JPH1121401A - Vinyl chloride resin composition and molded article using the same - Google Patents

Abstract

(57) [Summary] [Problem] A vinyl chloride-based material having a wood grain with excellent graininess, which suppresses a bleeding phenomenon that occurs with respect to weather resistance, particularly with respect to water and warm water, and does not require a surface treatment step. It is an object to provide a resin composition and a molded product thereof. A phenolic resin modified from cashew nut shell oil is 0.1 to 100 parts by weight based on 100 parts by weight of a vinyl chloride resin.
Parts by weight of the woody vinyl chloride resin composition and 100 to 100 parts by weight of the woody vinyl chloride resin composition, 0.2 to 30 parts by weight of the crosslinked vinyl chloride resin and / or vinyl polymer resin. A vinyl chloride resin composition having a woody grain obtained by mixing parts thereof and a molded product obtained by melt molding these compositions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a woody vinyl chloride resin composition, and more particularly, to a vinyl chloride resin composition having an excellent woody feel, and further to a woody wood grained vinyl chloride resin composition having a wood grain. The present invention relates to a molded article and a molded article obtained by melt molding the same.

[0002]

2. Description of the Related Art In recent years, wood-based materials, such as window frames, door frames, floors, ceilings, and stair railings, have been increasingly used as interior materials for houses. In addition, there is an increasing demand for a warmer house by attaching a wooden material to the exterior material. When wood itself is used, wood is a natural product, and thus lacks uniformity of color, and has problems such as weather resistance to water, light, and the like, combustibility, durability, and the like. Also, tree felling is a major problem for environmental issues such as deforestation. Therefore, many attempts have been made to obtain a wood-substituted wood substitute by mixing wood powder or the like with a hard synthetic resin as a substitute for wood. But,
These hard synthetic resins having a woody feel have a defect in weather resistance because wood powder is used at all. In particular, as an interior material, when used as a water supply material for kitchens, bathrooms, etc., cellulose contained in wood flour will cause a bleeding phenomenon due to the influence of water, hot water, etc. There is a problem that the wood texture and the grain pattern disappear completely.

[0003] In order to solve this problem, there is an example in which a surface of a molded product is coated by using a urethane resin, an acrylic resin, a melamine resin, a polyester resin or the like as a paint. However, in these methods, the wooden texture of the surface of the molded article is impaired, and in order to obtain a wooden texture, an attempt has been made to include a wood powder in the coating agent at the time of surface coating to give a wooden texture. There is no expectation of wood texture. In addition, as long as wood flour is used, the bleeding phenomenon that occurs in water or hot water is not substantially improved. Furthermore, in these methods, in addition to the molding process, as a surface treatment step, a coating agent coating step,
The addition of a drying step after painting, etc., necessitates an increase in the number of steps and complications, leaving a problem in economical aspects.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the conventional method, suppresses the bleeding phenomenon that occurs with respect to the weather resistance, particularly with respect to water or hot water, and requires a surface treatment step. It is an object of the present invention to provide a vinyl chloride resin composition and a molded article excellent in a woody texture, and a vinyl chloride resin composition and a molded article excellent in a woody texture provided with grain.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have made intensive studies to solve such problems with the aim of improving the weather resistance without impairing the feeling of wood, particularly the bleeding phenomenon caused by the influence of water or hot water. As a result, conventionally, instead of wood powder that was added to give the synthetic resin a woody feel, a phenolic resin modified with cashew nut shell oil was used, and a vinyl chloride resin By adding the cashew nut shell oil-modified phenolic resin, it is possible to suppress the bleeding phenomenon that occurs with respect to the weather resistance, especially with respect to water and hot water, and the bleeding phenomenon occurs in a system using wood flour. It has been found that surface coating, surface treatment, and the like applied to prevent the phenomenon are not required, and the present invention has been achieved.

That is, the present invention relates to a vinyl chloride resin 10
A woody vinyl chloride resin composition containing 0.1 to 100 parts by weight of a cashew nut shell oil-modified phenolic resin with respect to 0 parts by weight, and the present invention provides the woody vinyl chloride resin A vinyl chloride resin composition having a woody grain, obtained by mixing 0.2 to 30 parts by weight of a crosslinked vinyl chloride resin and / or vinyl polymer resin with 100 parts by weight of the composition. The present invention is also a resin molded product obtained by melt-molding the woody vinyl chloride resin composition and the woody grain-giving vinyl chloride resin composition, respectively.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a vinyl chloride resin refers to a vinyl chloride homopolymer, a copolymer of vinyl chloride and another monomer (vinyl chloride copolymer), Examples thereof include a graft copolymer with a polymer (vinyl chloride-based graft copolymer), and a chlorinated product of the above-described homopolymer, copolymer, and graft copolymer. These polymerization degrees are usually about 400-3000, preferably 600-2000, and more preferably 700-1.
500. If the degree of polymerization is less than 400, the strength is insufficient, and if it exceeds 3000, the moldability decreases.

[0008] In the case of vinyl chloride homopolymer, its production method is carried out by a conventionally known polymerization method, and examples thereof include those obtained by suspension polymerization and the like. These vinyl chloride homopolymers are easily available on the market, for example, TH-500, TH-600, and TH-70 manufactured by Taiyo PVC Co., Ltd.
0, TH-800, TH-1000, TH-1300,
TH-1400, TH-1700, TH-2000 and the like can be used, and the degree of polymerization is 500, 600, respectively.
700, 800, 1000, 1300, 1400, 17
00 and 2000.

Examples of the vinyl chloride copolymer include an ethylene-vinyl chloride copolymer and a vinyl acetate-vinyl chloride copolymer, and the production thereof is carried out by a conventionally known polymerization method. Polymerization and the like.

The ethylene-vinyl chloride copolymer includes:
It is easily available on the market, for example, Taiyo PVC Co., Ltd.
TE-650, TE-800, TE-1050,
TE-1300, TE-1700 and the like can be used, and the degree of polymerization is 650, 780, 1050, 13 respectively.
00, 1700. Further, as a vinyl acetate-vinyl chloride copolymer, for example, a TV manufactured by Taiyo PVC Co., Ltd.
-800 and a degree of polymerization of 780, which are also readily available on the market.

Next, a vinyl chloride graft copolymer obtained by graft copolymerizing vinyl chloride is a copolymer of alkyl acrylate and / or alkyl methacrylate with a polyfunctional monomer (hereinafter referred to as acrylic copolymer). Is copolymerized with vinyl chloride. More specifically, 99 to 70 parts by weight of vinyl chloride is graft-copolymerized with 1 to 30 parts by weight of an acrylic copolymer.

As the alkyl acrylate and / or alkyl methacrylate in the acrylic copolymer, it is advantageous that the secondary transition point of the alkyl acrylate alone is -10 ° C. or less from the viewpoint of improving impact resistance. Examples include, for example, ethyl acrylate, n-propyl acrylate, iso-butyl acrylate, n-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, n-octyl methacrylate, n-
Decyl methacrylate, n-dodecyl methacrylate, lauryl methacrylate and the like can be mentioned. In this case, the amount of the alkyl acrylate and / or alkyl methacrylate used is 99 to 7 in the acrylic copolymer.
0% by weight is preferred. If the amount exceeds 99% by weight, the flexural modulus decreases, and if it is less than 70% by weight, the impact resistance decreases, which is not preferable.

The polyfunctional monomer is a monomer that can be copolymerized with an alkyl acrylate and / or an alkyl methacrylate and that participates in crosslinking or the like in a copolymer or a graft copolymer. For example, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1,3- Acrylates or methacrylates of (poly) alkylene glycols such as butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, diallyl phthalate, diallyl , Diallyl fumarate, polyallyl compounds such as diallyl succinate, divinyl benzene, butadiene and the like. The amount of the polyfunctional monomer to be used is preferably 1 to 30% by weight in the acrylic copolymer. If it is less than 1% by weight, the flexural modulus is lowered. Is undesirably reduced.

As a method for obtaining these acrylic copolymers, any of polymerization methods such as emulsion polymerization, solution polymerization, bulk polymerization and the like can be used, and generally known emulsifiers, dispersants, catalysts and the like can be used. To obtain a polymer. For example, as a method for obtaining an acrylic copolymer by an emulsion polymerization method, pure water, an anionic emulsifier, and a water-soluble polymerization catalyst are put in a jacketed polymerization reactor, air in the can is eliminated, and then alkyl acrylate and After charging and / or emulsifying an alkyl methacrylate and a polyfunctional monomer, the inside of the can is heated by a jacket to carry out a copolymerization reaction. This copolymerization reaction is an exothermic reaction, and the internal temperature is controlled by a jacket as necessary. After the reaction,
Unreacted monomers are removed outside the can to obtain an acrylic copolymer. If necessary, a particle size adjuster for the acrylic copolymer, a catalyst decomposition accelerator for controlling the copolymerization reaction, and the like may be added.

Then, vinyl chloride is graft-copolymerized using the acrylic copolymer thus obtained as a trunk polymer of the graft copolymer to obtain a vinyl chloride-based graft copolymer. Here, examples of the graft copolymerization method include polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, and solventless polymerization. For example, when performing a suspension polymerization method, in a polymerization reactor with a jacket, pure water, a suspension stabilizer such as hydroxypropylmethylcellulose, a radical polymerization initiator,
After adding a polymerization degree reducing agent as needed, an acrylic copolymer is added and suspended. Here, the amount of pure water used is 1 to 5 with respect to the total amount of the acrylic copolymer and the vinyl chloride monomer.
And preferably 1 to 3 times. Then, after the air in the can is eliminated, vinyl chloride is inserted together with other vinyl compounds as required. Thereafter, the inside of the can is heated by a jacket, and the acrylic copolymer is dissolved in vinyl chlorides to start graft copolymerization. The graft copolymerization is an exothermic reaction, and the internal temperature is controlled by a jacket as necessary. After completion of the reaction, unreacted vinyl chlorides are removed outside the can to obtain a slurry-like graft copolymer. The slurry is dehydrated and dried according to a conventional method to obtain a vinyl chloride graft copolymer. The method of charging the polymerization reactor is not limited, and among the raw materials such as pure water, suspension stabilizer, acrylic copolymer, and vinyl chloride, the acrylic copolymer is converted to vinyl chloride. A method of dissolving and charging the solution is also adopted. The graft ratio here is represented by the tetrahydrofuran-insoluble weight% of the graft copolymer, usually 5 to 100% by weight, and generally about 10% by weight is preferably used.

The vinyl chloride graft copolymer thus obtained is mixed with a vinyl chloride resin by a generally known method so as to contain at least 10% by weight or more to obtain a vinyl chloride resin. Here, if the content of the vinyl chloride graft copolymer is less than 10% by weight, improvement in impact resistance cannot be expected. Further, the vinyl chloride graft copolymer itself can be used as the vinyl chloride resin without mixing with the vinyl chloride resin. The degree of polymerization of the vinyl chloride graft copolymer thus obtained is usually 4
About 00 to 3000, preferably 600 to 200
0, more preferably 700-1500. If the degree of polymerization is less than 400, the strength is insufficient, and if it exceeds 3000, the moldability decreases.

Examples of these vinyl chloride graft copolymers include TA-I200 manufactured by Taiyo Vinyl Co., Ltd.
TA-I100, TA-E200, TA-E230 and the like are available on the market, and the degree of polymerization is 500, respectively.
700, 1000, and 1300.

On the other hand, in the case of a vinyl chloride graft copolymer obtained by graft copolymerizing vinyl chloride with an ethylene-vinyl acetate copolymer, vinyl chloride is graft copolymerized with the above acrylic copolymer. In the same manner as described above, a vinyl chloride graft copolymer is obtained by graft copolymerizing vinyl chloride using an ethylene-vinyl acetate copolymer as a trunk copolymer for graft copolymerization. Here, examples of the graft copolymerization method include polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, and solventless polymerization. Since rubber elasticity is imparted by ethylene-vinyl acetate, it is extremely excellent in brittleness at low temperatures, impact resistance and weather resistance.

These vinyl chloride-based graft copolymers include, for example, TG-110, T.O.
G-120, TG-130, etc. are easily available on the market,
The polymerization degrees are 900, 700 and 850, respectively.

Examples of the chlorinated product of the vinyl chloride resin include, for example, chlorinated polyvinyl chloride, which can be easily obtained on the market. For example, H-305, manufactured by Kaneka Chemical Co., Ltd. H-526, H-727, H-829 and the like can be used, and the degree of polymerization is 500, 60, respectively.
0, 700, and 900, and the chlorine content was 63
%, 65%, 67%, and 68%.

Here, as the vinyl chloride resin, a vinyl chloride homopolymer, a vinyl chloride copolymer, a vinyl chloride graft copolymer, or the above homopolymer, copolymer, or graft copolymer is used. The chlorinated products can be used alone, or two or more of them can be used in combination by a generally known method.

Further, in addition to the above-mentioned vinyl chloride resin, a crosslinked vinyl chloride resin can also be used. The crosslinked vinyl chloride resin as the vinyl chloride resin has a polymerization degree of usually about 400 to 6000, preferably 600
3,000, more preferably 700-2,000. The degree of crosslinking is low at about 10%, and high at about 30%. This crosslinked vinyl chloride resin has a great effect of imparting a woody feeling, and when used together with a cashew nut shell oil-modified phenolic resin described later, the woody feeling is significantly increased due to a synergistic effect. This crosslinked vinyl chloride resin is easily available on the market, for example, SD7E, SD10E, SD1 manufactured by Chisso Corporation.
3E, SD7X, SD10X and TU manufactured by Taiyo PVC Co., Ltd.
-300, TU-400 and the like, and the degree of polymerization is 700, 1000, 1300, 750, respectively.
1000, 3000, 4000.

When the crosslinked vinyl chloride resin is used as the vinyl chloride resin, the content of the vinyl chloride resin should be up to 90% by weight in order to not reduce the effect of imparting the grain to half, and the rest should be as described above. Certain vinyl chloride homopolymers, vinyl chloride copolymers and vinyl chloride-based graft copolymers, and further, any of these homopolymers, copolymers and chlorinated products of the graft copolymers may be used alone or in combination of two or more. Are mixed and used by a general known method. When the content of the crosslinked vinyl chloride resin exceeds 90% by weight, the appearance of a grain pattern is reduced, and the moldability is also reduced.

The cashew nut shell oil-modified phenolic resin used in the present invention is used for the purpose of imparting a woody feel, and is used in the shell of the ash tree of the lacquer anacardium plant native to South America, India and Africa. A novolak-type cashew nut shell oil-modified phenolic resin obtained by subjecting the contained black-brown liquid (mainly curl and anacardic acid) to heat treatment with cardanol obtained by heat treatment with formaldehyde, etc., or a treatment using an alkali as a catalyst. It is a resole type cashew nut shell oil-modified phenolic resin or an alkylphenol-based cured resin having a crosslinked structure by other treatment. These are easily available on the market. For example, Tohoku Kako Co., Ltd.
Senlight Cashew Dust FF-1040, FF-1
045, FF-1148, FF-1085, FF109
0, FF-2090, etc., which are classified according to particle size distribution, color tone, flexibility, heat resistance and the like, and can be used properly according to the application. In addition, since cashew nut shell oil-modified phenolic resin is mainly black or brown,
The cashew nut shell oil-modified phenolic resin and white inorganic pigment such as titanium oxide can be premixed and whitened before use. As a result, the degree of freedom of the color is increased, and the toning with a colored pigment or the like becomes easy later.

A woody vinyl chloride resin composition can be obtained by mixing a cashew nut shell oil-modified phenolic resin and a vinyl chloride resin to give the appearance and feel of the woody feel to the wood. The added number of the cashew nut shell oil-modified phenolic resin is 0.1 to 100 parts by weight based on 100 parts by weight of the vinyl chloride resin.
Parts by weight, preferably 0.2 to 60 parts by weight,
More preferably, it is 0.5 to 30 parts by weight. If the number of added parts is less than 0.1 part by weight, the feeling of wood having a rough surface due to touch is small, and if it exceeds 100 parts by weight, moldability deteriorates. In addition, light brown pigments are further added in order to make the wood grain stand out with respect to the wood grain imparting described later.

The woody wood-grained vinyl chloride resin composition of the present invention refers to a crosslinked vinyl chloride resin and / or a vinyl polymer resin (hereinafter, woodgrain) with respect to the woody vinyl chloride resin composition. By adding the vinyl-based resin for application, a vinyl chloride resin composition having a woody grain can be obtained. Here, the vinyl-based resin for imparting wood grain refers to the above-mentioned crosslinked vinyl chloride-based resin and / or vinyl-based polymer resin, which is obtained by further adding a dark pigment to the wood grain to make the wood grain stand out.

These vinyl resins for imparting grain can be obtained as a vinyl chloride resin composition having a grain of wood by mixing with a vinyl chloride resin composition having a grain of wood. By melt-molding the resin composition, a vinyl chloride resin molded article having a woody grain can be obtained.

The degree of polymerization of the crosslinked vinyl chloride resin in the vinyl resin for imparting wood grain is usually about 400 to 6000, preferably 600 to 3000, and more preferably 700 to 2000. In addition, the degree of crosslinking is low and is 1
Although there is about 0% or as high as about 30%, the one that is particularly effective for imparting the grain is the one having a degree of crosslinking of 25% or more.

The higher the degree of crosslinking and the degree of polymerization, the higher the melt viscosity at the time of molding, the mixture of the woody vinyl chloride resin composition and the vinyl resin for imparting grain is extruded with the added dark pigment. The grain of the product appears. This crosslinked vinyl chloride resin is readily available on the market as described above.

The vinyl polymer resin in the vinyl resin for imparting wood grain may be a polymer resin which does not impair the effects of the present invention, and is used for the purpose of increasing the melt viscosity during molding. Styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene and other aromatic compounds, vinyl chloride, chlorinated vinyl chloride, methyl methacrylate, methyl acrylate and other methacrylic acid or alkyl acrylate Examples include unsaturated nitriles such as esters, acrylonitrile, and methacrylonitrile, and polymers such as maleimide, N-maleimide, and Nt-butylmaleimide. Not limited to one type, two or more types can be used simultaneously. .

The amount of the vinyl resin for imparting wood grain is 0.2 to 30 parts by weight, preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the woody vinyl chloride resin composition.
It is 20 parts by weight, more preferably 1 to 15 parts by weight. If the amount is less than 0.1 parts by weight, grain does not appear clearly,
When the amount exceeds the weight part, the grain overlaps, and the grain just added does not appear.

In the composition of the present invention, various additives can be used in combination depending on the use. For example, when the purpose is to impart impact resistance, the following impact strengthening agents are added. Can be used. Examples of the impact modifier include a methyl methacrylate-butadiene-styrene copolymer (hereinafter abbreviated as MBS resin), an acrylic resin, a silicon-modified acrylic resin, and chlorinated polyethylene.

Here, regarding the MBS resin, for example,
BTA-712, BTA-7 manufactured by Kureha Chemical Industry Co., Ltd.
Acrylic resins such as 31, BTA-751 and the like are, for example, FM and FM-2 manufactured by Kaneka Corporation.
0, FM-21 and the like. As for the silicone-modified acrylic resin, for example, S-2 manufactured by Mitsubishi Rayon Co., Ltd.
Chlorinated polyethylene, for example, Eraslen EXP-771 manufactured by Showa Denko KK
(A chlorine content of 36% by weight, a specific gravity of 1.16, and a blocking index of 1% by weight or less).

[0034] The number of parts of these impact modifiers to be added is 1 to 100 parts by weight of the woody vinyl chloride resin composition.
It is 60 parts by weight, preferably 3 to 30 parts by weight.
If the amount is less than 1 part by weight, improvement in impact resistance cannot be expected much. If the amount exceeds 60 parts by weight, it is not possible to expect an improvement in the impact resistance only by the number of the added parts, which is economically disadvantageous.

For the purpose of imparting heat resistance, the following heat-resistant improvers can be added for use. Examples of the heat resistance improver include α-methylstyrene-acrylonitrile-styrene copolymer (α-methylstyrene-AS resin) and α-methylstyrene-acrylonitrile-butadiene-styrene copolymer (α-methylstyrene- ABS-based resin), acrylonitrile-butadiene-styrene copolymer (ABS-based resin), acrylonitrile-ethylene-propylene-diene-styrene-based copolymer (AES-based resin), and the like. As the α-methylstyrene-AS resin, for example, S700N (α-methylstyrene 75% by weight, unsaturated nitrile 25% by weight), S802N (α-methylstyrene 70% by weight, 20% by weight of saturated nitrile,
N-aromatic maleimide 10% by weight), S803N (α-
35% by weight of methylstyrene, 25% by weight of unsaturated nitrile, 20% by weight of N-aromatic maleimide, 20% by weight of styrene), Telalloy A-50 manufactured by Kanegafuchi Chemical Industry Co., Ltd.
B and the like. Examples of the α-methylstyrene-ABS resin include H100N manufactured by Ube Sicon Co., Ltd. and Telalloy A-10, A-15 manufactured by Kaneka Chemical Industry Co., Ltd. There is also an improvement in the properties. ABS
For example, ST-based resins manufactured by Mitsui Chemicals, Inc.
-50, RT-21, GT-10, etc., which improve heat resistance and impact resistance. As for the AES resin, for example, AES110, AES110 manufactured by Nippon Synthetic Rubber Co., Ltd.
115, AES145 and the like. In these resins,
In addition to heat resistance, improvements in weather resistance and impact resistance are also seen.

The amount of these heat-resistant improvers is from 1 to 8 per 100 parts by weight of the woody vinyl chloride resin composition.
0 parts by weight, preferably 5 to 60 parts by weight. If the number of added parts is less than 1 part by weight, improvement in heat resistance cannot be expected much. If the amount exceeds 80 parts by weight, the heat resistance is improved, but the impact resistance is remarkably reduced, and the balance of physical properties is lost, resulting in disadvantages including physical properties and economy.

For the purpose of imparting foaming, the following foaming agents can be added and used. As the foaming agent, p, p'-oxybis-benzenesulfonylhydrazide (OBSH), azodicarbonamide (ADC)
A), sodium hydrogencarbonate (NaHCO3) and the like. These may be used alone or in combination. For example, SELVON SC manufactured by Eiwa Chemical Co., Ltd.
P (NaHCO3), DS-25 (ADCA + OBS)
H) and a cell microphone C1 (ADCA).

The total number of these foaming agents to be added is 0.05 to 3.0 parts by weight, preferably 0.1 to 100 parts by weight of the woody vinyl chloride resin composition.
1 to 1.5 parts by weight, more preferably 0.2 to 1.5 parts by weight.
1.0 part by weight. If the amount is less than 0.05 part by weight, there is no specific gravity reducing effect, and an improvement in the expansion ratio cannot be expected much. If the number of added parts exceeds 3.0 parts by weight, a high foaming state is obtained, the strength of the molded product cannot be sufficiently maintained, and only a very limited molded product can be obtained, which causes a problem in moldability.

As described above, the above-mentioned impact resistance enhancer, heat resistance improver and foaming agent are used for the woody vinyl chloride resin composition.
They may be used alone or in combination of two or more.

Other commonly used stabilizers, lubricants, plasticizers, processing aids, antioxidants, UV absorbers, pigments, fillers, and the like can be used as necessary. As the stabilizer here, any known one may be used, and an inorganic acid salt type, a metal soap type, an organometallic compound type, an organic compound type or the like is used. As the lubricant, a hydrocarbon type,
Any of a fatty acid type, an ester type, a metal soap type, a fatty alcohol type, a polyhydric alcohol type and the like, or a mixed type can be used. As the plasticizer, phthalic acid type, epoxy type, polyester type, chlorinated paraffin type and the like can be used. Examples of the processing aid include polymethyl methacrylate. Examples of the pigment include titanium oxide, red iron oxide, graphite, carbon black, and the like. Among them, titanium oxide is mainly used. Further fillers include, for example, calcium carbonate, clay,
Hydrous silicic acid, anhydrous silicic acid, calcium silicate, aluminum silicate asbestos powder, antimony oxide, talc, aluminum trihydrate, zinc borate hydrate, magnesia, sodium bicarbonate, nitric acid, calcium hydroxide, mica, synthetic fluorine mica, and the like, Among them, calcium carbonate is preferably used.

As described above, generally used additives are easily available on the market, are often used, and can be used or used in combination as needed.

The method of obtaining the woody vinyl chloride resin composition of the present invention includes the above-mentioned vinyl chloride resin, cashew nut shell oil-modified phenolic resin, stabilizer and lubricant, and if necessary, impact resistance. Agents, heat improvers, foaming agents, and other additives, for example, stirring and blending with a stirrer such as a Henschel mixer, a Banbury mixer, a ribbon blender, and the obtained blended powder or this blended powder, for example, Conical twin screw extruder,
It can be obtained as pellets granulated by a kneader such as a parallel twin-screw extruder, a single-screw extruder, a kneader-type kneader or a roll kneader. The blended powder or pellets, which are the woody vinyl chloride resin composition, are melt-processed by an extruder such as a conical twin-screw extruder, a parallel twin-screw extruder, a single-screw extruder, etc. It can be obtained as a vinyl resin molded product.

Further, a light-colored pigment is previously added to the woody vinyl chloride-based resin composition comprising the above-mentioned vinyl chloride-based resin, cashew nut shell oil-modified phenol-based resin, etc. in order to bring out the effect of imparting grain later. The added pellet can be used as a base pellet.

To the above-mentioned wood-like vinyl chloride resin composition, a wood-grain-applying vinyl resin is added, and the mixture is stirred and blended in the same manner as described above to obtain a wood-like wood-grain-applying vinyl chloride resin composition. Can be obtained. In this case, in order to give wood grain to the woody vinyl chloride resin,
When a dark pigment is added, the effect of imparting wood grain is brought out.

As in the case where the wood-like vinyl chloride resin is pellets (hereinafter abbreviated as base pellets), the vinyl resin for imparting grain is a stabilizer, a lubricant, a dark pigment, and other additives. , And the mixture is stirred and blended by a stirrer in the same manner as in the case of the base pellets, and the resulting blended powder can be granulated by an extruder to obtain pellets (hereinafter abbreviated as seed pellets).

These base pellets and seed pellets are preliminarily mixed and charged from a hopper opening, or only seed pellets are charged after a vent opening, and extruded by a conical twin-screw extruder, a parallel twin-screw extruder, a single-screw extruder, or the like. It can be obtained as a grain-grained molded product by melt molding with a machine. When extruding a wood-grained molded product, the wood-grain-imparting seed pellets do not sufficiently melt in the base pellets, resulting in uneven coloring due to the dark pigment. Since the dark portion due to the unevenness flows in parallel with the extrusion direction, the grain can be made very close to a natural grain.

[0047]

EXAMPLES The present invention will be described more specifically with reference to the following examples. In addition, the measuring method in an Example is as follows.

The resin compositions shown in the Examples and Table 1 were manufactured by Ikegai Iron Works Co., Ltd. equipped with a flat plate sizing die.
0mm single screw full flight screw extruder FS40
At -25 (screw diameter 40 mm, L / D = 25), cylinder set temperature 140-170 ° C, adapter set temperature 145-165 ° C, die set temperature 150-1
Under the condition of 70 ° C, width 84 mm, thickness 4 mm, length about 10
A flat plate of 0 mm was formed. At the time of molding, the moldability was evaluated. Using the obtained molded article, the woodiness, bleeding phenomenon, impact resistance, heat resistance, foaming, and grain were evaluated as follows.

Regarding the wooden texture, the gloss of the surface of the molded article was measured and evaluated. The measurement was carried out using a handy gloss meter gloss checker IG-320 manufactured by Horiba, Ltd. Here, it was determined that there was a woody feeling when the gloss value was 20 or less.

Regarding the molding processability, when either the motor load amperage of the extruder or the resin pressure at the time of the molding process shows a high value, the processability is determined to be poor. It was also determined that the workability was poor when the shape of was not uniform. The workability was comprehensively determined and ranked as follows. ○: good, ×: bad.

Regarding the bleeding phenomenon, a container containing water was placed in a circulating hot air dryer DG (DFR) -100 manufactured by Futaba Kagaku Co., Ltd. and heated so that the water temperature became 50 ° C. Then, the molded article was immersed in the warm water for 24 hours, and changes in the surface state of the molded article before and after immersion were observed. The surface conditions were ranked as follows.印: no change. X: Bleeding phenomenon occurs (the surface of the molded product becomes white, and the original color on the surface of the molded product disappears).

For impact resistance, Charpy impact strength was measured. A sample was cut out from the above molded product to obtain a test piece. The measurement was performed by a method according to JIS-K7111.

With respect to heat resistance, the main dispersion peak value (glass transition temperature) of tan δ when measured at a frequency of 1 Hz in dynamic viscoelasticity was evaluated. The glass transition temperature was measured using the above molded product as ASFA1 manufactured by Shinto Metal Industry Co., Ltd.
Pressed at a press temperature of 180 ° C using a 50-type compression molding machine, about 40 mm wide, about 10 mm long, and about 1 mm thick
A test piece was prepared by cutting out a sample piece of the above, and was manufactured by Seiko Electronic Industry Co., Ltd. (Dynamic Mechanical).
al Spectrometer DMS100) at a frequency of 1 Hz and a heating rate of 2 ° C./min.
The main dispersion peak value of tan δ was determined as the glass transition temperature.

Regarding foaming, the specific gravity was measured using a sample obtained by cutting the above molded product into an appropriate size. Measurement was made by Mirage Trading Co., Ltd., using an electronic hydrometer ED-12.
0T was used.

The wood grain pattern was evaluated by using the above-mentioned molded article by the presence or absence of grain streaks on the surface of the molded article.

Example 1 A vinyl chloride homopolymer (TH-700, manufactured by Taiyo Vinyl Co., Ltd.) having an average degree of polymerization of 700 was used as the vinyl chloride resin.
1 part by weight of methyltin mercapto (TM-181FSJ, manufactured by Katsuta Kako Co., Ltd.) as a stabilizer and distearyl phthalate ester (Roxyol G60, manufactured by Henkel Hakusui Co., Ltd.) as an internal lubricant. 2 parts by weight, 0.5 parts by weight of a polymer composite ester as an external lubricant, 2 parts by weight of a modified polyethylene, and PM as a processing aid
MA 10 parts by weight, calcium carbonate 5 parts by weight as a filler, cashew nut shell oil-modified phenolic resin (Cenlight Cashew Dust, FF-1 manufactured by Tohoku Kako Co., Ltd.)
045) 10 parts by weight were mixed with a Henschel mixer manufactured by Mitsui Miike Co., Ltd. to obtain a woody vinyl chloride resin composition. The obtained resin composition was melt-extruded with a single-screw extruder (PCM-30) having a diameter of 30 mm manufactured by Ikegai Iron Works Co., Ltd. to obtain pellets. Using the obtained pellet,
It was molded with an FS-40 extruder manufactured by Ikegai Iron Works Co., Ltd. to obtain a rectangular parallelepiped molded product. As a result of measuring the physical properties of the molded product of this rectangular parallelepiped, the gloss was low at a gloss value of 5.3, and the woody texture was sufficient. Both the motor load of the extruder and the resin pressure during molding do not rise so high that the moldability is good (○)
Met. No bleeding occurred, and there was no change in the surface condition of the molded product (全 く). Charpy impact strength is 5.3 kgf · cm / cm 2, glass transition temperature is 8
The molded product had a specific gravity of 1.34 at 0.2 ° C.

Example 2 As a vinyl chloride resin, a vinyl chloride graft copolymer having an average degree of polymerization of 1000 (TA-TAROH, manufactured by Taiyo PVC Co., Ltd.)
E 200) 100 parts by weight, 0.1 part by weight of cashew nut-modified phenolic resin (Cenlight Cashew Dust FF-1045, manufactured by Tohoku Kako Co., Ltd.), chlorinated polyethylene having a chlorine content of 36 wt% as an impact-resistant reinforcing agent 10 parts by weight (EXP-771, manufactured by Showa Denko KK) and 21 parts by weight of an α-methylstyrene-AS resin (S-700N, manufactured by Ube Sycon KK) as a heat resistance improver. Was performed in the same manner as in Example 1, and each item was measured. The gloss had a gloss value of 18.1 and was woody. Both the motor load of the extruder and the resin pressure during molding do not rise so high that the moldability is good (○)
Met. No bleeding occurred, and there was no change in the surface condition of the molded product (全 く). The Charpy impact strength was as high as 101.3 kgf · cm / cm 2, a non-destructive region, and the improvement in impact resistance was remarkable. The glass transition temperature was as high as 90.4 ° C., and the heat resistance was significantly improved.

Example 3 An ethylene-vinyl chloride copolymer having an average degree of polymerization of 780 (manufactured by Taiyo Vinyl Co., Ltd., TE-8) was used as the vinyl chloride resin.
00) 100 parts by weight, 50 parts by weight of cashew nut modified phenolic resin (Cenlight Cashew Dust FF-1045, manufactured by Tohoku Kako Co., Ltd.)
BS rubber (BTA-751 manufactured by Kureha Chemical Industry Co., Ltd.)
Was used in the same manner as in Example 1 except that 20 parts by weight was used, and each item was measured. The gloss has a low gloss value of 5.0,
The wood texture was sufficient. Both the motor load of the extruder and the resin pressure during the molding did not rise so high, and the moldability was good (良好). No bleeding occurred, and there was no change in the surface condition of the molded product (全 く).
The Charpy impact strength was as high as 10.3 kgf · cm / cm 2, and the impact resistance was improved.

Example 4 As a vinyl chloride resin, a vinyl acetate-vinyl chloride copolymer having an average degree of polymerization of 780 (manufactured by Taiyo Vinyl Co., Ltd., TV-
800) 100 parts by weight, 100 parts by weight of cashew nut modified phenolic resin (Cenlight Cashew Dust FF-1045, manufactured by Tohoku Kako Co., Ltd.), AD as a foaming agent
Except that 0.5 parts by weight of CA / 0.2 parts by weight of OBSH were used, the procedure was the same as in Example 1, and each item was measured.
The gloss had a low gloss value of 4.8, and the woody texture was sufficient.
Although the motor load of the extruder and the resin pressure at the time of molding were slightly increased, there was almost no drift of the resin, and thus the molding processability was good (）) as judged comprehensively. No bleeding occurred, and there was no change in the surface condition of the molded product (全 く). The specific gravity of the molded product was as low as 0.82, and the expansion ratio was significantly increased.

Example 5 As a vinyl chloride resin, a vinyl chloride graft copolymer having an average degree of polymerization of 1,000 (TA-TAROH, manufactured by Taiyo PVC Co., Ltd.)
E 200) 50 parts by weight and a crosslinked vinyl chloride resin having an average degree of polymerization of 1000 (SD10E, manufactured by Chisso Corporation)
Except for using 0 parts by weight, the same procedure as in Example 1 was carried out, and each item was measured. The gloss has a low gloss value of 4.7,
The wood texture was sufficient. The molding processability was good (機) without increasing the motor load and resin pressure of the extruder during the molding process. No bleeding occurred, and there was no change in the surface condition of the molded product (全 く).

Example 6 A vinyl chloride homopolymer (TH-700, manufactured by Taiyo Vinyl Co., Ltd.) having an average degree of polymerization of 700 was used as the vinyl chloride resin.
1 part by weight of methyltin mercapto (TM-181FSJ, manufactured by Katsuta Kako Co., Ltd.) as a stabilizer and distearyl phthalate ester (Roxyol G60, manufactured by Henkel Hakusui Co., Ltd.) as an internal lubricant. 2 parts by weight, 0.5 parts by weight of a polymer composite ester as an external lubricant, 2 parts by weight of a modified polyethylene, and PM as a processing aid
MA 10 parts by weight, calcium carbonate 5 parts by weight as a filler, ADCA 0.5 part by weight as a foaming agent, OBSH
0.2 parts by weight, 10 parts by weight of cashew nut shell modified phenolic resin (Cenlight Cashew Dust FF-1045, manufactured by Tohoku Kako Co., Ltd.), and 0.5 parts by weight of light brown pigment, manufactured by Mitsui Miike Co., Ltd. The mixture was mixed with a Henschel mixer to obtain a woody vinyl chloride resin composition. The obtained resin composition was melt-molded with a single-screw extruder (PCM-30) having a diameter of 30 mm manufactured by Ikegai Iron Works Co., Ltd. to obtain pellets. The obtained pellet was used as a base pellet (1).

On the other hand, as a vinyl resin for imparting grain, a crosslinked vinyl chloride resin having an average polymerization degree of 700 (Chisso Corporation)
1 part by weight instead of the dark brown pigment is added to 100 parts by weight of SD7E (manufactured by Tohoku Kako Co., Ltd., Senlight Cashew Dust, FF-1045) manufactured by Tohoku Kako Co., Ltd. A resin composition was obtained in the same manner as in the above-mentioned base pellet except that no was added, and was further melt-molded to obtain a seed pellet. The obtained seed pellet was used as a seed pellet (1). The composition is shown in Table 1.

5 parts by weight of the seed pellet (1) was mixed with 100 parts by weight of the base pellet (1), and the mixture was molded by an FS-40 extruder manufactured by Ikegai Iron Works Co., Ltd. to obtain a rectangular parallelepiped molded product. Obtained. At this time, the moldability was evaluated. The gloss, bleeding phenomenon, and grain of the wood were evaluated using the molded product.

The gloss had a low gloss value of 5.3, and the wood texture was sufficient. Both the motor load of the extruder and the resin pressure during molding did not rise so high, and the molding processability was good. No bleeding occurred, and there was no change in the surface condition of the molded article. The grain streaks appeared remarkably, and a molded article having good woody grain was obtained. Table 2 shows the results.

Example 7 For the base pellet, the base pellet (1) was used in the same manner as in Example 6, and the seed pellet had an average degree of polymerization of 1300.
Cross-linked vinyl chloride resin (SD13, manufactured by Chisso Corporation)
E) A seed pellet (2) was obtained in the same manner as in Example 6, except that 100 parts by weight was used. 3 parts by weight of the seed pellet (2) was mixed with 100 parts by weight of the base pellet (1), and the mixture was molded using an FS-40 extruder manufactured by Ikegai Iron Works Co., Ltd. to obtain a rectangular parallelepiped molded product. The evaluation was performed in the same manner as in Example 6.

The gloss had a low gloss value of 5.4, and the wood texture was sufficient. Both the motor load of the extruder and the resin pressure during molding did not rise so high, and the molding processability was good. No bleeding occurred, and there was no change in the surface condition of the molded article. The grain streaks appeared remarkably, and a molded article having good woody grain was obtained. Table 1 shows the composition and Table 2 shows the results.

Example 8 For the base pellet, a vinyl chloride-based graft copolymer having an average degree of polymerization of 1000 (TA-TA-C, manufactured by Taiyo PVC Co., Ltd.)
E200) A mother body pellet (2) was obtained in the same manner as in Example 6 except that 100 parts by weight was used. Regarding the seed pellets, a vinyl polymer resin composed of 20% by weight of acrylonitrile, 70% by weight of α-methylstyrene, and 10% by weight of N-phenylmaleimide (manufactured by Ube Sycon Co., Ltd .;
Seed pellet (3) was obtained in the same manner as in Example 6 except that 100 parts by weight of S802N) was used. 3 parts by weight of the seed pellet (3) was mixed with 100 parts by weight of the base pellet (2), and the mixture was molded using an FS-40 extruder manufactured by Ikegai Iron Works Co., Ltd. to obtain a rectangular parallelepiped molded product. The evaluation was performed in the same manner as in Example 6.

The gloss had a low gloss value of 5.4, and the wood texture was sufficient. Both the motor load of the extruder and the resin pressure during molding did not rise so high, and the molding processability was good. No bleeding occurred, and there was no change in the surface condition of the molded article. The grain streaks appeared remarkably, and a molded article having good woody grain was obtained. Table 1 shows the composition and Table 2 shows the results.

Example 9 For the base pellet, the base pellet (1) was used in the same manner as in Example 6, and the seed pellet had an average degree of polymerization of 700.
Vinyl chloride homopolymer (manufactured by Taiyo Vinyl Co., Ltd., TH
-700) A seed pellet (4) was obtained in the same manner as in Example 6 except that 100 parts by weight was used. The mother pellet (1)
20 parts by weight of the seed pellet (4) was mixed with 100 parts by weight, and the mixture was molded using an FS-40 extruder manufactured by Ikegai Iron Works, Ltd. to obtain a rectangular parallelepiped molded product. Example 6 for evaluation
The procedure was performed in the same manner as described above.

The gloss had a low gloss value of 5.7, and the wood texture was sufficient. Both the motor load of the extruder and the resin pressure during molding did not rise so high, and the molding processability was good. No bleeding occurred, and there was no change in the surface condition of the molded article. The grain streaks appeared remarkably, and a molded article having good woody grain was obtained. The composition is shown in Table 1 and the results are shown in 2.

Example 10 For the base pellet, a vinyl chloride homopolymer (TH-700, manufactured by Taiyo Vinyl Co., Ltd.) having an average polymerization degree of 700 was used.
A base pellet (3) was obtained in the same manner as in Example 6, except that 0 parts by weight and 50 parts by weight of a crosslinked vinyl chloride resin (SD7E, manufactured by Chisso Corporation) having an average degree of polymerization of 700 were used.
Seed pellets (2) were prepared in the same manner as in Example 6.
I got Otherwise, in the same manner as in Example 6, 3 parts by weight of the seed pellet (2) was mixed with 100 parts by weight of the base pellet (3), and the mixture was mixed with FS-4 manufactured by Ikegai Iron Works Co., Ltd.
Molding was performed with a 0 extruder to obtain a rectangular parallelepiped molded product. The evaluation was performed in the same manner as in Example 6. The gloss had a low gloss value of 4.7, and the woody texture was sufficient. Both the motor load of the extruder and the resin pressure during molding did not rise so high, and the molding processability was good. No bleeding occurred, and there was no change in the surface condition of the molded article. The grain streaks appeared remarkably, and a molded article having good woody grain was obtained. Table 1 shows the composition and Table 2 shows the results.

Comparative Example 1 Cashew nut shell oil-modified phenolic resin (Cenlight Cashew Dust FF-104, manufactured by Tohoku Kako Co., Ltd.)
Each item was evaluated in the same manner as in Example 1 except that 5) was replaced with 0.05 part by weight. Both the motor load of the extruder and the resin pressure during the molding did not rise so high, and the moldability was good (良好). The bleeding phenomenon was good (（), but the gloss value as an index of gloss was as high as 25.4, and the woody feel was insufficient.

Comparative Example 2 Cashew nut shell oil-modified phenolic resin (Cenlight Cashew Dust FF-104, manufactured by Tohoku Kako Co., Ltd.)
Each item was evaluated in the same manner as in Example 1 except that 5) was changed to 110 parts by weight. Although the woody texture was confirmed, the motor load of the extruder during the molding process was increased, and the resin drift was large and the shape of the molded product was uneven,
Moldability was poor (x).

Comparative Example 3 Each item was evaluated in the same manner as in Example 6, except that 0.1 part by weight of the seed pellet (1) was mixed with 100 parts by weight of the base pellet (1). Gloss value is 5.8
And low, there was enough wood texture. Both the motor load of the extruder and the resin pressure during molding did not rise so high, and the molding processability was good. No bleeding occurred, and there was no change in the surface condition of the molded article. In addition, although what seemed to be a wood grain line was observed, a clear wood grain did not appear. Table 1 shows the composition and Table 2 shows the results.

Comparative Example 4 Each item was evaluated in the same manner as in Example 6, except that 40 parts by weight of the seed pellet (2) was mixed with 100 parts by weight of the base pellet (2). The gloss had a low gloss value of 5.2, and the woody texture was sufficient. Both the motor load of the extruder and the resin pressure during molding did not rise so high, and the molding processability was good. No bleeding occurred, and there was no change in the surface condition of the molded article. In addition, although grain appeared, the grain overlapped, and a molded article having good woody grain was not obtained. Table 1 shows the composition and Table 2 shows the results.

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[Table 1]

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[Table 2]

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According to the method of the present invention, it is possible to provide a vinyl chloride resin composition having no bleeding phenomenon and excellent in woody feeling, and a molded article using the same. In addition, a vinyl chloride resin composition having a wood-like grain and a molded article using the same can be provided, which is very useful for application development and is industrially superior.

Continuing from the front page (72) Inventor Shuichi Murakami 1-6-6 Takasago, Takaishi-shi, Osaka Mitsui Chemicals, Inc. (72) Inventor Cho Chokami 1-6-6 Takasago, Takaishi-shi, Osaka Mitsui Chemicals, Inc. (72) Invention Takeshi Ohira 1-6-6 Takasago, Takaishi-shi, Osaka Mitsui Chemicals, Inc.

Claims (4)

[Claims] 1. A cashew nut shell oil-modified phenolic resin 0.1 to 100 parts by weight per 100 parts by weight of a vinyl chloride resin.
A wood-like vinyl chloride resin composition containing parts by weight. 2. A woody material obtained by mixing 0.2 to 30 parts by weight of a crosslinked vinyl chloride resin and / or vinyl polymer resin with 100 parts by weight of the woody vinyl chloride resin composition according to claim 1. Vinyl chloride resin composition with wood grain. 3. A woody vinyl chloride resin molded product obtained by melt-molding the woody vinyl chloride resin composition according to claim 1. 4. A molded article of vinyl chloride resin having a woody grain obtained by melt-molding the vinyl chloride resin composition having a woody grain according to claim 2.