JPH10152593A - Vinyl chloride resin composition and vinyl chloride resin molding product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride resin composition and vinyl chloride resin molding products which have excellent wood-like quality with reduced color changes, discoloration and chalking, even in the case that they are used outdoor for a long period of time. SOLUTION: The objective vinyl chloride resin composition and the vinyl chloride resin molding products therefrom contains (A) 100 pts.wt. of vinyl chloride resin, (B) 5-150 pts.wt. of wood flour with an average particle size of 30-500μm, (C) 0.01-1 pts.wt. of a Cu(II) carboxylate salt, (D) 0.01-5 pts.wt. of hydrotalcite and (E) 0.1-10 pts.wt. of at least one kind of pigment selected from quinacridone pigment, perylene pigment, polyazo condensate pigment, isoindolinone pigment, copper phthalocyanine pigment, cadmium pigment, titanium white and carbon black.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a vinyl chloride resin composition and a molded article of a vinyl chloride resin. More specifically, the present invention relates to a vinyl chloride-based resin composition and a vinyl chloride-based resin molded product containing wood flour, which has a rich woody texture similar to natural wood and is used outdoors for a long time. The present invention also relates to a vinyl chloride-based resin composition and a vinyl chloride-based resin molded product which hardly cause discoloration, fading, and chalking.

[0002]

2. Description of the Related Art Wood can be repeatedly produced by photosynthesis, and is therefore being reviewed as a promising resource different from petroleum-based resins. Attempts are being made to grow forests with fast-growing species and reduce the concentration of carbon dioxide that has increased in the atmosphere to regenerate a healthy global environment, while at the same time cutting down systematically and using it as a wood resource for human life. Is being done. Under these circumstances, if we can develop a vinyl chloride-based resin composition that is frequently used in building materials by blending wood powder with vinyl chloride-based resin, which is a general-purpose resin with high mechanical strength and easy molding processing The harmonious use of earth resources will be greatly pioneered. 2. Description of the Related Art Conventionally, for the purpose of producing an appearance and a tactile sensation similar to wood, molding is often performed by blending wood powder with a vinyl chloride resin. But,
When a considerable amount of wood flour is blended, there are problems such as that mechanical strength such as tensile strength is greatly reduced, and natural wood texture has not yet been realized. In order to improve the clarity and ease of processing of wood grain, a vinyl chloride resin composition in which a urea resin is added in addition to wood flour has been proposed (Japanese Unexamined Patent Publication No. Sho 6).
0-42007, JP-A-60-73807, JP-A-60-73808). In addition, in addition to wood flour, an inorganic filler such as mica, and a vinyl chloride resin composition to which polyethylene, ethylene-vinyl acetate copolymer or ABS resin is added, have a low coefficient of linear expansion, impact resistance and moldability. (JP-A-60-1)
No. 92746, JP-A-60-192747). However, even with these, it is not easy to uniformly mix the wood flour, and the appearance of the woody texture of the molded product is insufficient. Dispersion uniformity was greatly improved by blending wood powder to which inorganic powder or plastic powder was attached at the time of plastic processing (JP-A-5-177610, JP-A-5-261708). By simply blending natural wood flour into a vinyl chloride resin, a resin molded product rich in wood texture has not yet been obtained. The present inventors have previously obtained a resin composition in which a vinyl chloride resin was blended with a methacrylate ester resin and wood powder having an average particle size of 50 to 500 μm, and the mechanical strength was large by molding and the wood texture was excellent. It was found to give molded articles. Molded articles obtained from this resin composition, taking advantage of its properties, fittings,
It has been widely used as a substitute for natural wood for furniture and the like. However, this molded product, door frame, bay window frame,
When used in a sunny place such as a baseboard, discoloration or fading or chalking occurs for a long period of time, so that it can be used for outdoor applications and has excellent weather resistance and a rich woody feel. A system resin molded product has been desired. As a vinyl chloride resin composition having little chalking, a composition containing copper acetate (Japanese Patent Publication No. 62-41532)
JP-A-6-322206), a composition containing an A-type zeolite substituted with copper or cobalt (Japanese Patent Publication No. 1-44421), and a composition containing copper acetate and a hydrotalcite compound (JP-A-6-322206) , A composition containing copper stearate and melamine (JP-A-7-292193) and the like have been proposed. However, in a vinyl chloride resin composition containing wood flour, an effect of preventing chalking cannot be obtained and an effect of improving color fastness cannot be obtained depending on these compositions.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to a vinyl chloride resin composition and a vinyl chloride resin composition which have an excellent woody feeling and are less likely to cause discoloration, fading or chalking even when used outdoors for a long period of time. The purpose is to provide a resin molded product.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a composition containing a vinyl chloride resin and wood flour was further added with a copper carboxylic acid.
(II) A molded product obtained from a composition colored with a pigment and containing hydrotalcite supporting a salt and hydrotalcite or a copper (II) salt is discolored or discolored even when used outdoors for a long period of time. The inventors have found that fading and chalking rarely occur, and have completed the present invention based on this finding. That is, the present invention provides (1) (A) 100 parts by weight of a vinyl chloride resin, (B) 5-150 parts by weight of wood powder having an average particle size of 30 to 500 μm,
(C) Copper (II) salt of a carboxylic acid having 1 to 3 carbon atoms 0.01 to 0.01
1 part by weight, (D) 0.01 to 5 parts by weight of hydrotalcite and (E) quinacridone pigment, perylene pigment, polyazo condensed pigment, isoindolinone pigment, copper phthalocyanine pigment, cadmium pigment, titanium white And at least one pigment selected from the group consisting of carbon black and 0.1 to 10 parts by weight, (2) (A) 100 parts by weight of the vinyl chloride resin (B) 5-150 parts by weight of wood flour having an average particle size of 30 to 500 μm;
(F) Hydrotalcite supporting copper (II) salt 0.0
1 to 5 parts by weight and (E) a quinacridone pigment, a perylene pigment, a polyazo condensed pigment, an isoindolinone pigment,
A copper phthalocyanine-based pigment, a cadmium-based pigment, a vinyl chloride-based resin composition comprising 0.1 to 10 parts by weight of at least one pigment selected from the group consisting of titanium white and carbon black, and (3) A vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition according to the above item (1) or (2). Further, as a preferred embodiment of the present invention, (4) (A) per 100 parts by weight of the vinyl chloride resin,
(G) the vinyl chloride resin composition according to item (1) or (2), containing not more than 30 parts by weight of a methacrylate resin, and (5) (A) 100 parts by weight of a vinyl chloride resin. Hit
(H) No. (1) containing 5 to 15 parts by weight of impact modifier
Or the vinyl chloride resin composition described in the item (2).

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. Examples of the vinyl chloride resin used as the component (A) in the composition of the present invention include a vinyl chloride copolymer having 50% by weight or more of vinyl chloride units, in addition to a vinyl chloride homopolymer. Examples of monomers copolymerized with vinyl chloride include olefins such as ethylene and propylene; halogenated olefins such as allyl chloride, vinylidene chloride, vinyl fluoride, and ethylene trifluoride chloride; vinyl acetate and propionic acid Carboxylic acid vinyl esters such as vinyl; isobutyl vinyl ether;
Vinyl ethers such as cetyl vinyl ether; allyl ethers such as allyl-3-chloro-2-oxypropyl ether and allyl glycidyl ether; acrylic acid, maleic acid, itaconic acid, 2-hydroxyethyl acrylate, methyl methacrylate, and maleic acid Unsaturated carboxylic acids such as monomethyl acid, diethyl maleate, and maleic anhydride, esters or acid anhydrides thereof; acrylonitrile, unsaturated nitriles such as methacrylonitrile; acrylamide, N-methylolacrylamide,
Acrylamides such as acrylamide-2-methylpropanesulfonic acid and (meth) acrylamidopropyltrimethylammonium chloride; allylamine such as allylamine benzoate and diallyldimethylammonium chloride; and derivatives thereof. The monomers exemplified above are only a part of copolymerizable monomers, and are exemplified in “Polyvinyl Chloride” edited by Kinki Chemical Association Vinyl Subcommittee, Nikkan Kogyo Shimbun (1988), pp. 75-104. Various monomers can be used. One or two or more of these comonomers can be copolymerized. Further, a resin such as ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, chlorinated polyethylene, vinyl chloride or a copolymerizable monomer described above with vinyl chloride. And resins obtained by graft polymerization of These vinyl chloride resins may be produced by any conventionally known production method such as suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization. The average degree of polymerization of the vinyl chloride resin is preferably from 400 to 1,500 as measured according to JIS K6721.
More preferably, it is １1,100. If the average degree of polymerization of the vinyl chloride resin is less than 400, the mechanical properties of the obtained molded article are low, and the color fastness and the choking resistance may be poor. If the average degree of polymerization of the vinyl chloride resin exceeds 1,500, kneading and molding become difficult, and it may be difficult to uniformly disperse the wood powder in the resin composition.

In the composition of the present invention, wood powder having an average particle diameter of 30 to 500 μm, more preferably 50 to 100 μm is contained as the component (B). The content of the wood powder is 5 to 150 per 100 parts by weight of the vinyl chloride resin.
Parts by weight, preferably 22 to 120 parts by weight, more preferably 25 to 100 parts by weight. There is no particular limitation on the wood flour used in the present invention, and for example, coniferous or hardwood timber pieces such as cedar, hemlock and lauan, and wood such as planing and sawdust can be used. In order to obtain wood flour used as the component (B) in the composition of the present invention from these woods, for example, a wood having an average particle size of 30 to 5 using a pulverizer is used.
It is preferable to use a relatively round wood powder of 00 μm. In the composition of the present invention, as wood powder,
Wood powder having hard small particles adhered to the surface disclosed in 177610 and JP-A-5-261708 can be used. The mode in which the hard small particles adhere to the surface of the wood flour includes hard small particles such as an entanglement bond including biting of the hard small particles into the wood flour, and a pinch bond between a plurality of hard small particles that have been bitten bonded. Adhesion by pressing against the surface of the wood powder may be applied, or hard small particles may be attached to the wood powder by an adhesive. In this case, it is preferable that the wood flour is charged together with 1 to 50% by weight of hard small particles in a ball mill or the like, and is subjected to a treatment for preventing dust explosion such as placing it in a nitrogen atmosphere. In the composition of the present invention, the average particle size of the wood flour, the powder is classified by a sieve to create a cumulative weight% curve with respect to the opening,
The value of the aperture corresponding to 50% by weight is read. When the average particle size of the wood flour is less than 30 μm, the bulk specific gravity becomes small, and the mixing operability for preparing the composition may be deteriorated. If the average particle size of the wood flour exceeds 500 μm, the surface of the molded product may be roughened, and the wood texture may be reduced. If the content of the wood powder is less than 5 parts by weight per 100 parts by weight of the vinyl chloride resin, it may be difficult to give a molded article a sufficient woody feel. If the content of the wood powder exceeds 150 parts by weight per 100 parts by weight of the vinyl chloride resin, the mechanical strength of the molded article may be reduced. The water content of the wood flour is preferably 10% by weight or less, more preferably 5% by weight or less.

In the composition of the present invention, a copper (II) salt of a carboxylic acid having 1 to 3 carbon atoms is contained as the component (C).
As a copper (II) salt of a carboxylic acid having 1 to 3 carbon atoms, for example, copper (II) formate, copper (II) acetate, copper (II) propionate, copper oxalate (II), copper malonate (II) ). The content of the copper (II) salt of a carboxylic acid having 1 to 3 carbon atoms is
The amount is 0.01 to 1 part by weight, more preferably 0.1 to 0.5 part by weight, per 100 parts by weight of the vinyl chloride resin.
If the content of the copper (II) salt of a carboxylic acid having 1 to 3 carbon atoms is less than 0.01 part by weight per 100 parts by weight of the vinyl chloride resin, the molded article may be liable to be chalked. If the content of the copper (II) salt of a carboxylic acid having 1 to 3 carbon atoms exceeds 1 part by weight per 100 parts by weight of the vinyl chloride resin, the thermal stability of the vinyl chloride resin composition may be reduced. Further, in place of the copper (II) salt of a carboxylic acid having 1 to 3 carbon atoms, a copper (II) salt of a carboxylic acid having 4 or more carbon atoms or a metal salt other than copper (II) of a carboxylic acid is contained. There is a possibility that the ability to suppress discoloration of the vinyl chloride resin molded product due to long-term exposure to ultraviolet light may be reduced. In the composition of the present invention, hydrotalcite is contained as the component (D). Hydrotalcite has the general formula [Mg _1-x Al _x (O
H) ₂ ] ^{x +} [(CO ₃ ) _{x / 2} · mH ₂ O] ^x− , a non-stoichiometric compound and a positively charged base layer [Mg _1-x Al _x (O
H) ₂ ] ^{x +} and a negatively charged intermediate layer [(CO ₃ ) _{x / 2}
mH ₂ O] ^x- is an inorganic substance having a layered crystal structure. Here, x is a number greater than 0 and less than 0.33. Natural products are Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂
O, and the synthetic product is mainly composed of Mg _4.5 Al ₂ (O
H) ₁₃ CO ₃ .3.5H ₂ O is commercially available.
In the composition of the present invention, the content of the hydrotalcite as the component (D) is 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, per 100 parts by weight of the vinyl chloride resin. . If the content of hydrotalcite is less than 0.01 part by weight per 100 parts by weight of the vinyl chloride resin, the molded article may be liable to be chalked.
Hydrotalcite content of vinyl chloride resin 100
If the amount exceeds 5 parts by weight per part by weight, the thermal stability of the vinyl chloride resin composition may decrease.

In the composition of the present invention, instead of the copper (II) salt of a carboxylic acid having 1 to 3 carbon atoms of the component (C) and the hydrotalcite of the component (D), copper (II) is used as the component (F). ) It can contain hydrotalcite carrying a salt. There is no particular limitation on the method of supporting the copper (II) salt on the hydrotalcite, for example, a predetermined amount of an aqueous solution of the copper (II) salt is added to water in which the hydrotalcite is suspended, and the mixture is thoroughly stirred, and then By filtering and drying, hydrotalcite supporting a copper (II) salt can be obtained. The copper (II) salt used is not particularly limited as long as it is a water-soluble salt, and examples thereof include sulfates, hydrochlorides, nitrates, and acetates. The amount of copper (II) added to hydrotalcite is not particularly limited, but the amount of copper (II) is preferably 0.1 to 15 parts by weight based on 100 parts by weight of hydrotalcite. The amount of copper (II) added is hydrotalcite 1
If the amount is less than 0.1 part by weight per 100 parts by weight, the molded article may be liable to be chalked. When the addition amount of copper (II) exceeds 15 parts by weight per 100 parts by weight of hydrotalcite, unsupported copper (II) salt is present, and the thermal stability of the vinyl chloride resin composition may be reduced. In the composition of the present invention, the content of the hydrotalcite supporting the copper (II) salt as the component (F) is 0.01 to 5 parts by weight per 100 parts by weight of the vinyl chloride resin, and is more preferably. 0.1 to 3 parts by weight. The content of hydrotalcite carrying copper (II) salt is vinyl chloride resin 10
If the amount is less than 0.01 parts by weight per 0 parts by weight, the molded product may be liable to be chalked. If the content of the hydrotalcite supporting the copper (II) salt exceeds 5 parts by weight per 100 parts by weight of the vinyl chloride resin, the thermal stability of the vinyl chloride resin composition may be reduced.

In the composition of the present invention, the component (E) is a group consisting of quinacridone pigments, perylene pigments, polyazo condensation pigments, isoindolinone pigments, copper phthalocyanine pigments, cadmium pigments, titanium white and carbon black. And at least one pigment selected from the group consisting of: The quinacridone pigment is obtained by treating p-phenylenedianthranilic acids with concentrated sulfuric acid,
From yellowish red to reddish purple hue, quinacridone red,
There are quinacridone magenta, quinacridone violet and the like. Perylene pigments are perylene-3,4,9,10
-Obtained by a condensation reaction of tetracarboxylic anhydride and an aromatic primary amine, the hue ranges from red to purple-red, brown,
There are perylene red, perylene orange, perylene maroon, perylene vermilion, perylene bordeaux and the like. Polyazo condensed pigments are those obtained by condensing an azo dye in a solvent to have a high molecular weight, and as a hue are yellow and red pigments, such as polyazo red, polyazo yellow, chromophthal orange, chromophthal red, and chromophthal scarlet. There is. Isoindolinone pigments are 4,5,
It is obtained by a condensation reaction of 6,7-tetrachloroisoindolinone and an aromatic primary diamine, and its hue ranges from greenish yellow to red to brown, and includes isoindolinone yellow. Copper phthalocyanine pigments are pigments in which copper is coordinated to phthalocyanines, and have a hue from yellowish green to vivid blue, and include phthalocyanine green and phthalocyanine blue. Cadmium-based pigments are pigments composed of a solid solution containing cadmium sulfide, and have a hue range of yellow,
Red, maroon, cadmium red, cadmium orange, cadmium yellow, etc. Titanium white is a white pigment made of titanium dioxide, which has a large hiding power and has an anatase type and a rutile type. Carbon black is a black pigment containing carbon, oxygen, hydrogen, and nitrogen as its main components. Thermal black, acetylene black, channel black, furnace black, lamp black,
Bone black and others. The composition of the present invention is not only beautifully colored and full of a natural woody feeling by adding the above-mentioned pigment and coloring, but also causes discoloration or fading even when used outdoors for a long period of time. Less likely to cause chalking. In addition to the above pigments, monoazo red, monoazo yellow, bisazo red, titanium yellow, graphite, chrome vermillion,
Ultramarine blue and the like are known to improve the weather resistance of the resin by absorbing and reflecting ultraviolet light by coloring. However, in the composition of the present invention, only the pigments listed as the component (E) can exert the effects of excellent color fastness and chalking resistance. In the composition of the present invention, the content of the pigment as the component (E) is 0.1 to 10 parts by weight per 100 parts by weight of the vinyl chloride resin,
More preferably, it is 1 to 5 parts by weight. When the content of the pigment as the component (E) is less than 0.1 part by weight per 100 parts by weight of the vinyl chloride resin, it may be difficult to give a molded article a rich woody feel. When the content of the pigment as the component (E) exceeds 10 parts by weight per 100 parts by weight of the vinyl chloride resin, the natural woody feeling of the molded article may be rather deteriorated.

[0010] In the composition of the present invention, a methacrylic ester resin can be contained as the component (G). Examples of the methacrylate resin include a methyl methacrylate homopolymer and a methyl methacrylate copolymer having 50% by weight or more, preferably 70% by weight or more of methyl methacrylate units. Examples of the monomer to be copolymerized with methyl methacrylate include, for example, ethyl acrylate, butyl acrylate, ethoxyethyl acrylate, 2-ethylhexyl methacrylate,
Examples thereof include 2-hydroxypropyl methacrylate, glycidyl methacrylate, acrylonitrile, and vinyl acetate. One or two or more of these comonomers can be copolymerized. This methacrylic ester resin is a methacrylic ester resin disclosed in Japanese Patent Publication No. 5-38014, that is, the inside of the particles is a copolymer of methyl methacrylate and acrylate, and the outside is methacrylic acid. Resin particles such as a two-stage resin coated with a methyl homopolymer or a copolymer mainly composed of methyl methacrylate may be used. In the composition of the present invention, wood flour, for example, when blended as high as 10 parts by weight or more, by further blending a methacrylate ester resin as a component (G), the wood flour and vinyl chloride resin Since it is familiar and can be uniformly dispersed, a rich woody feeling can be exhibited. The methacrylate resin used as the component (G) preferably has a specific viscosity at 25 ° C. of a 0.2 g / dl chloroform solution of 1.5 to 4.0, and more preferably 2.0 to 4.0.
More preferably, it is 3.0. The value of this specific viscosity is
If it is less than 1.5, the woodiness of the molded article may be reduced. When the value of the specific viscosity exceeds 4.0, the time required for uniformly kneading the composition may be long. In the composition of the present invention, the content of the methacrylic ester-based resin can be appropriately selected according to the content of the wood flour.
It is preferable that the content be not more than part by weight. When the content of the methacrylate ester resin exceeds 30 parts by weight per 100 parts by weight of the vinyl chloride resin, the melt viscosity of the resin composition becomes high, and the resin may be easily deteriorated by heat.

When the composition of the present invention is intended for a molded article having a particularly high impact strength, an impact resistance improver can be contained as a component (H). Examples of the impact modifier include acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, chlorinated polyethylene, ethylene-
Vinyl chloride graft copolymer to vinyl acetate copolymer,
Examples thereof include an ethylene-vinyl acetate copolymer and chlorosulfonated polyethylene. In these impact modifiers, fine elastic particles are dispersed in a heterogeneous phase in a vinyl chloride resin composition, and chains and polar groups graft-polymerized on the elastic particles are compatible with the vinyl chloride resin. By doing so, the impact resistance of the vinyl chloride resin composition is improved. When a molded article comprising the composition of the present invention is used for outdoor applications, by blending an impact resistance improver, even when the outside air temperature decreases in winter, the number of accidents in which the molded article is damaged by impact is reduced. preferable. In the composition of the present invention, (H)
When an impact modifier is included as a component, the content is preferably 5 to 15 parts by weight per 100 parts by weight of the vinyl chloride resin in order to improve the impact resistance. If the content of the impact resistance improver is less than 5 parts by weight per 100 parts by weight of the vinyl chloride resin, a remarkable impact resistance improvement effect may not be obtained. If the content of the impact resistance improver exceeds 15 parts by weight per 100 parts by weight of the vinyl chloride resin, mechanical strength other than impact strength may be reduced. The composition of the present invention, in addition to the above components, in addition to heat stabilizers and lubricants blended in the ordinary vinyl chloride resin composition, ultraviolet absorbers, plasticizers, antistatic agents, foaming agents and the like It can be added as appropriate.

To prepare the composition of the present invention,
(A) vinyl chloride resin, (B) wood flour, (C) copper (II) salt of carboxylic acid having 1 to 3 carbon atoms and (D) hydrotalcite or
(F) hydrotalcite supporting copper (II) salt and (E)
The pigments are collectively charged into a mixer such as a Henschel mixer, and the temperature is increased to 120 to 160 ° C. with vigorous stirring and mixing. During this mixing process, the moisture absorbed by the wood flour is volatilized. By using a Henschel mixer or the like to charge and mix all components at once, a mixture having a large bulk specific gravity and uniformly dispersed additives such as pigments can be obtained. After reaching the above-mentioned temperature, the mixture is transferred to a cooling mixer, and if necessary for the blending, a pyrolytic foaming agent is added, and the temperature is raised to 50 to 60 ° C. After the temperature of the mixture in the cooling mixer has sufficiently decreased, the mixture is taken out of the cooling mixer in the form of a powder. The powdery mixture taken out can be used as a molding compound as it is, but it is usually preferable to subsequently pelletize it. As a preferred method of pelletization, for example, using a vented single-screw extruder or twin-screw extruder,
A method in which the temperature of the cylinder and the temperature of the die are set to 150 to 170 ° C., and the pellets are formed while discharging the residual moisture in the wood flour through the vent hole. Using the composition of the present invention, there is no particular limitation on a molding method for obtaining a vinyl chloride resin molded article rich in woody texture similar to natural wood, and is usually extrusion molding, calender roll molding, injection molding. It can be molded by a vacuum molding method or a vacuum molding method.

[0013]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In Examples and Comparative Examples, color fastness and chalking were evaluated by the following methods. (1) Color Fastness Evaluated according to JIS K 7102. That is,
A sheet molded from a vinyl chloride resin composition is 60 mm x
A test piece cut into 120 mm was used as a test piece, and subjected to water spraying at 2,000 using a sunshine carbon arc lamp type weather resistance tester [Duecycle Sunshine Weather Meter WEL-SUN-DC, Suga Test Machine Co., Ltd.].
Irradiation was performed for 0 hours, and the color difference ΔE of the test pieces before and after the irradiation was measured using a color computer [SM-4-2, Suga Test Instruments Co., Ltd.]. (2) Chalking For the test pieces for which the color fastness was examined, the chalking degree was determined according to the following criteria. A: No choking at all. ：: Slight chalking. Δ: fairly choking. ×: There is significant choking. Example 1 Vinyl chloride resin [ZEST700L, Shin-Daiichi PVC Co., Ltd.
Average polymerization degree 680] 100 parts by weight, methacrylate resin [Hybrene B403, Nippon Zeon Co., Ltd., copolymer having about 90% by weight of methyl methacrylate unit, specific viscosity 2.06] 2 parts by weight, wood flour [Selund, Shimada Shokai Co., Ltd., average particle size 80 μm, water content 5% by weight] 50 parts by weight, 0.2 parts by weight of copper (II) acetate, hydrotalcite [D
HT-6, Kyowa Chemical Industry Co., Ltd., synthetic hydrotalcite, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O, average particle size 0.5 μm] 1.5 parts by weight, heat stabilizer [ Tribasic lead sulfate / lead stearate composite heat stabilizer] 5 parts by weight, lubricant [polyethylene wax, ACPE6A, Allied Chemical Co.] 1 part by weight, filler [calcium carbonate, CCR, Shiroishi calcium Co., Ltd., average particle size] 0.08 μm] and 4 parts by weight of quinacridone red were charged into a Henschel mixer, and steam was evaporated while mixing. After the temperature rose to 140 ° C., the mixture was transferred to a cooling mixer and cooled while further mixing to obtain a powdery mixture. The obtained powdery mixture was pelletized using a vented single-screw extruder having a cylinder diameter of 65 mm under the following conditions. In addition, the moisture remaining in the wood powder was volatilized from the vent hole. Screw: L / D = 24, compression ratio 2.5, rotation speed 30 rpm Set temperature: C ₁ = 130 ° C., C ₂ = 140 ° C., C ₃ = 150 ° C. C ₄ = 160 ° C., head 160 ° C., die 160 ° C. Die: 3 mmφ pellet × 12 holes Land length: 10 mm The obtained pellet is heated at 160 ° C. using an 8-inch roll.
And kneaded for 5 minutes to form a 1 mm thick sheet.
Pressing at 5 ° C. for 5 minutes gave a red sheet rich in woody texture with a thickness of 1 mm. The obtained sheet was subjected to an accelerated weathering test for 2,000 hours. The color difference ΔE after the accelerated weathering test was 2.5, and no choking was observed. Examples 2 to 25 For the compositions having the compositions shown in Table 1, a sheet having a thickness of 1 mm was prepared in the same manner as in Example 1, and an accelerated weathering test was performed for 2,000 hours. The color difference ΔE and the degree of choking were determined. The results are shown in Table 1. Comparative Examples 1 to 9 For the compositions having the formulations shown in Table 2, a sheet having a thickness of 1 mm was prepared in the same manner as in Example 1 and subjected to an accelerated weathering test for 2,000 hours. The color difference ΔE and the degree of choking were determined. The results are shown in Table 2.

[0014]

[Table 1]

[0015]

[Table 2]

[0016]

[Table 3]

[0017]

[Table 4]

[0018]

[Table 5]

[0019]

[Table 6]

[0020]

[Table 7]

[Note] 1) ZEST 700L, Shin-Daiichi PVC Co., Ltd., average polymerization degree 6
80. 2) Hybrene B403, Nippon Zeon Co., Ltd., a copolymer having about 90% by weight of methyl methacrylate units, specific viscosity 2.06. 3) Cellyund, Shimada Shokai, average particle size 80 μm,
Water content 5% by weight. 4) E60-T5-3, Misawa Techno Co., Ltd., wood powder with titanium oxide particles attached, titanium oxide content 5% by weight, average particle size 6
0 μm, water content 5% by weight. 5) DHT-6, Kyowa Chemical Industry Co., Ltd., synthetic hydrotalcite, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O, average particle size 0.5 μm. 6) Copper (II) salt-supported hydrotalcite, DHT-6 above
Was stirred and suspended in 900 parts by weight of deionized water, 20 parts by weight of a 10% by weight aqueous solution of cupric sulfate pentahydrate was added, and the mixture was stirred for 1 hour, suctioned, filtered and washed with water. ,
The dried solid is dried in an oven at 150 ° C. and then ground in a mortar. 7) Tribasic lead sulfate / lead stearate composite heat stabilizer. 8) Polyethylene wax, ACPE6A, Allied Chemical Company. 9) Calcium carbonate, CCR, Shiraishi calcium, Inc., average particle size 0.08 μm. 10) (MgCO ₃ ) ₄ .Mg (OH) ₂ .5H ₂ O. From the results in Tables 1 and 2, the sheet obtained from the vinyl chloride resin composition of the present invention has a small value of the color difference ΔE in the accelerated weathering test for 2,000 hours, and is excellent in color fastness. You can see that. In addition, it can be seen that no chalking occurs and the choking resistance is excellent. On the other hand, copper of carboxylic acid having 1 to 3 carbon atoms
(II) The composition of Comparative Example 1 containing no salt, the composition of Comparative Example 2 containing copper (II) citrate instead of the copper (II) salt of a carboxylic acid having 1 to 3 carbon atoms, Copper of carboxylic acid of ~ 3
(II) The composition of Comparative Example 3 containing nickel acetate instead of the salt, the composition of Comparative Example 4 containing no hydrotalcite, and the composition of Comparative Example 5 containing magnesium hydroxycarbonate instead of hydrotalcite All of the sheets obtained from (1) and (2) had remarkable discoloration or fading in the accelerated weathering test for 2,000 hours, had a large value of color difference ΔE, and were inferior in color fastness. In addition, it chokes considerably or remarkably, and is inferior in choking resistance. Furthermore, the compositions of Comparative Examples 4 and 5 containing no hydrotalcite caused thermal discoloration during molding. As pigments, quinacridone pigments, perylene pigments, polyazo condensation pigments,
Sheets obtained from the compositions of Comparative Examples 6 to 9 containing an isoindolinone-based pigment, a copper phthalocyanine-based pigment, a cadmium-based pigment, a pigment other than titanium white and carbon black, all had accelerated weatherability of 2,000 hours. In the test, the color was significantly discolored or faded, the value of the color difference ΔE was large, and the color fastness was poor. In addition, it chokes considerably or remarkably, and is inferior in choking resistance. Example 26 Vinyl chloride resin [ZEST700L, Shin-Daiichi PVC Co., Ltd.
Average polymerization degree 680] 100 parts by weight, methacrylate resin [Hybrene B403, Nippon Zeon Co., Ltd., copolymer having about 90% by weight of methyl methacrylate unit, specific viscosity 2.06] 2 parts by weight, wood flour [Selund, Shimada Shokai Co., Ltd., average particle size 80 μm, water content 5% by weight] 50 parts by weight, 0.2 parts by weight of copper (II) acetate, hydrotalcite [D
HT-6, Kyowa Chemical Industry Co., Ltd., synthetic hydrotalcite, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O, average particle size 0.5 μm] 1.5 parts by weight, heat stabilizer [ Tribasic lead sulfate / lead stearate composite heat stabilizer] 5 parts by weight, lubricant [polyethylene wax, ACPE6A, Allied Chemical Co.] 1 part by weight, filler [calcium carbonate, CCR, Shiroishi calcium Co., Ltd., average particle size] 0.08 μm] 5 parts by weight and a mixed pigment 4 of quinacridone red / isoindolinone yellow / titanium white = 1/1 / 0.02 (weight ratio)
The weight part was charged into a Henschel mixer, and steam was volatilized while mixing. After the temperature rose to 140 ° C., the mixture was transferred to a cooling mixer and cooled while further mixing to obtain a powdery mixture. The obtained powdery mixture was extruded into pellets in the same manner as in Example 1 and further kneaded using a roll, and pressed to a thickness of 1 mm.
An ocher sheet rich in wood texture was obtained. The obtained sheet was subjected to an accelerated weathering test for 2,000 hours. The color difference ΔE after the accelerated weathering test was 4.3, and no chalking was observed. Example 27 Wood powder [E60-T5-
3, Misawa Techno Co., Ltd., titanium oxide content 5% by weight, average particle size 60 μm, water content 5% by weight], and as a pigment, perylene orange / phthalocyanine green = 1/0.
Example 26 except that a mixed pigment of 02 (weight ratio) was used.
In the same manner as in the above, an ocher-colored sheet rich in woody texture with a thickness of 1 mm was obtained. The obtained sheet was subjected to an accelerated weathering test for 2,000 hours. Color difference ΔE after accelerated weathering test
Was 3.8 and she did not chalk at all. Example 28 The methacrylate resin [Hybrene B403, Nippon Zeon Co., Ltd., a copolymer having a methyl methacrylate unit of about 90% by weight, specific viscosity of 2.06] was used in an amount of 15 parts by weight. 4 parts by weight of a mixed pigment of indolinone yellow / cadmium orange / titanium white = 1 / 0.3 / 1 (weight ratio) was added, and when the temperature of the mixture was lowered to 60 ° C. in a cooling mixer, a blowing agent [azo Dicarbonamide] was obtained in the same manner as in Example 26 except that 1 part by weight of dicarbonamide was added to obtain a pale orange sheet having a thickness of 1 mm and rich in woody texture. About the obtained sheet,
An accelerated weathering test of 2,000 hours was performed. The color difference ΔE after the accelerated weathering test was 4.1, and no choking was observed. Example 29 Synthetic hydrotalcite [DHT-6, Kyowa Chemical Industry
Co., Ltd., Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O, average particle size 0.5 μm] 100 parts by weight in a state of being stirred and suspended in 900 parts by weight of deionized water, 10 parts by weight 5% cupric sulfate 5
Add 20 parts by weight of the hydrate aqueous solution, stir for 1 hour,
After filtering, washing with water and drying the solid substance taken out in an oven at 150 ° C., it was pulverized with a mortar to prepare hydrotalcite supporting copper (II). Instead of 0.2 parts by weight of copper (II) acetate and 1.5 parts by weight of hydrotalcite, 1.5 parts by weight of the above-mentioned hydrotalcite supporting copper (II) is blended, and isoindolinone yellow / cadmium is used as a pigment. Orange / titanium white = 1 / 0.3 / 1 (weight ratio)
In the same manner as in Example 26 except that 4 parts by weight of the mixed pigment was mixed, a pale orange sheet having a thickness of 1 mm and rich in woody texture was obtained. The obtained sheet was subjected to an accelerated weathering test for 2,000 hours. The color difference ΔE after the accelerated weathering test was 3.9, and no choking was observed. Table 3 shows the composition and results of Examples 26 to 29. Comparative Examples 10 to 16 For the compositions having the compositions shown in Table 4, a sheet having a thickness of 1 mm was prepared in the same manner as in Example 26, and an accelerated weathering test was performed for 2,000 hours. The color difference ΔE and the degree of choking were determined. The results are shown in Table 4.

[0022]

[Table 8]

[0023]

[Table 9]

[0024]

[Table 10]

[Note] 1) ZEST 700L, Shin-Daiichi PVC Co., Ltd., average degree of polymerization 6
80. 2) Hybrene B403, Nippon Zeon Co., Ltd., a copolymer having about 90% by weight of methyl methacrylate units, specific viscosity 2.06. 3) Cellyund, Shimada Shokai, average particle size 80 μm,
Water content 5% by weight. 4) E60-T5-3, Misawa Techno Co., Ltd., wood powder with titanium oxide particles attached, titanium oxide content 5% by weight, average particle size 6
0 μm, water content 5% by weight. 5) DHT-6, Kyowa Chemical Industry Co., Ltd., synthetic hydrotalcite, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O, average particle size 0.5 μm. 6) Copper (II) salt-supported hydrotalcite, DHT-6 above
Was stirred and suspended in 900 parts by weight of deionized water, 20 parts by weight of a 10% by weight aqueous solution of cupric sulfate pentahydrate was added, and the mixture was stirred for 1 hour, suctioned, filtered and washed with water. ,
The dried solid is dried in an oven at 150 ° C. and then ground in a mortar. 7) Tribasic lead sulfate / lead stearate composite heat stabilizer. 8) Polyethylene wax, ACPE6A, Allied Chemical Company. 9) Calcium carbonate, CCR, manufactured by Shiraishi Calcium Co., Ltd.
Average particle size 0.08 μm. 11) A mixed pigment of quinacridone red / isoindolinone yellow / titanium white = 1/1 / 0.02 (weight ratio). 12) Perylene orange / phthalocyanine green = 1
/0.02 (weight ratio) mixed pigment. 13) A mixed pigment of isoindolinone yellow / cadmium orange / titanium white = 1 / 0.3 / 1 (weight ratio). 14) Azo lake / cobalt blue = 1 / 0.01 (weight ratio) mixed pigment. 15) A mixed pigment of polyazo red / ultramarine = 1 / 0.3 (weight ratio). 16) A mixed pigment having a red handle / chrome vermillion = 1/1 (weight ratio). 17) Azodicarbonamide. From the results in Tables 3 and 4, the sheet obtained from the vinyl chloride resin composition of the present invention has a small color difference ΔE in the accelerated weathering test for 2,000 hours and is excellent in color fastness. You can see that. In addition, it can be seen that there is no choking at all and the choking resistance is excellent. In contrast, copper (II) of a carboxylic acid having 1 to 3 carbon atoms
The composition of Comparative Example 10 in which copper (II) citrate was blended in place of the salt, the composition of Comparative Example 11 in which nickel acetate was blended in place of the copper (II) salt of a carboxylic acid having 1 to 3 carbon atoms, and a pigment Comparative examples in which pigments other than quinacridone pigments, perylene pigments, polyazo condensed pigments, isoindolinone pigments, copper phthalocyanine pigments, cadmium pigments, titanium white and carbon black are blended in some or all of the blended pigments Sheets obtained from the composition of Comparative Example 16 containing no composition of 12 to 15 and no hydrotalcite,
In all cases, discoloration or fading was remarkable in the accelerated weathering test for 2,000 hours, the value of the color difference ΔE was large, and the color fastness was poor. Also choking considerably or significantly,
Poor chalking resistance. Furthermore, the composition of Comparative Example 16 containing no hydrotalcite caused thermal discoloration during molding.

[0026]

By molding the vinyl chloride resin composition of the present invention, it is possible to obtain a molded article which is beautifully colored and has a natural woody texture. This molded article is less likely to be discolored or faded even when used outdoors for a long period of time, and hardly causes chalking.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 97/02 C08L 97/02

Claims (3)

[Claims] (A) 100 parts by weight of a vinyl chloride resin,
(B) 5-150 parts by weight of wood powder having an average particle size of 30 to 500 μm, and (C) copper (II) salt of a carboxylic acid having 1 to 3 carbon atoms, 0.0.
1 to 1 part by weight, (D) hydrotalcite 0.01 to 5
Parts by weight and at least one pigment selected from the group consisting of (E) quinacridone pigments, perylene pigments, polyazo condensation pigments, isoindolinone pigments, copper phthalocyanine pigments, cadmium pigments, titanium white and carbon black A vinyl chloride resin composition comprising 0.1 to 10 parts by weight. (A) 100 parts by weight of a vinyl chloride resin,
(B) 5-150 parts by weight of wood powder having an average particle size of 30 to 500 μm, (F) 0.01 to 5 parts by weight of hydrotalcite supporting copper (II) salt, and (E) quinacridone-based pigment, perylene-based Pigment, polyazo condensed pigment, isoindolinone pigment, copper phthalocyanine pigment, cadmium pigment, titanium white and carbon black containing 0.1 to 10 parts by weight of at least one pigment selected from the group consisting of Characteristic vinyl chloride resin composition. 3. A vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition according to claim 1.