JP2003171526A - Polyvinyl chloride-based resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyvinyl chloride-based resin composition, and a molding thereof, excellent in linear expansion coefficient and in impact resistance. <P>SOLUTION: The polyvinyl chloride-based resin composition and the molding thereof are prepared by adding 10-60 pts.wt. of a needle-like or lamellar inorganic matter to 100 pts.wt. of a polyvinyl chloride-based resin obtained by graft copolymerization of 70-99 wt.% of a vinyl chloride-based monomer onto 1-30 wt.% of an elastomer component. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a vinyl chloride resin composition and a molded article made of the composition.

[0002]

2. Description of the Related Art Originally, polyvinyl chloride resins are used in many applications as materials having excellent mechanical strength and chemical resistance. Furthermore, a vinyl chloride resin composition to which a needle-like or plate-like inorganic substance is added in order to reduce the heat shrinkability and the linear expansion coefficient when used for a rain gutter or a window frame member has been proposed. If an inorganic substance is added,
It has the drawback of reduced impact resistance. As a method for improving the impact resistance of the vinyl chloride resin composition filled with the inorganic material, for example, JP-A-2000-355646 can be used.
In the publication, a vinyl chloride resin composition to which various impact modifiers are added is proposed, but it is not always sufficient,
Further, a vinyl chloride resin composition having excellent linear expansion coefficient and impact resistance has been demanded.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art, and is a vinyl chloride resin composition having a linear expansion coefficient and impact resistance superior to those of conventional products, and It is to provide the molded body.

[0004]

As a result of repeated studies on the above-mentioned problems, the present inventors have found that the elastomer components 1-3
By linearly expanding the needle-like inorganic substance in an amount of 10 to 60 parts by weight in 100 parts by weight of a vinyl chloride resin obtained by graft-copolymerizing 0 to 70% by weight of a vinyl chloride monomer in an amount of 70 to 99% by weight. It was found that a vinyl chloride-based resin composition having an excellent rate and impact resistance can be obtained. Further, it was found that a composition having more excellent linear expansion coefficient and impact resistance can be obtained by adding a specific polyethylene terephthalate (PET) fiber or chlorinated polyethylene to the above composition.

The needle-shaped inorganic substances used in the present invention include wollastonite, potassium titanate, basic magnesium sulfate, sepiolite, zonotolite, aluminum borate, etc., and the plate-shaped inorganic substances include talc, mica and synthetic. Examples include hydrosaltite. The acicular shape referred to in the present invention means a particle shape such as a acicular shape, a spindle shape, or a cylindrical shape whose major axis is 3 times or more of the minor axis. Further, the plate shape means not only a so-called plate shape but also a scale shape or a flaky shape. Of these inorganic materials, needle-shaped inorganic materials are preferable, and wollastonite is particularly preferable. The added amount of the above inorganic substances is 10 to 60 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the addition amount is less than 10 parts by weight, the effect of improving the linear expansion coefficient is insufficient, and if it exceeds 60 parts by weight, impact resistance and moldability are deteriorated.

The chlorinated polyethylene used in the present invention must have an appropriate compatibility with the matrix resin containing polyvinyl chloride as a main component, and the degree of chlorination is 20.
There is no particular limitation so long as it is up to 45%. Specifically, for example, JMR-135C (chlorination degree 35%, manufactured by Daiso Co., Ltd.) and the like can be mentioned. The amount of the chlorinated polyethylene added is 0.1 to 10 parts by weight, preferably 3 to 8 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the addition amount is less than 0.1 part by weight, the effect of improving impact resistance is not recognized, and if it exceeds 10 parts by weight, the tensile strength is lowered. It is considered that the chlorinated polyethylene is present in the vinyl chloride resin composition in a mesh shape, and when the vinyl chloride resin composition is broken, the impact strength is improved in order to suppress the propagation of cracks due to the inorganic substance.

The PET fiber used in the present invention is not particularly limited, but if the fiber length is too short, the effect of improving impact strength is small, and if it is too long, problems such as hopper drop during molding tend to occur. Is preferably 0.5 mm to 20 mm. The fiber thickness is preferably 100 to 500 denier, because if the fiber thickness is too thin, the fiber is likely to break during mixing or molding, and if it is too thick, the effect of improving impact strength is small. As the PET fiber, one having a high degree of crystallinity and being hard to be heat-shrinked is preferable. The amount of PET fiber added is
0.1 to 10 per 100 parts by weight of vinyl chloride resin
Parts by weight, preferably 0.5 to 5 parts by weight. 0.
If it is less than 1 part by weight, the effect of improving impact strength is not seen,
If it exceeds 10 parts by weight, the moldability is deteriorated and the appearance of the molded product is deteriorated.

The above-mentioned elastomer component is blended in order to improve the impact resistance of the vinyl chloride graft copolymer resin, and is not particularly limited as long as it is grafted with a vinyl chloride monomer, but an acrylic elastomer. Is preferably used. As the acrylic elastomer, from the viewpoint of improving impact resistance, a radical-polymerizable monomer containing a (meth) acrylate as a main component, whose homopolymer has a glass transition temperature of −140 ° C. or higher and lower than 0 ° C., and polyfunctionality. An acrylic copolymer composed of a monomer is preferable. Incidentally, (meth) acrylate means acrylate or methacrylate.

The glass transition temperature of the above homopolymer is -14.
The (meth) acrylate having a temperature of 0 ° C. or higher and lower than 0 ° C. imparts sufficient impact resistance to the vinyl chloride-based graft copolymer, and therefore the type is not particularly limited as long as the glass transition temperature is lower than 0 ° C. In view of the glass transition temperature of commonly used polymers, −140 ° C. or higher is suitable.

The glass transition temperature of the above homopolymer is -14.
Examples of the (meth) acrylate having a temperature of 0 ° C. or higher and lower than 0 ° C. include, for example, n-butyl acrylate (Tg = −54 ° C., only the temperature is shown in parentheses below), n-hexyl acrylate (−57 ° C.), and 2-ethylhexyl. Acrylate (-
85 ° C), n-octyl acrylate (-85 ° C), n
-Nonyl acrylate, isononyl acrylate (-8
5 ° C.), n-decyl acrylate (−70 ° C.), lauryl acrylate, lauryl methacrylate (−65
C), ethyl acrylate (-24 C), n-propyl acrylate (-37 C), n-butyl acrylate (-54 C), isobutyl acrylate (-24 C),
sec-butyl acrylate (-21 ° C), n-hexyl acrylate (-57 ° C), n-octyl methacrylate (-25 ° C), isooctyl acrylate (-45).
C.), n-nonyl methacrylate (-35.degree. C.), n-decyl methacrylate (-45.degree. C.) and the like. These may be used alone or in combination of two or more.

The form and structure of the acrylic copolymer are not particularly limited, and the resin particles as a whole may have a single-layer structure or a multi-layer structure. As a multi-layer structure, for example, a core-shell structure in which the monomer composition of the inside (core layer) of the resin particle and the surface layer portion (shell layer) is different, the core layer and the shell layer have different functions depending on the target performance. It is possible because it is possible.

As the (meth) acrylate used in the core layer, the homopolymer has a glass transition temperature of preferably -140 ° C or higher and lower than -60 ° C in consideration of improving impact resistance of the molded product. Specific examples of these (meth) acrylates include n-heptyl acrylate, n-octyl acrylate, 2-methylheptyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, 2-methyloctyl acrylate, 2-ethylheptyl acrylate, n-decyl acrylate, 2
-Methylnonyl acrylate, 2-ethyloctyl acrylate and the like can be mentioned. These may be used alone or in combination of two or more.

As the (meth) acrylate used in the shell layer, the impact resistance of the vinyl chloride resin is improved and the low glass transition polymer of the core layer is coated to reduce the tackiness of the particles of the acrylic copolymer. Therefore, the glass transition temperature of the homopolymer is preferably −55 ° C. or higher and lower than 0 ° C., and specific examples of these (meth) acrylates include ethyl acrylate, n-propyl acrylate,
Isopropyl acrylate, n-butyl (meth) acrylate, isobutyl acrylate, sec-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, cumyl acrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-methylheptyl methacrylate, 2-ethylhexyl methacrylate, n-nonyl methacrylate, 2-methyloctyl methacrylate, 2-ethylheptyl methacrylate,
Examples thereof include n-decyl methacrylate, 2-methylnonyl methacrylate, 2-ethyloctyl methacrylate and lauryl methacrylate. These are single or 2
A combination of two or more species can be used. The glass transition temperature of the homopolymer of the (meth) acrylate monomer whose homopolymer has a glass transition temperature of −140 ° C. or higher and lower than 0 ° C. is shown in “Polymer Data Handbook (Basic Edition)” edited by The Society of Polymer Science, Japan. (Baifukansha, 1986).

The radical-polymerizable monomer other than the (meth) acrylate constituting the acrylic copolymer and having a glass transition temperature of the homopolymer of −140 ° C. or higher and lower than 0 ° C. may be a radical-polymerizable monomer. There is no particular limitation as long as it is appropriately selected and used as necessary.

The polyfunctional monomer improves the impact resistance of the vinyl chloride graft copolymer resin by cross-linking the acrylic copolymer, and further when the acrylic copolymer is produced. And to prevent coalescence of the particles of the acrylic copolymer after production.

Examples of the polyfunctional monomer include
Examples of the di (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate.
Acrylate, 1.6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate and the like can be mentioned, and as tri (meth) acrylate,
Examples thereof include trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. Further, other polyfunctional monomers include pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, diallyl phthalate, diallyl malate, diallyl fumarate, diallyl succinate, triallyl isocyanurate, etc. And divinyl compounds such as divinylbenzene and butadiene. These can be used alone or in combination of two or more kinds.

The blending amount of the polyfunctional monomer in the acrylic copolymer is (meth) acrylate which forms an acrylic copolymer and has a glass transition temperature of a homopolymer of −140 ° C. or higher and lower than 0 ° C. With respect to a total of 100 parts by weight of the radical-polymerizable monomer copolymerizable with
1 to 10 parts by weight is preferable. When the blending amount of the polyfunctional monomer is less than 0.1 part by weight, it is difficult for the acrylic copolymer to maintain an independent particle shape in the vinyl chloride-based graft copolymer resin. Impact resistance decreases. On the other hand, if it exceeds 10 parts by weight, the crosslink density of the acrylic copolymer becomes high, and effective impact resistance cannot be obtained.

In the present invention, the method for copolymerizing the (meth) acrylate having a glass transition temperature of the above-mentioned homopolymer of not less than −140 and less than 0 ° C., a radically polymerizable monomer and the above polyfunctional monomer is, for example, Examples thereof include emulsion polymerization method and suspension polymerization method. Among these, the emulsion polymerization method is preferable because it has good impact resistance and is easy to control the particle size of the acrylic copolymer. The above-mentioned copolymerization means all copolymerization such as random copolymerization, block copolymerization and graft copolymerization.

The above emulsion polymerization method can be carried out by a conventionally known method, and if necessary, an emulsion dispersant, a polymerization initiator, a pH adjusting agent, an antioxidant and the like may be added.

The above-mentioned emulsifying dispersant is used for improving the dispersion stability of a mixture of monomers constituting the acrylic copolymer (hereinafter, also referred to as a mixed monomer) in an emulsion and for carrying out the polymerization efficiently. It is a thing. The emulsifying dispersant is not particularly limited, for example, an anionic surfactant,
Examples include nonionic surfactants, partially saponified polyvinyl acetate, cellulose-based dispersants, gelatin and the like. Among these, anionic surfactants are preferable, and specific examples of the anionic surfactant include, for example, polyoxyethylene nonylphenyl ether sulfate (“Hitenol N-08” manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and the like. Is mentioned.

The above polymerization initiator is not particularly limited,
For example, potassium persulfate, ammonium persulfate, water-soluble polymerization initiators such as hydrogen peroxide water, organic peroxides such as benzoyl peroxide, lauroyl peroxide, azo initiators such as azobisisobutyronitrile, etc. Can be mentioned.

The type of the emulsion polymerization method is not particularly limited,
For example, a batch polymerization method, a monomer dropping method, an emulsion dropping method and the like can be mentioned.

In the above batch polymerization method, pure water, an emulsifying dispersant, and a mixed monomer are added all at once into a polymerization reactor with a jacket, and the mixture is sufficiently emulsified by stirring under a nitrogen stream pressure.
This is a method in which the inside of the reactor is heated to a predetermined temperature with a jacket and then polymerized.

In the above monomer dropping method, pure water, an emulsifying dispersant and a polymerization initiator are put in a jacketed polymerization reactor, oxygen is removed and pressurized under a nitrogen stream, and the inside of the reactor is predetermined by a jacket. After the temperature is raised to the above temperature, a constant amount of a mixed monomer is added dropwise to polymerize.

In the above-mentioned emulsion dropping method, a mixed monomer, an emulsifying dispersant, and pure water are stirred to prepare an emulsified monomer liquid in advance, and then pure water and a polymerization initiator are placed in a jacketed polymerization reactor. This is a method in which oxygen is removed and pressurized under a nitrogen stream, the inside of the reactor is heated to a predetermined temperature by a jacket, and then the above-mentioned emulsified monomer liquid is added dropwise in a constant amount for polymerization.

Even when the acrylic copolymer has a core-shell structure, its forming method is not particularly limited. For example, first, an emulsion monomer prepared from a mixed monomer for forming the core layer, pure water and an emulsifier. Polymerization reaction is carried out by adding a polymerization initiator to the liquid to form resin particles of the core layer, and then an emulsion monomer liquid prepared from a mixed monomer constituting the shell layer, pure water and an emulsifier is added, and the shell is added to the core layer. Examples include a method of graft-copolymerizing the layer.

In the acrylic copolymer thus obtained, the shell layer three-dimensionally covers the surface of the core layer, and the copolymer constituting the shell layer and the core layer are copolymerized. The polymer partially binds covalently, and the shell layer forms a three-dimensional crosslinked structure. In the above method, the graft copolymerization of the shell layer may be continuously performed in the same polymerization process as the polymerization of the core layer.

The ratio of the core layer to the shell layer can be adjusted by adjusting the ratio of the mixed monomer forming the core layer to the mixed monomer forming the shell layer in the emulsion polymerization method, and if necessary, it can be adjusted appropriately. It is determined.

In the above-mentioned polymerization method, the solid content ratio of the acrylic copolymer obtained after the reaction is 10 to 60% by weight from the viewpoint of the productivity of the acrylic copolymer and the stability of the polymerization reaction. preferable.

The vinyl chloride-based graft copolymer of the present invention can be obtained by graft-polymerizing 1 to 30% by weight of the above acrylic copolymer with 70 to 99% by weight of a vinyl chloride monomer. The vinyl chloride-based monomer is a mixed monomer composed of vinyl chloride or 50% or more vinyl chloride and less than 50% vinyl chloride and another monomer copolymerizable with vinyl chloride. The other monomer copolymerizable with vinyl chloride is not particularly limited as long as it is copolymerizable with vinyl chloride, and is appropriately selected and used as necessary.

The average particle size of the acrylic copolymer in the vinyl chloride resin is preferably 0.01 to 1 μm. If the average particle size is smaller than 0.01 μm, a large number of fine particles will be included, which easily causes mold adhesion during molding and poor appearance. Also, if the average particle size is too large, both impact resistance and mechanical strength decrease. I have something to do.

The amount of the acrylic copolymer compounded in the vinyl chloride resin is 1 to 30% by weight, preferably 4 to 20% by weight. If the amount is less than 1% by weight, the vinyl chloride-based graft copolymer produced cannot obtain sufficient impact resistance, and if it exceeds 30% by weight,
1-30% by weight because mechanical strength such as bending strength and tensile strength of the vinyl chloride-based graft copolymer produced becomes low.
Limited to

If the degree of polymerization of polyvinyl chloride in the vinyl chloride-based graft copolymer resin is too small or too large, the moldability is lowered and it becomes difficult to obtain a good molded product. 4000 is suitable, preferably 40
It is 0-1600. The average degree of polymerization means that the vinyl chloride resin is dissolved in tetrahydrofuran (THF), the insoluble components are removed by filtration, and then THF in the filtrate is used.
The resin obtained by drying and removing is used as a sample, and JIS K-67 is used.
21 means the average degree of polymerization measured in accordance with "Test method for vinyl chloride resin".

The method for graft copolymerizing vinyl chloride onto the acrylic copolymer is not particularly limited,
For example, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, a bulk polymerization method and the like can be mentioned, and among them, the suspension polymerization method is preferable.

When carrying out the polymerization by the above suspension polymerization method,
You may use a dispersant, a polymerization initiator, etc.

The above dispersant is added for the purpose of improving the dispersion stability of the above acrylic copolymer and efficiently carrying out the graft polymerization of vinyl chloride. The dispersant is not particularly limited, and specifically, for example, poly (meth) acrylate, (meth) acrylate-alkyl acrylate copolymer, methyl cellulose, ethyl cellulose,
Examples thereof include hydroxypropylmethyl cellulose, polyethylene glycol, polyvinyl acetate and partially saponified products thereof, gelatin, polyvinylpyrrolidone, starch, and maleic anhydride-styrene copolymer, and these can be used alone or in combination of two or more kinds.

The above polymerization initiator is not particularly limited, but a radical polymerization initiator is preferably used because it is advantageous for graft copolymerization. Specifically, for example, lauroyl peroxide, t-butyl peroxypivalate, diisopropyl peroxy dicarbonate, dioctyl peroxy dicarbonate, t-butyl peroxy neodecanoate, α-cumyl peroxy neodecanoate. Organic peroxides such as 2,2-azobisisobutyronitrile, 2,2-azobis-2,4
-Azo compounds such as dimethylvaleronitrile and the like can be mentioned.

When graft-copolymerizing vinyl chloride,
A coagulant may be added to the dispersion solution of the acrylic copolymer for the purpose of reducing the scale attached to the inside of the polymerization tank during the polymerization, and further, if necessary, a pH adjusting agent and an antioxidant. Etc. may be added.

As the suspension polymerization method, for example, the following method can be used. That is, in a reaction vessel equipped with a temperature controller and a stirrer, pure water, the acrylic copolymer dispersion solution, a dispersant, a polymerization initiator, and, if necessary, a water-soluble thickener, a polymerization degree. Add regulator. After that, the air in the polymerization vessel is discharged by a vacuum pump, vinyl chloride-based monomers are further added under stirring conditions, and then the inside of the reaction vessel is heated by a jacket to perform graft copolymerization of vinyl chloride. At this time, the polymerization temperature is preferably 30 to 90 ° C., and the polymerization time is preferably 2 to 20 hours.

In the suspension polymerization method described above, the temperature in the reaction vessel, that is, the polymerization temperature can be controlled by changing the jacket temperature. After the reaction is completed, vinyl chloride graft copolymer is produced by removing unreacted vinyl chloride and the like to form a slurry and then dehydrating and drying.

The vinyl chloride-based graft copolymer obtained by the above-mentioned production method is excellent in impact resistance and mechanical strength because a part of polyvinyl chloride is directly bonded to the acrylic copolymer. Is also excellent.

The method for producing the above vinyl chloride-based graft copolymer is not particularly limited, and for example, it can be produced using the above-described method for producing the vinyl chloride-based graft copolymer of the present invention.

Since such a vinyl chloride-based graft copolymer has the above-mentioned characteristics, it is preferably used for a molded article requiring impact resistance and mechanical strength. A molded product using the above vinyl chloride-based graft copolymer is also one aspect of the present invention.

The linear expansion coefficient of the molded product of the present invention is 4.0.
X10-5 or less is preferable, and more preferably 3.0x1
It is 0-5 or less. When the linear expansion coefficient of the molded product is more than 4.0 × 10 −5, when it is used for building materials such as rain gutters, for example, it may be damaged or deformed due to thermal expansion and contraction due to temperature changes in summer and winter, day and night. Is not preferred. Further, the Charpy impact value at 23 ° C. of the molded product of the present invention is 6.0.
kJ / m2 is preferable, and more preferably 8.0 kJ / m.
2 or more. If the Charpy impact value of the molded product at 23 ° C. is less than 6.0 kJ / m 2, for example, when it is used for building materials such as rain gutters, cracking may occur during transportation or construction, which is not preferable. The molded product according to claim 2 of the present invention is a product manufactured by roll pressing as shown in the examples, and the linear expansion coefficient and the Charpy impact strength of the obtained molded product are measured by the method described in the example. It is the value.

When the molded product of the present invention is obtained by molding the above vinyl chloride-based graft copolymer, a heat stabilizer, a stabilizing aid, a lubricant, a processing aid, an antioxidant may be added, if necessary. A light stabilizer, a pigment, a filler and the like may be added.

The heat stabilizer is not particularly limited,
For example, dimethyl tin mercapto, dibutyl tin mercapto, dioctyl tin mercapto, dibutyl tin malate, dibutyl tin malate polymer, dioctyl tin malate, dioctyl tin malate polymer, dibutyl tin laurate,
Organotin stabilizer such as dibutyltin laurate polymer, lead stearate, dibasic lead phosphite, lead stabilizer such as tribasic lead sulfate, calcium-zinc stabilizer, barium-zinc stabilizer, Examples thereof include barium-cadmium stabilizers. These may be used alone or in combination of two or more.

The above-mentioned stabilizing aid is not particularly limited, and examples thereof include epoxidized soybean oil, epoxidized linseed oil epoxidized tetrahydrophthalate, epoxidized polybutadiene, and phosphoric acid ester. These may be used alone or in combination of two or more.

The lubricant is not particularly limited, and examples thereof include montanic acid wax, paraffin wax, polyethylene wax, stearic acid, stearyl alcohol, and butyl stearate. These may be used alone or in combination of two or more.

The above-mentioned processing aid is not particularly limited,
For example, an acrylic processing aid which is an alkyl acrylate / alkyl methacrylate copolymer having a weight average molecular weight of 100,000 to 2,000,000 can be mentioned, and specific examples thereof include n-butyl acrylate / methyl methacrylate copolymer, 2
-Ethylhexyl acrylate / methyl methacrylate / butyl methacrylate copolymer and the like can be mentioned. These may be used alone or in combination of two or more.

The antioxidant is not particularly limited, and examples thereof include phenolic antioxidants and the like. These may be used alone or in combination of two or more.

The light stabilizer is not particularly limited,
Examples thereof include salicylic acid ester-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based ultraviolet absorbers, hindered amine-based light stabilizers, and the like. These may be used alone or in combination of two or more.

The above-mentioned pigment is not particularly limited, and examples thereof include azo-based, phthalocyanine-based, slene-based, dye lake-based organic pigments, oxides, molybdenum chromate-based, sulfide / selenide-based, and ferrocyanine. Inorganic pigments such as compound type are listed. These may be used alone or in combination of two or more.

The filler is not particularly limited, and examples thereof include calcium carbonate and talc. These may be used alone or in combination of two or more.

When obtaining the above-mentioned molded product, a plasticizer may be added to the above vinyl chloride-based graft copolymer for the purpose of improving the processability during molding. The plasticizer is not particularly limited, and examples thereof include dibutyl phthalate, di-2-ethylhexyl phthalate and di-2-ethylhexyl adipate. These may be used alone or in combination of two or more.

The method of mixing the above-mentioned various compounding agents and plasticizers with the vinyl chloride-based graft copolymer is not particularly limited, and examples thereof include a hot blending method and a cold blending method. The molding method of the vinyl chloride-based graft copolymer is not particularly limited, and examples thereof include an extrusion molding method, an injection molding method, a calender molding method, and a press molding method.

[0056]

EXAMPLES Examples of the present invention will be described below.
It is not limited to the following example. [Production of Acrylic Copolymer] The core layer shown in Table 1,
And a monomer for forming the shell layer (hereinafter, referred to as a core layer forming monomer and a shell layer forming monomer, respectively) in a predetermined amount of pure water (60 parts by weight based on 100 parts by weight of the monomer) and polyfunctionality. Monomers (0.5 parts by weight per 100 parts by weight of each monomer) and polyoxyethylene nonylphenyl ether ammonium sulfate (emulsifying dispersant) were mixed and stirred to prepare respective emulsified monomer liquids. Next, pure water was put into a reactor equipped with a stirrer and a reflux condenser (160 parts by weight with respect to 100 parts by weight of all monomers), oxygen in the container was replaced with nitrogen, and the reaction temperature was adjusted to 70 with stirring. The temperature was raised to ° C.
After the temperature was raised, an initiator (0.5 parts by weight of ammonium persulfate based on 100 parts by weight of all the monomers) and 50% of the core layer-forming monomer were charged all at once to start the polymerization. Then, the rest of the core layer-forming monomer was dropped. As soon as the dropping of the core layer forming monomer was completed, the shell layer forming monomer was sequentially dropped. The dropping of all emulsified monomers was completed in 3 hours, and after aging for 1 hour, the polymerization was terminated and the acrylic copolymer latex having a solid content concentration of about 30% by weight and a particle diameter of 0.1 μm. (Hereinafter referred to as latex) was obtained.

[Preparation of Vinyl Chloride-Based Graft Copolymer]
According to the composition shown in Table 1, 170 parts by weight of pure water, a predetermined amount of acrylic copolymer latex (as solid content), partially saponified polyvinyl alcohol (Kuraray Co., Ltd., Kuraray Co., Ltd.) were placed in a polymerization vessel equipped with a stirrer and a jacket. Poval L-8)
5% by weight of a 3% aqueous solution of 3% of hydroxypropylmethylcellulose (Metronose 60SH50 manufactured by Shin-Etsu Chemical Co., Ltd.)
% Aqueous solution 2.5 parts by weight, t-butyl peroxypivalate 0.03 parts by weight, aluminum sulfate is added to the acrylic copolymer (solid content conversion) to obtain 3000 aluminum ions.
It was charged all at once to the ppm, then the air in the polymerization vessel was discharged with a vacuum pump, and vinyl chloride was added under stirring conditions.
00 parts by weight was added. After that, graft polymerization was started at a polymerization temperature of 57.5 ° C. by controlling the jacket temperature.

When the pressure in the polymerization vessel dropped to 0.72 MPa, the vinyl chloride monomer polymerization rate reached 80%.
%, The completion of the reaction was confirmed, and the reaction was stopped after a defoaming agent (Toray Silicon SH5510 manufactured by Toray) was added under pressure. Thereafter, unreacted vinyl chloride monomer was removed, and dehydration drying was performed to obtain vinyl chloride-based graft copolymers A1, A2, A3, B1 and B2. The degree of polymerization of vinyl chloride in the obtained vinyl chloride resin is about 100.
It was 0.

[Preparation of Vinyl Chloride Resin Composition] Based on 100 parts by weight of the vinyl chloride graft copolymer obtained above, a predetermined amount of acrylic rubber (Kaneace FM, bell Fuchi Chemical Co., Ltd., MBS (M51
1, Kanebuchi Chemical Co., Ltd., chlorinated polyethylene (trade name: J
MR-135C, Daiso Co., Ltd., Wollastonite (trade name: SH600, Kinseimatic Co., Ltd.), mica (trade name: A300, Otsuka Chemical Co., Ltd.), PET fiber (average fiber length 10 mm, average fiber thickness 250 denier) , Toyobo Co., Ltd.), organotin stabilizer (trade name: ONZ-7F, Sankoki Gosei Co., Ltd.) 1.0 parts, and lubricant (trade name: WA).
0.5 part of X-OP, Hoechst Japan) was mixed by stirring with a super mixer (100 L, manufactured by Kawata Co., Ltd.) to obtain a vinyl chloride resin composition.

On the other hand, according to the composition shown in Table 3, a vinyl chloride resin having a polymerization degree of 1000 (TS1000R, manufactured by Tokuyama Sekisui Co., Ltd.), acrylic rubber (Kane Ace FM, manufactured by Kanebuchi Kagaku), MBS (M511, Kanebuchi Kagaku). 1) each and chlorinated polyethylene (JMR135C, Daiso)
0 parts by weight, 1.0 part of an organotin stabilizer (trade name: ONZ-7F, manufactured by Sansha Machine Gosei Co., Ltd.), and a lubricant (trade name: WAX).
-OP, Hoechst Japan) 0.5 part was stirred and mixed with a super mixer (100 L, manufactured by Kawata Co., Ltd.) to obtain a vinyl chloride resin composition.

[Production of Molded Sample] Each vinyl chloride resin composition obtained was roll-kneaded at 190 ° C. for 3 minutes and then pressed at 200 ° C. for 3 minutes to prepare a vinyl chloride resin molded sample having a thickness of 3 mm. did.

[Evaluation] The following evaluations were performed using the obtained molded samples. The results are shown in Tables 2 and 3. (Linear Expansion Coefficient) Using the above-mentioned molded sample, the linear expansion coefficient was measured at a measurement temperature of 23 ° C. to 70 ° C. and a heating rate of 5 ° C./min in accordance with the plastic linear expansion test method (JIS K 7197). (Impact resistance) The Charpy impact strength was measured at 23 ° C. with an edgewise impact test piece in accordance with the Charpy impact test method (JIS K 7111) for hard plastics.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

The polyvinyl chloride resin composition of the present invention has 100 parts by weight of a vinyl chloride resin obtained by graft copolymerizing 1 to 30% by weight of an elastomer component with 70 to 99% by weight of a vinyl chloride monomer. A molded product containing 10 to 60 parts by weight of an acicular or plate-like inorganic substance, and a molded product obtained from the vinyl chloride resin composition has a line shape as compared with a system in which an impact modifier is added to an inorganic substance-filled vinyl chloride resin. Expansion rate,
The impact resistance can be further improved, and it is particularly suitable for housing materials such as rain gutters and window frame members, hard vinyl chloride pipes, pipeworking equipment such as joints, etc., which require linear expansion coefficient and impact resistance. Used for. Further, the effect can be further enhanced by adding a specific chlorinated polyethylene or PET fiber to the vinyl chloride resin composition.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI theme code (reference) C08L 23:28) (72) Inventor Hiroki Fumi 2-2 Kamitowajochokocho, Minami-ku, Kyoto City Sekisui Kagaku Kogyo Co., Ltd. F-term (reference) 4F071 AA24X AA33 AA46 AA77 AA78 AB26 AD01 AD05 AE17 AF23 AF62 AH03 BA01 BB03 BB04 BB05 BB06 BC07 4J002 BB242 BN121 CF062 DE146 DG046 DJ006 DJ046 DJ056 DK006 FA016 FD01 FA016 FA042 FA0 FA02 FA012

Claims (8)

[Claims] 1. A needle-like or plate-like inorganic substance is added to 100 parts by weight of a vinyl chloride resin obtained by graft-copolymerizing 1 to 30% by weight of an elastomer component with 70 to 99% by weight of a vinyl chloride monomer, and 10 to 60 parts by weight of an inorganic substance. A vinyl chloride resin composition characterized by being contained. 2. The vinyl chloride resin according to claim 1, wherein the molded product has a linear expansion coefficient of 4.0 × 10 −5 or less and a 23 ° C. Charpy impact value of 6.0 kJ / m 2 or more. Composition. 3. The elastomer component comprises 100 parts by weight of a radical-polymerizable monomer containing at least one type of (meth) acrylate whose main polymer has a glass transition temperature of −140 ° C. or higher and lower than 0 ° C. as a main component. The vinyl chloride resin composition according to claim 1 or 2, which is an acrylic copolymer composed of 0.1 to 10 parts by weight of a functional monomer. 4. The vinyl chloride resin composition according to claim 3, wherein the acrylic copolymer has a core-shell structure of 2-ethylhexyl acrylate and n-butyl acrylate. 5. The vinyl chloride resin composition according to any one of claims 1 to 4, wherein the acicular inorganic material is wollastonite. 6. A needle-like or plate-like inorganic substance is added to 100 parts by weight of a vinyl chloride-based resin obtained by graft-copolymerizing 1 to 30% by weight of an elastomer component with 70 to 99% by weight of a vinyl chloride-based monomer, and 10 to 60 parts by weight of an inorganic substance. , And chlorination degree 20-
The vinyl chloride resin composition according to any one of claims 1 to 5, which contains 0.1% to 10% by weight of 45% chlorinated polyethylene. 7. 10 to 60 parts by weight of needle-like or plate-like inorganic substance to 100 parts by weight of vinyl chloride resin obtained by graft-copolymerizing 70 to 99% by weight of vinyl chloride monomer to 1 to 30% by weight of an elastomer component. And a polyethylene terephthalate fiber in an amount of 0.1 to 10% by weight, the vinyl chloride resin composition according to any one of claims 1 to 5. 8. A molded article comprising the vinyl chloride resin composition according to any one of claims 1 to 7.