JPH0819197B2 - Resin composition for wood decorative material, treated wood decorative material and composite board - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition for wood decorative materials, and more particularly to a wood decorative material which can be suitably used as a finishing material for constructions and a surface material for furniture in which oak materials are used as floor materials. The present invention relates to a resin composition for use, a treated wood decorative material, and a composite board.

[0002]

2. Description of the Related Art Conventionally, wood has been 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, it is prone to wear, damage, feathering, and the like, and also has a problem that it is contaminated or discolored, and is contaminated in a short time.

In order to solve this problem, a coating film is usually applied to the surface of the wood. However, since the coating film thickness needs to be 30 μ or more, the view of the material of the wood is impaired and the thickness of such a film is also reduced. In order to apply the coating film, the undercoating and drying steps must be repeated, which has the drawback of decreasing 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, a polymerizable monomer, etc., and the conduit portion of the veneer is impregnated with the resin or the like (hereinafter, referred to as the mixture. An impregnated veneer is called an impregnated veneer), and a method has been developed to heat and compress the veneer and synthetic resin to form a composite (wood-plastic combination, hereinafter abbreviated as WPC). What is obtained is called a treated veneer). Although this WPC significantly increases the strength of the surface of the treated veneer, it is more difficult to use it as a flooring material for stores such as more durability, surface hardness, stain resistance and dimensional stability. It is necessary, and the color tone and feel of natural wood are required.

However, in the conventional method, particularly when using oak veneer as a treated veneer, cracks may occur on the surface due to repeated heat and cooling at the boundary between the spring wood part and the autumn wood part, or the spring wood part. However, there was a drawback that the difference in the density of the autumn wood part could not be maintained as it was and the color changed. In order to improve these drawbacks, a method of treating the veneer itself has been developed (Japanese Patent Laid-Open No. 63-5).
6402, JP-A-63-56403), there is a drawback that coating workability is significantly reduced.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems of the prior art, and in particular, it is excellent in durability, hardness, dimensional stability and finish even when oak is used as a single plate. Another object of the present invention is to provide a resin composition for a veneer capable of obtaining a coating film of the treated veneer, a treated veneer and a composite plate using the same.

[0007]

Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventors have found that an unsaturated polyester (A) having a specific component, a molecular weight and an acid value, and a polymerizable monomer containing styrene ( The present inventors have found that a composition containing B) and an organic peroxide (C) containing benzoyl peroxide in a fixed ratio can solve the above-mentioned problems, and arrived at the present invention.

That is, the present invention provides (A) maleic anhydride 1.0 to 0.2 mol, isophthalic acid 0 to 0.8 mol,
An average molecular weight of 300 is obtained by reacting polyalkylene glycol having an average molecular weight of 300 to 2000 derived from ethylene glycol or propylene glycol in an amount of 0.03 to 0.30 mol and diethylene glycol of 1.5 to 0.7 mol. Unsaturated polyester having an acid value of 50 to 5,000 and (B) styrene of 100 to 5
20 to 80% by weight of the polymerizable monomer containing 0% by weight and (C) an organic peroxide containing 100 to 50% by weight of benzoyl peroxide (A) based on the total amount of (A) and (B). ) And (B) in an amount of 0.1 to 10 wt% and a viscosity (25 ° C, Gardner) of 50 to 500.
Centipoise resin composition for wood decorative material, a wood decorative material impregnated with the resin composition for wood decorative material, and cured, and a composite obtained by adhering the treated wood decorative material to a substrate. Regarding the board.

The polybasic acid component of the unsaturated polyester (A) used in the present invention includes maleic anhydride (a) as the unsaturated polybasic acid and isophthalic acid as the saturated polybasic acid.
(b) is used, and the usage ratio is (a) :( b) = in molar ratio.
1.0-0.2: 0-0.8, preferably 1.0-0.
It is set to 4: 0 to 0.6. When the amount of maleic anhydride (a) is less than 0.2 mol, the impregnated veneer is heated and compression-molded, and when the veneer is treated, the curing of the resin composition is insufficient and the surface hardness is not sufficient. Cracks tend to occur when used.
If unsaturated polybasic acid other than maleic anhydride is used, or if saturated polybasic acid other than isophthalic acid is used, the finish of the treated veneer is inferior and the difference in concentration between spring wood and autumn wood becomes clear. It does not appear. The reason for this is not clear, but it is presumed that it is due to the refractive indexes of the resin composition and the oak material.

If necessary, an unsaturated polybasic acid other than maleic anhydride or a saturated polybasic acid other than isophthalic acid is added in an amount of 0 to 10 mol% as long as it does not affect the finish of the treated veneer. Can be used. Examples of unsaturated polybasic acids other than maleic anhydride include fumaric acid and itaconic acid, and examples of saturated polybasic acids other than isophthalic acid include phthalic acid, phthalic anhydride, tetrahydrophthalic anhydride and hymic acid. , Trimellitic acid and the like.

As the polyhydric alcohol component, polyalkylene glycol derived from ethylene glycol or polypropylene glycol and having an average molecular weight of 300 to 2000 (hereinafter referred to as polyglycol) (c) and diethylene glycol (d) are used. Ratio is molar ratio
(c): (d) = 0.03 to 0.30: 1.50 to 0.70
Mol, preferably 0.05-0.20: 1.50-0.
80. If a component other than polyglycol (c) or diethylene glulycol (d) is used, the durability of the oak treated veneer will be poor and, for example, it will not be possible to prevent surface cracking due to repeated heat and cooling, and dimensional stability. In addition, it is impossible to improve the finish. Polyglycol
The treated veneer using another glycol instead of (c), such as ethylene glycol, is heated at 80 ° C for 2 hours and-
In a cooling cycle of 2 hours at 20 ° C., a crack is generated on the surface in one cycle and the treated veneer is distorted. Further, when other polyhydric alcohol component such as propyl glycol is used instead of diethylene glycol (d), the finishability of the treated veneer using oak wood is remarkably deteriorated.

When the amount of the polyglycol (c) used is less than 0.03 mol, the durability of the treated veneer is insufficient, and 0.3
If it exceeds 0 mol, the molecular weight of the resin composition becomes large, and the impregnation of the single plate into the conduit portion becomes insufficient. Polyglycol (c)
It is preferable to appropriately adjust the amount to be used within the above range depending on the molecular weight of polyglycol. Also polyglycol (c)
If the average molecular weight of is less than 300, the durability of the treated veneer is not sufficient, and if it exceeds 2000, the molecular weight of the resin composition becomes large and impregnation of the veneer part of the veneer is insufficient and the strength of the treated veneer decreases. To do. When the amount of diethylene glycol (d) used exceeds 1.5 moles, the resin composition has a small molecular weight and the hardness of the cured product is insufficient. When it is less than 0.7 moles, the resin composition has a large molecular weight and acid value. Is not sufficiently lowered, impregnation into the veneer conduit is insufficient, the strength of the treated veneer is reduced, and the water resistance of the coating film is reduced.

If necessary, diethylene glycol may be used as long as the finish of the oak-treated veneer is not deteriorated.
0 to 10 mol% of (d) can be replaced with other polyhydric alcohol components. Other polyhydric alcohol components include, for example, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, hydrogenated bisphenol A, glycerin, and triglyceride. Methylolpropane, pentaerythritol, trimethylolethane and the like can be mentioned.

The unsaturated polyester (A) is synthesized by a known method. For example, maleic anhydride in the above proportion
(a), isophthalic acid (b), polyglycol (c), diethylene glycol (d), if necessary, other materials and a small amount of a polymerization inhibitor are charged into a reaction kettle while removing reaction water at 150 to 220 ° C. It is heated for 1 to 20 hours and adjusted so as to have a predetermined average molecular weight and acid value, or isophthalic acid (b), polyglycol (c), diethylene glycol (d) and a small amount of a polymerization inhibitor are added in the above proportions. After charging in a reaction kettle and heating at 140 to 220 ° C for 1 to 10 hours, maleic anhydride (a) and other materials as needed are charged, and again heating at 140 to 220 ° C for 1 to 15 hours to obtain predetermined characteristics. Adjust so that Hydroquinone, parabenzoquinone, toluquinone and the like are used as the polymerization inhibitor.

In the present invention, the unsaturated polyester (A) is prepared to have an average molecular weight of 300 to 5,000, preferably 300 to 2,000, and an acid value of 50 or less, preferably 30 or less. Alcohol (c) and
It is preferable to adjust the total amount of (d) so that the total amount of polybasic acids (a) and (b) is in the range of equimolar or more and 1.80 or less. When the total amount of (c) and (d) is less than equimolar, the acid value of the unsaturated polyester (A) exceeds 50, and the water resistance of the treated veneer deteriorates. If the total amount of (c) and (d) exceeds 1.80 mol, the unsaturated polyester (A)
Has a molecular weight of less than 300. When the average molecular weight of the unsaturated polyester (A) is less than 300, the coating film after curing is brittle and cracks are likely to occur on the surface of the treated veneer in a heat cycle test or the like. Further, when the average molecular weight of the unsaturated polyester (A) exceeds 5000, the permeation into the conduit of the veneer becomes insufficient, the resin adheres only to the surface of the veneer and the color tone of the natural wood tube cannot be obtained, and the cold heat Cracks easily occur on the surface of the treated veneer in the cycle test.

When synthesizing the unsaturated polyester (A), an allyl-containing compound such as trimethylolpropane diallyl ether and Epicoat 8 are used as long as the finish and the thermal cycleability of the oak wood treated plate are not deteriorated.
Epoxy resin such as 28 (trade name of Shell Chemical Co., Ltd.), animal and vegetable oil, petroleum resin, etc. may be used in combination.

Polymerizable monomer (B) used in the present invention
Is 100 to 50% by weight of styrene in the polymerizable monomer,
Preferably it contains 100 to 70% by weight. When the content of styrene is less than 50% by weight, the heat compression molding time of the oak-impregnated veneer becomes long, the workability is remarkably reduced, and the finished veneer is not sufficiently finished. Other polymerizable monomers can be used, if necessary, within a range that does not deteriorate the curability and finishability. As other polymerizable monomers, for example, vinyltoluene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, glycyl methacrylate, 2-hydroxyethyl (meth)
Examples thereof include acrylate and 2-hydroxy (meth) propyl acrylate, and these may be used alone or in combination of two or more.

The amount of the polymerizable monomer (B) used is 20 to 80% by weight, preferably 3% with respect to the total amount of (A) and (B).
It is 0 to 70% by weight. When the amount of the polymerizable monomer (B) 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 it exceeds 80% by weight, the curability is deteriorated, and the finishability, especially the natural color tone of wood is deteriorated.

Organic peroxide (C) used in the present invention
Benzoyl peroxide in an organic peroxide
The content is 0 to 50% by weight, preferably 100 to 70% by weight. If the amount of benzoyl peroxide is less than 50% by weight, the finish of the treated veneer using oak wood is inferior, and the density difference between the spring wood part and the autumn wood part is not clearly shown. Other organic peroxides can be used if necessary, as long as they do not deteriorate the finishability and the curability. Examples of other organic peroxides include ketone peroxides such as methylethylketone peroxide and methylcyclohexane peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl. Peroxyketals such as -4,4-bis (t-butylperoxy) valerate, t-butyl hydroperoxide, hydroperoxides such as diisopropylbenzene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide And the like, diacyl peroxides such as acetone peroxide, diacyl peroxides such as octanol peroxide and lauryl peroxide, and the like. These may be used alone or in combination of two or more.

The amount of the organic peroxide (C) used is 0.1 to 10% by weight, preferably 0.1 to 5.0% by weight, based on the total amount of (A) and (B). If the amount used is less than 0.1% by weight, the coating film after heat compression molding will be insufficiently cured, and the surface hardness, thinner resistance, etc. will decrease, and if it exceeds 10% by weight, organic peroxides will suffice. Acts as a plasticizer and the cured coating film becomes soft.

The resin composition for a single plate of the present invention has a viscosity (25
C., Gardner) is adjusted to 50 to 500 centipoise, preferably 100 to 300 centipoise. When the viscosity is less than 50 centipoise, the single plate is easily impregnated, but the amount of the polymerizable monomer (B) must be more than 80% by weight, and the coating film after heat compression molding becomes brittle. . On the other hand, if it exceeds 500 centipoise, the impregnating property into a single plate is lowered and a molded product having toughness cannot be obtained.

As a method for impregnating the single plate with the resin composition, a known method can be adopted. Generally, the veneer is placed under reduced pressure ( ^{2 to 5} mmHg / cm ² ) and impregnated with the composition so that the composition can easily enter the conduit in the veneer, and then immediately decompressed to normal pressure or pressure (normal It is carried out by leaving at 30 kg / cm ² ) for several hours (usually about 10 to 24 hours). The impregnated veneer thus obtained is heated and compressed (for example, at 80 to 150 ° C. for 3 to 20 minutes, 8 to 20 kg / cm 2).
² ) Then, harden it into a treated veneer. The treated veneer may be used by adhering it to a base material such as plywood, or the impregnated veneer may be heated and pressed simultaneously at the time of adhering to cure. A known adhesive can be used for bonding the treated veneer and the substrate.

The veneer resin composition of the present invention is remarkably effective in the finish and durability of the treated veneer made of oak, but the veneer used is not limited and may be used depending on the purpose. It can also be used for veneer made of cedar, pine, cypress, beech, etc.

The treated veneer is bonded to a base material such as plywood to form a composite plate. The treated veneer adhered to the plywood is ground with sandpaper, blast sander, etc. to remove excess resin adhering to the surface, exposing the surface layer and revealing the original fine grain of wood. As well as being discharged, it gives adhesion to the top coat paint (urethane paint, lacquer paint). The treated veneer and composite plate using the veneer resin composition of the present invention are easy to grind and have excellent workability.

[0025]

The present invention will be described below with reference to examples. "Parts" and "%" in the following examples mean "parts by weight" and "% by weight" unless otherwise specified. (1) Production of unsaturated polyester (A-1) In a 2 liter flask equipped with a stirrer, a gas introduction tube, a reflux condenser and a thermometer, 539 parts (5.5 mol) of maleic anhydride and Sanix diol PP- 1000
[Sanyo Chemical Co., Ltd., polypropylene glycol, average molecular weight 1000] 550 parts (0.55 mol), diethylene glycol 699.6 parts (6.6 mol) and tolhydroquinone 0.18 parts are charged, while blowing nitrogen gas. The temperature was raised to 200 ° C in 4 hours, and the acid value was 15 (KO
The reaction was carried out until it became Hmg / g, the same hereinafter, to obtain an unsaturated polyester (A-1). The reaction time required 8 hours.

The average molecular weight of the resulting unsaturated polyester (A-1) was measured by HLC (High Speed Liquid Chromatograph, Hitachi Chromatograph 635, manufactured by Hitachi, Ltd.).
-0200) using polystyrene as a standard substance, the average molecular weight was 1200. (2) Production of unsaturated polyester (A-2) Isophthalic acid 1 was added to a 2 liter flask similar to (1).
76.0 parts (1.06 mol), Sanix diol PP
-1000, 530 parts (0.53 mol), diethylene glycol 674.2 parts (6.3 mol) and tolhydroquinone 0.18 parts were charged and the temperature was raised to 220 ° C. in 4 hours, and the acid value was 18 at the same temperature. It was made to react until it became. The reaction time required 1.5 hours. Next, the mixture was cooled to 120 ° C., 415.5 parts (4.24 mol) of maleic anhydride was added, the temperature was again raised to 220 ° C., and after heating at the same temperature for 8 hours, the acid value was 8.6.
To obtain unsaturated polyester (A-2). When this molecular weight was measured in the same manner as in (1), the average molecular weight was 13
It was 50. (3) Production of unsaturated polyester (A-3) Isophthalic acid 2 in a 2 liter flask similar to (1).
74.0 parts (1.66 mol), Sanix diol PP
-1000, 712.5 parts (0.71 mol), 503.5 parts of diethylene glycol (4.75 mol) and 0.18 parts of tolhydroquinone were charged and 220 ° C in 5 hours.
The temperature was raised to, and the acid value was reacted until the acid value reached 25. The reaction time required 4.5 hours. Then, the mixture was cooled to 120 ° C., 302.6 parts (3.09 mol) of maleic anhydride was added, the temperature was raised to 220 ° C. again, the mixture was heated at the same temperature for 7 hours, and then the acid value was 7.8.
The unsaturated polyester (A-3) was obtained. When this molecular weight was measured in the same manner as in (1), the average molecular weight was 1550.
Met. (4) Production of Unsaturated Polyester (Z-1) 371.8 parts (2.24 mol) of isophthalic acid and 1017.6 parts (9.60 mol) of diethylene glycol were placed in the same 2 liter flask as in Example (1). Then, 0.18 part of toluhydroquinone was charged, the temperature was raised to 220 ° C. in 5 hours, and the reaction was carried out at the same temperature until the acid value became 26. The reaction time required 4.8 hours. Next, the mixture was cooled to 120 ° C., 407.7 parts (4.16 mol) of maleic anhydride was added, the temperature was raised to 220 ° C. again, and after heating at the same temperature for 8.5 hours, an unsaturated polyester having an acid value of 5.8. (Z-1) was obtained. When this molecular weight was measured in the same manner as in (1), the average molecular weight was 1
It was 250. (5) Manufacture of unsaturated polyester (Z-2) 267.3 parts (1.61 mol) of isophthalic acid, Sanix diol PP-1000, 690.0 parts (in a 2 liter flask similar to Example (1) ( 0.69 mol), diethylene glycol 487.6 parts (4.6 mol) and tolhydroquinone 0.18 parts were charged, and 22 in 5 hours.
The temperature was raised to 0 ° C., and the reaction was carried out at the same temperature until the acid value became 24. The reaction time required 3.5 hours. Next, the mixture was cooled to 120 ° C., 346.8 parts (2.99 mol) of fumaric acid was added, the temperature was raised to 220 ° C. again, and after heating at the same temperature for 6.5 hours, an unsaturated polyester (acid value 8.6 ( Z-2) was obtained. When this molecular weight was measured in the same manner as in Example (1), the average molecular weight was 1580. (6) Production of unsaturated polyester (Z-3) In a 2 liter flask similar to that used in Example (1), 313.7 parts (1.89 mol) of isophthalic acid, 810 parts of sanix diol PP-1000 (0. 81 mol), 334.8 parts (5.40 mol) of ethylene glycol and 0.18 part of toluhydroquinone were charged, and 220 ° C in 6 hours.
The temperature was raised to, and the acid value was allowed to react up to 24 at the same temperature. The reaction time required 4.5 hours. Then, the mixture was cooled to 120 ° C., 344.0 parts (3.51 mol) of maleic anhydride was added, the temperature was raised to 220 ° C. again, and the mixture was heated at the same temperature for 7.6 hours, then the acid value was 1
0.5 unsaturated polyester (Z-3) was obtained. When this molecular weight was measured in the same manner as in Example (1), the average molecular weight was 1750.

Examples 1 to 3 and Comparative Examples 1 to 5 Resin compositions for veneer were prepared with the compositions and blending amounts (unit is parts by weight) shown in Table 1.

[0028]

[Table 1] <Test Example> A 1.5 mm-thick oak veneer was placed in a 4-liter stainless steel tank, the tank was depressurized to 4 mmHg / cm ² , left for 4 hours, and then decompressed. Inject the substance, the pressure in the tank is 30kg pressure /
The pressure was applied to cm ² , and after standing for 20 hours in that state, the pressure was released to obtain an impregnated veneer.

This impregnated single plate was taken out and hot pressed (1
A treated veneer was obtained by curing at 20 ° C. for 7 minutes at a pressure of 15 kg / cm ² ). Further, this treated veneer was bonded to plywood with an adhesive to obtain a composite plate. Grindability, finishability, hardness and durability (cold heat repetition test) of this composite plate were examined as follows, and the results are shown in Table 2. Grindability: The ease of grinding when the surface of the treated single plate on the composite plate was ground with a belt sander of water resistant paper # 240 was compared, and evaluated as follows.

⊚: Surface can be completely ground by one-time polishing ○: Surface can be completely ground by two-time polishing △: Surface can be completely ground by five-time polishing Finishability: visually as shown below Evaluated to.

◯: The pattern (density difference) of the spring wood part and the autumn wood part of the treated veneer on the composite plate becomes clear. Δ: The pattern of the spring wood part and the autumn wood part of the treated veneer on the composite plate looks slightly blurred (the density difference is not clear). X: The pattern of the spring wood part and the autumn wood part of the treated veneer on the composite board appears blurred (there is almost no difference in density). Hardness: The hardness of the surface of the composite plate was examined using Barcol 935. Cold / heat cyclic test: The composite plate 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 cycle was repeated to perform a repeated test, and the state of cracks on the surface of the composite plate was visually observed. Observed at.

[0032]

[Table 2] From Table 2, it was shown that in the example, a composite plate having excellent grindability and having high finishability and high durability was obtained even when oak material was used as the single plate.

[0033]

EFFECTS OF THE INVENTION According to the resin composition for a single plate of the present invention, it is possible to obtain a treated single plate which is excellent in durability, hardness, dimensional stability, finish and grinding workability even when oak is used for the single plate. Plates and composite plates can be obtained.

Claims (3)

[Claims] 1. (A) Polyalkylene glycol 0.03 having an average molecular weight of 300 to 2000 derived from maleic anhydride 1.0 to 0.2 mol, isophthalic acid 0 to 0.8 mol, ethylene glycol or propylene glycol.
~ 0.30 mol and diethylene glycol 1.5 ~
An unsaturated polyester having an average molecular weight of 300 to 5,000 and an acid value of 50 or less, which is obtained by reacting at a composition ratio of 0.7 mol, and (B) a polymerizable monomer containing styrene in an amount of 100 to 50% by weight. 20 to the total amount of (A) and (B)
An organic peroxide containing 80% by weight and 100 to 50% by weight of (C) benzoyl peroxide is contained in an amount of 0.1 to 10% by weight based on the total amount of (A) and (B), and a viscosity (25 ° C., Gardner) 50-500 centipoise resin composition for wooden decorative materials. 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 wood decorative material according to claim 2 to a base material.