was increased as in the case of (1), and the reaction was proceeded while removing xylol. The mixture was heated at the same temperature for 3 hours to obtain an unsaturated polyester (A-2) having an acid value of 10.8. When this molecular weight was measured in the same manner as in (1), the average molecular weight was 1,850.

(3) Production of unsaturated polyester (A-3) In the same manner as in (1), the flask No. 2 was charged with Cardura E, 94.
(0.34 mol), 954 parts of diethylene glycol (9.0 mol), 498 (3.0 mol) of isophthalic acid and 0.1 part of hydroquinone are charged, and the temperature is raised to 220 ° C as in (1), and the acid value becomes 20 at the same temperature. Reacted. The desired time was 4 hours. Then cool to 120 ° C and maleic anhydride 441
Part (4.5 mol) and 50 g of xylol were charged, the temperature was raised to 200 ° C. in the same manner as in (1), and the esterification reaction was proceeded while measuring the acid value of the contents in the kettle. After heating for 9 hours, cool to 200 ° C when the acid value shows 12.5, increase the blowing amount of nitrogen gas as in (1), measure the acid value while removing the xylol, and after heating for 2.5 hours. An unsaturated polyester (A-3) having an acid value of 8.6 was obtained. When the molecular weight was measured in the same manner as in (1), the average molecular weight was 1250.

Production of Unsaturated Polyester (X) of Comparative Example (4) Unsaturated Polyester (X-1) Diethylene glycol was added to the flask of 2 similarly to (1).
108 parts (10.22 mol), isophthalic acid 339 parts (2.04 mal)
And 0.1 parts hydroquinone, 220 as in (1)
The temperature was raised at 0 ° C. and the reaction was carried out until the acid value reached 12.6. The time required was 3.5 hours. Then cooled to 120 ° C., charged with 467 parts of maleic anhydride (4.77 mol) and 50 g of xylol,
The esterification reaction was allowed to proceed at 220 ° C. as in (1). After heating for 6 hours, when the acid value showed 16.5, it was cooled to 200 ° C and the reaction was allowed to proceed at the same temperature while removing the xylol.
After heating for an hour, the unsaturated polyester (X-
1) was obtained. When this molecular weight was measured in the same manner as in (1), the average molecular weight was 1050.

(5) Unsaturated Polyester (X-2) As in (1), Cardura E, 438 parts (1.75 mol), 631 parts (5.95 mol) of diethylene glycol, 518 parts (3.50 mol) of phthalic anhydride and hydroquinone were placed in the flask. Charge 0.1 part, raise to 220 ° C as in (1),
The reaction was carried out until the acid value reached 7. The desired time was 7 hours. Then, the mixture was cooled to 120 ° C and 343 parts of maleic anhydride (3.50
Mol) and 50 g of xylol, and 2 as in (1).
After raising the temperature to 20 ° C and heating at the same temperature for 5.5 hours, cool to 200 ° C when the acid value shows 14.8, increase the nitrogen gas amount and remove the xylol as at (1), while maintaining the same temperature. In 3
After heating for an hour, unsaturated polyester (X-2) with an acid value of 9.8
Got When its molecular weight was measured as in (1),
The average molecular weight was 1920.

(6) Unsaturated polyester (X-3) In the same manner as in (1), Cardura E, 193 parts (0.77 mol), propylene glycol 819 parts (10.78 mol), isophthalic acid 511 parts (3.08 mol) and hydroquinone were added to the flask of 2. Charge 0.1 parts, heat at 190 ° C for 2 hours, then in 4 hours
The temperature was raised to 210 ° C., and the mixture was heated at the same temperature until the acid value reached 18.5. The time required was 4.5 hours. Then, the mixture was cooled to 120 ° C., charged with 435 parts (4.62 mol) of maleic anhydride and 50 g of xylol, heated to 220 ° C. in the same manner as in (1), and after heating at the same temperature for 4.5 hours, the acid value showed 19.5. By the way, after cooling to 200 ℃, increasing the amount of nitrogen gas as in (1) and heating at the same temperature for 2.5 hours while removing xylol, the acid value was 13.5.
The unsaturated polyester (X-3) of was obtained. When this molecular weight was measured in the same manner as in (1), the average molecular weight was 1800.

Examples 1 to 6 and Comparative Examples 1 to 10 Resin compositions for veneer were prepared with the compositions and blending amounts (unit: parts by weight) shown in Table 1.

<Test Example> A pine or oak veneer with a thickness of 1.5 mm was placed in a stainless steel tank of 4, and the inside of the tank was depressurized to 4 mmHg / cm ² and allowed to stand for 4 hours, then decompressed, and each resin composition prepared was injected. Then
The pressure in the tank was increased to 30 kg / cm ² and the state was left for 16 hours, then the pressure was released to obtain an impregnated veneer. The impregnated veneer was taken out and cured with a hot press (140 ° C. for 3 minutes; 12 kg pressure / cm ² ) to obtain a treated veneer. Further, this treated veneer was bonded to a plywood with an adhesive to obtain a composite plate. Grindability, finishability, hardness and durability (cooling and heat repeating test) of this composite plate were examined as follows, and the results are shown in Table 2.

(1) Grindability: With a belt sander of water resistant paper # 240, the ease of grinding when the surface of the treated single plate on the composite plate was ground was evaluated as follows.

○: The surface can be completely ground by polishing once.

Δ: The surface can be completely ground by polishing 3 times.

(2) Finishability: It was visually evaluated as follows.

◯: The pattern of the spring wood part and winter wood part of the treated veneer on the composite board is clear and looks three-dimensional.

Δ: The patterns of the spring wood part and the winter wood part are three-dimensional, but they appear somewhat blurred.

×: The patterns of the spring wood part and the winter wood part appear to be blurred, and there is almost no stereoscopic view.

(3) Pencil hardness: A Mitsubishi Uni-Pencil was strongly pressed against the surface of the treated veneer at an angle of 45 °, and the hardness until scratches were examined.

(4) Barcol hardness: The hardness of the treated veneer was investigated using Barcor 935.

(5) Cold / heat cyclic test: The composite was left in a dryer at 80 ° C. for 2 hours and then immediately left in a refrigerator at −20 ° C. for 2 hours, and this was repeated as one cycle, and a repeated test was performed, and cracks were generated on the surface of the composite plate. The state was visually observed.

From Table 2, it is shown that, according to the examples, a composite plate having excellent grindability and having high finish and durability even when pine wood is used as the single plate is obtained.

[Effects of the Invention] According to the resin composition for a veneer of the present invention, a treated veneer and a composite having excellent durability, hardness, dimensional stability and grinding workability even when a pine wood is used for the veneer. The board can be obtained.

Claims (3)

[Claims] 1. (A) (a) General formula (I) (In the formula, R ₁ , R ₂ and R ₃ are each independently a carbon number of 1 to 1.
(Meaning 15 alkyl groups), (b) diethylene glycol, (c) isophthalic acid and (d) maleic anhydride in a molar ratio of (a):
(B): (c): (d) = 0.03-0.30: 1.47-0.70: 0.20
Unsaturated polyester having a molecular weight of 300 to 5000 and an acid value of 50 or less, obtained by reacting at a composition ratio of 0.80: 0.80 to 0.20, and (B) styrene to 20 relative to the total amount of (A) and (B).
To 80% by weight and (C) t-butylperoxyisopropyl carbonate in an amount of 0.1 to 10.0% by weight based on the total amount of (A) and (B).
A resin composition for wood-based decorative materials, which contains 100 to 500 centipoise of viscosity (25 ° C, Gardner). 2. A treated wooden decorative material obtained by impregnating a wooden decorative material with the resin composition for a wooden decorative material according to claim 1 and curing it. 3. A composite board obtained by adhering the treated woody decorative material according to claim 2 to a base material.