JP2003313391A - Polyvinyl chloride resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyvinyl chloride resin composition exhibiting a linear expansion coefficient, impact resistance, tensile strength and heat resistance each superior to those of conventional one, and its molded article. <P>SOLUTION: The polyvinyl chloride resin composition comprises 100 pts.wt. of a vinyl chloride resin composition comprising 70-99 pts.wt. of a vinyl chloride resin (A), obtained by graft copolymerizing 70-99 wt.% of a vinyl monomer mainly composed of vinyl chloride to 1-30 wt.% of an elastomer component, and 1-30 pts.wt. of a chlorinated vinyl chloride resin (B), the total amount of (A) and (B) being 100 pts.wt., and 10-60 pts.wt. of needle-shaped or plate-shaped inorganic matter. The molded article of the polyvinyl chloride resin composition is also provided. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyvinyl chloride resin composition and a molded article thereof.

[0002]

2. Description of the Related Art Originally, polyvinyl chloride resin is used for many purposes as a material having excellent mechanical strength and chemical resistance. When it is used for rain gutters and window frame members,
It has been proposed to add a needle-like or plate-like inorganic substance to the polyvinyl chloride resin in order to reduce the heat shrinkability and the linear expansion coefficient.

However, the addition of such an inorganic substance has a drawback that the impact resistance is deteriorated, and a polyvinyl chloride resin obtained by further adding various impact modifiers to this inorganic substance-filled polyvinyl chloride resin composition. Resin compositions have been proposed (for example, JP 2000-355646 A).

However, if such an impact modifier is added too much to the above polyvinyl chloride resin composition, there is a drawback that the tensile strength and heat resistance of the obtained molded article are lowered.

Therefore, there is a demand for a polyvinyl chloride resin composition capable of obtaining a molded product having excellent tensile strength and heat resistance while maintaining excellent properties such as linear expansion coefficient and impact resistance.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has a coefficient of linear expansion, impact resistance, tensile strength and heat resistance superior to those of conventional products. An object is to provide a vinyl chloride resin composition and a molded product thereof.

[0007]

As a result of repeated studies on the above-mentioned problems, the present inventors have found that the elastomer components 1-3
Vinyl monomer whose main component is vinyl chloride in 0% by weight 7
Vinyl chloride resin composition (A + B) comprising 70 to 99 parts by weight of vinyl chloride resin (A) obtained by graft copolymerizing 0 to 99% by weight and 1 to 30 parts by weight of chlorinated vinyl chloride resin (B). ) 100 parts by weight and 10 to 60 parts by weight of needle-like or plate-like inorganic substances are used in the polyvinyl chloride resin composition, and the linear expansion coefficient, impact resistance, tensile strength and heat resistance are superior to conventional products. It was found that a polyvinyl chloride resin molded product can be obtained.

The polyvinyl chloride resin composition of the present invention is
70 to 99 parts by weight of vinyl chloride resin (A) obtained by graft copolymerizing 1 to 30% by weight of an elastomer component with 70 to 99% by weight of a vinyl monomer containing vinyl chloride as a main component and chlorinated vinyl chloride resin 1 ~ 30 parts by weight (B)
100 parts by weight of a vinyl chloride resin composition (A + B) consisting of 10 to 60 parts by weight of needle-like or plate-like inorganic material.

The vinyl chloride resin composition used in the present invention comprises 70 to 99 parts by weight of vinyl chloride resin (A) and 1 to 30 parts by weight of chlorinated vinyl chloride resin (B).

The vinyl chloride resin (A) used in the present invention is a resin obtained by graft copolymerizing 1 to 30% by weight of an elastomer component with 70 to 99% by weight of a vinyl monomer containing vinyl chloride as a main component. is there.

The above-mentioned elastomer component is for improving the impact resistance of the vinyl chloride resin (A), and at least one kind of homopolymer having a glass transition temperature of -140 ° C or higher and lower than 0 ° C ( An acrylic copolymer composed of 100 parts by weight of a radically polymerizable monomer containing a meth) acrylate as a main component and 0.1 to 10 parts by weight of a polyfunctional monomer is preferable.

The radical-polymerizable monomer containing (meth) acrylate as a main component contains (meth) acrylate as a main component. That is, it is a mixture of (meth) acrylate and a vinyl monomer copolymerizable with (meth) acrylate as a main component (containing 50% by weight or more) and copolymerizable with (meth) acrylate.

The (meth) acrylate preferably has flexibility at room temperature, and the homopolymer has a glass transition temperature of -140 ° C or higher and lower than 0 ° C. In order to impart sufficient flexibility to the vinyl chloride resin (A) obtained by graft-copolymerizing a vinyl monomer containing vinyl chloride as a main component, the homopolymer has a glass transition temperature of less than 0 ° C. The kind is not particularly limited as long as it is present, but −140 ° C. or higher is suitable in view of the glass transition temperature of the (meth) acrylate polymer generally used in industry.

Examples of the (meth) acrylate 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 (meth)
Acrylate, n-octyl (meth) acrylate, 2
-Methylheptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, 2-methyloctyl (meth) acrylate,
2-ethylheptyl (meth) acrylate, n-decyl (meth) acrylate, 2-methylnonyl (meth) acrylate, 2-ethyloctyl (meth) acrylate,
Examples thereof include lauryl (meth) acrylate, and these can be used alone or in combination of two or more kinds.

In the present invention, the glass transition temperature of the homopolymer is based on "Polymer Data Handbook (Basic Edition)" edited by Japan Society of Polymer Science (1986, Baifukan Co.).

The vinyl monomer copolymerizable with the (meth) acrylate is, for example, a vinyl ester such as vinyl acetate or vinyl propionate; its homopolymer has a glass transition temperature in the range of -140 ° C to less than 0 ° C. (Meth) acrylates such as ethylene and propylene; (meth) acrylic acid, maleic anhydride, acrylonitrile, styrene, vinylidene chloride and the like.

The polyfunctional monomer improves the impact resistance of the vinyl chloride resin (A) obtained by graft-copolymerizing a vinyl monomer containing vinyl chloride as a main component, and further the above acrylic copolymer. It is added in the production of and in order to suppress the coalescence of the particles of the above acrylic copolymer.

Examples of the polyfunctional monomer include, for example,
Di (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1.6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate; Examples include tri (meth) acrylates such as 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 acrylic copolymer is a radical-polymerizable monomer containing the (meth) acrylate as a main component,
It is composed of the above polyfunctional monomer, and the compounding amount of the above polyfunctional monomer is 0.
It is 1 to 10 parts by weight.

The compounding amount of the above polyfunctional monomer is 0.1
If the amount is less than about 1 part by weight, the acrylic copolymer cannot maintain the independent particle shape in the vinyl chloride resin (A), so that the impact resistance of the vinyl chloride resin (A) decreases. On the other hand, 1
If it exceeds 0 part by weight, the crosslink density of the acrylic copolymer becomes high, and effective impact resistance cannot be obtained, so the range is limited to the above range.

Further, a different preferred elastomer component is 100 parts by weight of a radical-polymerizable monomer containing at least one (meth) acrylate as a main component and having a glass transition temperature of a homopolymer of not less than −140 ° C. and less than −60 ° C. And 40 to 90% by weight of an acrylic copolymer composed of 0.1 to 1 part by weight of a polyfunctional monomer, a (meth) acrylate whose homopolymer has a glass transition temperature of −55 ° C. or higher and lower than 0 ° C. It is a copolymer having a core-shell structure obtained by graft-copolymerizing 100 parts by weight of a radical polymerizable monomer as a main component and 10 to 60% by weight of a mixed monomer of 1.5 to 10 parts by weight of a polyfunctional monomer.

The radical-polymerizable monomer containing (meth) acrylate as a main component contains (meth) acrylate as a main component. That is, it is a mixture of (meth) acrylate and a vinyl monomer copolymerizable with (meth) acrylate as a main component (containing 50% by weight or more) and copolymerizable with (meth) acrylate.

The glass transition temperature of the above homopolymer is -14.
The radical-polymerizable monomer containing at least one (meth) acrylate as a main component and having a temperature of 0 ° C. or higher and lower than −60 ° C. forms a central part (hereinafter referred to as a core) of the copolymer particles, and a vinyl chloride resin ( It is intended to improve the impact resistance of A), and it is preferable that sufficient flexibility is required even for high-speed strain, and the homopolymer has a glass transition temperature of -60 ° C.
It is necessary that the temperature is less than 60 ° C., and the type is not particularly limited as long as it is −60 ° C., but in view of the glass transition temperature of the (meth) acrylate polymer generally used industrially, −1
40 ° C or higher is suitable.

Examples of the (meth) acrylate include n-heptyl acrylate, n-octyl acrylate, 2-methylheptyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, 2-methyloctyl acrylate and 2-ethylheptyl acrylate. , N-decyl acrylate, 2-methylnonyl acrylate, 2-ethyloctyl acrylate and the like, and these can be used alone or in combination of two or more kinds.

The vinyl monomer copolymerizable with the (meth) acrylate is, for example, a vinyl ester such as vinyl acetate or vinyl propionate; its homopolymer has a glass transition temperature in the range of -140 ° C to less than 0 ° C. No, for example, (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate; olefins such as ethylene and propylene; (meth) acrylic acid, maleic anhydride, acrylonitrile, styrene, vinylidene chloride, etc. .

The above acrylic copolymer comprises the above radical polymerizable monomer and a polyfunctional monomer, and the above-mentioned polyfunctional monomer is used as the polyfunctional monomer. Further, the compounding amount of the polyfunctional monomer is 0.1 to 10 with respect to 100 parts by weight of the radical polymerizable monomer.
Parts by weight.

The compounding amount of the polyfunctional monomer is 0.1
If the amount is less than about 1 part by weight, the acrylic copolymer cannot maintain the independent particle shape in the vinyl chloride resin (A), so that the impact resistance of the vinyl chloride resin (A) decreases. On the other hand, 1
If it exceeds 0 part by weight, the crosslink density of the acrylic copolymer becomes high, and effective impact resistance cannot be obtained, so the range is limited to the above range.

The above-mentioned copolymer is obtained by adding 100 parts by weight of a radical-polymerizable monomer containing a (meth) acrylate as a main component, the homopolymer of which has a glass transition temperature of −55 ° C. or higher and lower than 0 ° C. to the acrylic copolymer. And polyfunctional monomer 1.5
It is a copolymer having a core-shell structure obtained by graft-copolymerizing 10 to 60 parts by weight of a mixed monomer of 10 to 60% by weight.

The radical-polymerizable monomer containing (meth) acrylate as a main component contains (meth) acrylate as a main component. That is, it is a mixture of (meth) acrylate and a vinyl monomer copolymerizable with (meth) acrylate as a main component (containing 50% by weight or more) and copolymerizable with (meth) acrylate.

The homopolymer has a glass transition temperature of -55.
The radical-polymerizable monomer having a (meth) acrylate as a main component, which is at least 0 ° C and less than 0 ° C, is polymerized in the presence of a core polymer to form a main component of an outer shell portion (hereinafter referred to as a shell) of the copolymer particles, The impact resistance of the vinyl chloride resin (A) is improved, and the low glass transition polymer of the core is coated to reduce the tackiness of the copolymer particles.

Therefore, the homopolymer has a glass transition temperature of −
It is necessary to be 55 ° C or higher, and to be lower than 0 ° C in order to maintain some flexibility.

The homopolymer has a glass transition temperature of -55.
Examples of the radically polymerizable monomer having a temperature of 0 ° C. or higher and lower than 0 ° C. 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, n-decyl methacrylate, 2-methylnonyl methacrylate, 2-ethyloctyl methacrylate,
Examples thereof include lauryl (meth) acrylate. These may be used alone or in combination of two or more.

The vinyl monomer copolymerizable with the (meth) acrylate is, for example, a vinyl ester such as vinyl acetate or vinyl propionate; its homopolymer has a glass transition temperature in the range of -55 ° C to less than 0 ° C. (Meth) acrylates such as ethylene and propylene; (meth) acrylic acid, maleic anhydride, acrylonitrile, styrene, vinylidene chloride and the like.

The mixed monomer is composed of the radically polymerizable monomer and a polyfunctional monomer, and the above-mentioned polyfunctional monomer is used as the polyfunctional monomer.
Moreover, the compounding amount of the polyfunctional monomer is 1.5 to 10 parts by weight with respect to 100 parts by weight of the radically polymerizable monomer.

If the blending amount of the above-mentioned polyfunctional monomer is small, the particles of the copolymer are likely to coalesce, and the impact resistance of the vinyl chloride resin (A) is lowered. On the other hand, if the amount exceeds 10 parts by weight, the crosslink density of the acrylic copolymer becomes high, and effective impact resistance cannot be obtained, so the range is limited to the above range.

The above copolymer is a copolymer having a core-shell structure in which 40 to 90% by weight of the acrylic copolymer is graft-copolymerized with 10 to 60% by weight of a mixed monomer.

When the amount of the acrylic copolymer is small, the flexibility of the vinyl chloride resin (A) is low and the impact resistance is low, and when it is large, the tackiness of the surface of the copolymer particles is high, The above range is preferable because the production of the vinyl chloride resin (A) becomes difficult.

Examples of the method for copolymerizing the radical-polymerizable monomer with the polyfunctional monomer include emulsion polymerization method and suspension polymerization method. Among them, impact resistance is not exhibited. Well, the emulsion polymerization method is preferable because the particle size of the acrylic copolymer can be easily controlled. 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 any conventionally known method. For example, if necessary, an emulsion dispersant, a polymerization initiator, a pH adjusting agent, an antioxidant, etc. are added to carry out polymerization. May be.

The above-mentioned emulsifying dispersant improves the dispersion stability of a mixture of a radically polymerizable monomer component and a polyfunctional monomer (hereinafter also referred to as a mixed monomer) in an emulsion,
It is used for efficient polymerization.

The emulsifying dispersant is not particularly limited as long as it is an emulsifying dispersant generally used in emulsion polymerization, and examples thereof include anionic surfactants, nonionic surfactants and partially saponified polyvinyl acetate. , Cellulose-based dispersants, gelatin and the like.

Of these, anionic surfactants are preferable, and specific examples of the anionic surfactant include, for example, polyoxyethylene nonylphenyl ether ammonium sulfate (“Hitenol N- manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.”). 08 ") and the like.

The polymerization initiator is not particularly limited as long as it is an emulsion dispersant generally used in emulsion polymerization.
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 includes, for example, a batch polymerization method, a monomer dropping method, an emulsion dropping method and the like.

In the batch polymerization method, pure water is placed in the polymerization reactor,
This is a method in which the emulsifying dispersant and the mixed monomer are added all at once, the mixture is stirred in a nitrogen stream to sufficiently emulsify, and then the temperature in the reactor is raised to a predetermined temperature for polymerization.

In the monomer dropping method, pure water, an emulsifying dispersant and a polymerization initiator are added to the polymerization reactor, oxygen is removed under a nitrogen stream, and the temperature inside the reactor is raised to a predetermined temperature. This is a method in which a fixed amount of a mixed monomer is dropped and polymerized.

In the emulsion dropping method, the mixed monomer, the emulsifying dispersant and the pure water are stirred to prepare the emulsifying monomer in advance, and then the pure water and the polymerization initiator are supplied into the polymerization reactor and the mixture is fed under a nitrogen stream. This is a method in which oxygen is removed, the temperature inside the reactor is raised to a predetermined temperature, and then the above-mentioned emulsified monomer is added dropwise in a fixed amount to polymerize.

The method for producing the core-shell structured copolymer is also not particularly limited, and for example, first,
Polymerization reaction is performed by adding a polymerization initiator to an emulsion monomer prepared from a mixed monomer (radical polymerizable monomer component and polyfunctional monomer) forming the core part, pure water and an emulsifier to form resin particles of the core part. Then, a method of adding a mixed monomer constituting the shell part (the radically polymerizable monomer component and the polyfunctional monomer), an emulsifying monomer prepared from pure water and an emulsifier, and graft-copolymerizing the shell part to the core part is used. Can be mentioned.

The copolymer obtained in this manner is a copolymer in which the surface of the core portion is three-dimensionally covered by the shell portion, and the copolymer constituting the shell portion and the copolymer constituting the core portion. And are partially covalently bonded, and the shell portion forms a three-dimensional crosslinked structure.

In the above method, the graft copolymerization of the shell part may be continuously carried out in the same polymerization process as the polymerization of the core part.

The ratio of the core part to the shell part can be adjusted by adjusting the ratio of the mixed monomer forming the core part to the mixed monomer forming the shell part in the emulsion polymerization method.

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 resin (A) used in the present invention comprises 70 to 99% by weight of a vinyl monomer containing vinyl chloride as a main component in the elastomer component of 1 to 30% by weight.
Is obtained by graft copolymerization.

The average particle size of the elastomer component in the vinyl chloride resin (A) 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 contained, which will cause mold adhesion and poor appearance during molding, and if the average particle size is too large, both impact resistance and mechanical strength will decrease. .

The blending amount of the above elastomer component is 1% by weight.
If less than 30% by weight, the resulting vinyl chloride resin (A) cannot obtain sufficient impact resistance, and if it exceeds 30% by weight, mechanical strength such as bending strength and tensile strength of the obtained vinyl chloride resin is increased. Since it becomes low, it is limited to the above range, more preferably 4 to 20% by weight.

The vinyl monomer containing vinyl chloride as a main component is mainly composed of a vinyl chloride monomer. That is, mainly vinyl chloride monomer or vinyl chloride monomer (5
0% by weight or more), which is a mixture of a vinyl chloride monomer and a polymerizable vinyl monomer.

Examples of the vinyl monomer include vinyl esters such as vinyl acetate and vinyl propionate:
(Meth) acrylic acid esters such as methyl (meth) acrylate and ethyl (meth) acrylate: olefins such as ethylene and propylene: (meth) acrylic acid, maleic anhydride, acrylonitrile, styrene, vinylidene chloride and the like.

If the degree of polymerization of polyvinyl chloride in the vinyl chloride resin (A) is too small or too large, it is difficult to obtain sufficient moldability of a molded product, so that it is 300 to 400.
0 is suitable, and preferably 400 to 1600.

The method of graft-copolymerizing a vinyl monomer containing vinyl chloride as a main component with the elastomer component is not particularly limited, and examples thereof include suspension polymerization method, emulsion polymerization method, solution polymerization method, and bulk polymerization method. And the suspension polymerization method is preferable.

When carrying out the graft copolymerization by the above suspension polymerization method, a dispersant, a polymerization initiator or the like may be used.

The dispersant is added for the purpose of improving the dispersion stability of the elastomer component and efficiently carrying out the graft copolymerization of a vinyl monomer containing vinyl chloride as the main component.

The dispersant is not particularly limited, but for example, poly (meth) acrylate, (meth) acrylate-alkyl acrylate copolymer, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, polyethylene glycol, poly Examples thereof include vinyl acetate and its partially saponified product, gelatin, polyvinylpyrrolidone, starch, and maleic anhydride-styrene copolymer, and these can be used alone or in combination of two or more kinds.

The polymerization initiator is not particularly limited, but a radical polymerization initiator is preferably used because it is advantageous for graft copolymerization. For example, organic peroxides such as lauroyl peroxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, dioctyl peroxydicarbonate, t-butyl peroxy neodecanoate, α-cumylperoxy neodecanoate Examples thereof include azo compounds such as 2,2-azobisisobutyronitrile and 2,2-azobis-2,4-dimethylvaleronitrile.

When graft-copolymerizing a vinyl monomer containing vinyl chloride as a main component, an aggregating agent is added to the dispersion solution of the above-mentioned elastomer component for the purpose of reducing the scale attached to the inside of the polymerization tank during the polymerization. Is also good. Furthermore, if necessary, a pH adjuster, an antioxidant and the like may be added.

As the suspension polymerization method, for example, the following method can be used. That is, pure water, the above-mentioned elastomer component dispersion solution, a dispersant, a polymerization initiator and, if necessary, a water-soluble thickener and a polymerization degree modifier are charged into a reaction vessel equipped with a temperature controller and a stirrer.

After that, the air in the polymerization vessel is evacuated with a vacuum pump, and a vinyl monomer containing vinyl chloride as a main component is added under stirring conditions, and then the reaction vessel is heated to carry out graft copolymerization.

At this time, the polymerization temperature is preferably 30 to 90 ° C. and the polymerization time is preferably 2 to 20 hours. After completion of the reaction, vinyl chloride resin is obtained by removing unreacted vinyl chloride and the like to form a slurry and further dehydrating and drying.

The vinyl chloride resin (A) obtained by the above-mentioned production method is impact-resistant because a part of the graft copolymer of vinyl monomer containing vinyl chloride as a main component is directly bonded to the elastomer component. Excellent mechanical properties and mechanical strength.

The chlorinated vinyl chloride resin (B) used in the present invention (hereinafter referred to as "CVPC") is a vinyl chloride monomer (hereinafter referred to as "VCM") alone or VCM.
And a resin obtained by polymerizing a mixture of VCM and another monomer copolymerizable with VCM by a known method.

The chlorine content of CPVC (B) is 60.
˜72 wt% is preferred. If the chlorine content is less than 60% by weight, the heat resistance is insufficiently improved, and if it exceeds 72% by weight, the molding process becomes difficult and gelation becomes insufficient. It is preferably 63 to 70% by weight.

The amount of CPVC (B) added is 30 to 1 part by weight per 100 parts by weight of the vinyl chloride resin composition (A + B). If the amount of CPVC added is less than 1 part by weight, improvement in tensile strength and heat resistance is insufficient, and if it exceeds 30 parts by weight, it becomes difficult to secure impact resistance. Preferably 20
~ 5 parts by weight.

Therefore, the vinyl chloride resin composition (A +
The addition amount of the vinyl chloride resin in B) is 70 to 99 parts by weight, preferably 80 to 95 parts by weight in the vinyl chloride resin composition (A + B).

The polyvinyl chloride resin composition of the present invention is
It is composed of the above vinyl chloride resin composition and an acicular or plate-like inorganic substance.

The acicular shape means a acicular shape, a spindle shape, a cylindrical shape, or the like, whose major axis is 3 times or more of the minor axis, or more. Further, the plate shape means not only a so-called plate shape but also a scale shape or a flaky shape.

Examples of the needle-shaped inorganic substances include wollastonite, potassium titanate, basic magnesium sulfate, sepiolite, zonotolite, aluminum borate, and the like, and plate-shaped inorganic substances include, for example, talc,
Examples thereof include mica and synthetic hydrosaltite, and wollastonite is preferably used.

The amount of these inorganic substances added is 10 to 60 relative to 100 parts by weight of the vinyl chloride resin composition (A + B).
Parts by weight are added. 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 molding processability are deteriorated.

The invention according to claim 5 is a molded product comprising the polyvinyl chloride resin composition. Since the polyvinyl chloride resin composition has the above-mentioned properties, the obtained molded product is excellent in impact resistance, mechanical strength and the like.

When molding the polyvinyl chloride resin composition of the present invention, a heat stabilizer, a stabilizing aid, which has been conventionally used when molding the polyvinyl chloride resin composition,
Lubricants, processing aids, antioxidants, light stabilizers, pigments, inorganic fillers, plasticizers and the like may be added as necessary.

The heat stabilizer is not particularly limited as long as it is a heat stabilizer used when molding a polyvinyl chloride resin composition, and examples thereof include dimethyltin mercapto, dibutyltin mercapto and dioctyltin. Mercapto,
Dibutyltin maleate, dibutyltin maleate polymer, dioctyltin maleate, dioctyltin maleate polymer,
Organotin stabilizers such as dibutyltin laurate and dibutyltin laurate polymers, lead stabilizers such as lead stearate, dibasic lead phosphite and tribasic lead sulfate, calcium-zinc stabilizers, barium-zinc Examples thereof include system stabilizers and barium-cadmium system stabilizers. These may be used alone or in combination of two or more.

The above-mentioned stabilizing aid is not particularly limited as long as it is a stabilizing aid used in molding a polyvinyl chloride resin composition, and examples thereof include epoxidized soybean oil and epoxidized flaxseed. Examples include soybean 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 as long as it is a lubricant used when molding a polyvinyl chloride resin composition, and examples thereof include montanic acid wax, paraffin wax, polyethylene wax, stearic acid and stearyl. Examples thereof include 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 as long as it is a processing aid used when molding a polyvinyl chloride resin composition, and examples thereof include alkyl having a weight average molecular weight of 100,000 to 2,000,000. Acrylic processing aids that are acrylate / alkyl methacrylate copolymers can be mentioned,
Specific examples include n-butyl acrylate / methyl methacrylate copolymer, 2-ethylhexyl acrylate / methyl methacrylate / butyl methacrylate copolymer and the like. These may be used alone or in combination of two or more.

The antioxidant is not particularly limited as long as it is an antioxidant used when molding a polyvinyl chloride resin composition, and examples thereof include a phenolic antioxidant. These may be used alone or 2
You may use together 1 or more types.

The light stabilizer is not particularly limited as long as it is a light stabilizer inhibitor used in molding a polyvinyl chloride resin composition, and examples thereof include salicylate ester-based, benzophenone-based, and benzo Examples thereof include triazole-based and 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 as long as it is a pigment used when molding a polyvinyl chloride resin composition, and examples thereof include azo-based, phthalocyanine-based, slene-based and dye lake-based pigments. Examples thereof include organic pigments, oxide pigments, molybdenum chromate pigments, sulfide / selenide pigments, ferrocyanide pigments and the like. These may be used alone or in combination of two or more.

The inorganic filler is not particularly limited as long as it is an inorganic filler used when molding a polyvinyl chloride resin composition, and examples thereof include calcium carbonate and
Examples include talc. These may be used alone,
You may use 2 or more types together.

The plasticizer is not particularly limited as long as it is a plasticizer used when molding a polyvinyl chloride resin composition, and examples thereof include dibutyl phthalate, di-2-ethylhexyl phthalate and di-. 2-ethylhexyl adipate and the like can be mentioned. These may be used alone or in combination of two or more.

The method of mixing the above-mentioned various compounding agents with the polyvinyl chloride resin composition is not particularly limited as long as it is a mixing method used when molding the polyvinyl chloride resin composition. For example, a method by hot blending, a method by cold blending and the like can be mentioned.

The molding method is not particularly limited as long as it is a molding method conventionally used for molding a polyvinyl chloride resin composition, and examples thereof include an extrusion molding method, an injection molding method and a calender. A molding method, a press molding method and the like can be mentioned.

[0090]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below, but the present invention is not limited to the following examples.

Preparation of Emulsified Monomer 50 parts by weight of pure water, 0.5 parts by weight of polyoxyethylene nonylphenyl ether ammonium sulfate, and a predetermined amount of 2-ethylhexyl acrylate (hereinafter referred to as "2-EHA") and tri- Methylolpropane triacrylate (hereinafter referred to as "TMPTA") was mixed to prepare an emulsified monomer for forming a core layer.

Further, 50 parts by weight of pure water and polyoxyethylene nonylphenyl ether ammonium sulfate of 0.
An emulsified monomer for shell layer formation was prepared by mixing 5 parts by weight of n-butyl acrylate (hereinafter referred to as "n-BA") and TMPTA in the predetermined amounts shown in Table 1.

Preparation of acrylic copolymer Next, pure water 16 was added to a reactor equipped with a stirrer and a reflux condenser.
After supplying 0 parts by weight of oxygen and replacing the oxygen in the reactor with nitrogen, the temperature of pure water was raised to 70 ° C. with stirring. After the temperature was raised, 0.5 parts by weight of ammonium persulfate and 50% by weight of the emulsified monomer for forming the core layer were put into the reactor all at once to start the polymerization. Then, the rest of the core layer-forming monomer was dropped. Furthermore, as soon as the dropping of the core layer forming monomer was completed, the shell layer forming emulsifying monomer was sequentially dropped.

The dropping of all emulsified monomers was completed in 3 hours, and after the aging period of 1 hour, the polymerization was terminated to obtain an acrylic copolymer having a solid content concentration of about 30% by weight and a particle diameter of 0.1 μm. A polymer latex (hereinafter referred to as "latex") was obtained.

Preparation of Vinyl Chloride Resin Next, in a polymerization vessel equipped with a stirrer and a jacket, 170 parts by weight of pure water, 9 parts by weight of the above acrylic copolymer latex, partially saponified polyvinyl alcohol (manufactured by Kuraray Co., Ltd.,
5 parts by weight of a 3% by weight aqueous solution of Kuraray Poval L-8), 2.5 parts by weight of a 3% by weight aqueous solution of hydroxypropylmethylcellulose (Metronose 60SH50 manufactured by Shin-Etsu Chemical Co., Ltd.), 0.03 parts by weight of t-butylperoxypivalate. And aluminum sulfate were added all at once so that the aluminum ion content was 3000 ppmm with respect to 9 parts by weight of the solid content of the acrylic copolymer.

Thereafter, the air in the polymerization vessel was evacuated with a vacuum pump, and vinyl chloride monomer was further added under stirring conditions. After that, the polymerization temperature is adjusted to 5 by controlling the jacket temperature.
Graft polymerization was initiated at 7.5 ° C.

When the pressure in the polymerization vessel was reduced to 0.72 MPa, the polymerization rate of vinyl chloride monomer was 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.

Then, the unreacted vinyl chloride monomer was removed, and the vinyl chloride resin (A1 to 3 and B1 and B2) made of vinyl chloride shown in Table 1 and vinyl chloride was removed by dehydration drying. Obtained. The degree of polymerization of vinyl chloride in the vinyl chloride resin was about 1000.

(Examples 1-5, Comparative Examples 1-6) Predetermined amounts of vinyl chloride resin and CPVC (produced by Tokuyama Sekisui Industry Co., Ltd., HA-54K, degree of chlorination 66.5 wt%) shown in Table 2 were obtained. , Wollastonite (Kinseimatic, SH60
0), mica (A300 manufactured by Otsuka Chemical Co., Ltd.), organotin heat stabilizer (Sanko Machine Synthetic Co., Ltd., ONZ-7F), and lubricant (Hoechst Japan Co., WAX-OP) super mixer (Kawata Co., Ltd.). , 100 L) with stirring to obtain a vinyl chloride resin composition.

The obtained vinyl chloride resin composition was added to 190
After roll kneading at 3 ° C for 3 minutes, pressing was performed at 200 ° C for 3 minutes to form a vinyl chloride resin flat plate having a thickness of 3 mm. The obtained flat plate was used to measure linear expansion coefficient, impact resistance, tensile strength and Vicat softening temperature, and the results are shown in Tables 2 and 3.

The methods for evaluating the physical properties are as follows. (1) Linear expansion coefficient Plastic linear expansion test method (JIS K 719
The coefficient of linear expansion was measured according to 7). Measurement temperature is 23 ℃
The temperature rise rate is 5 ° C / min, and the unit is (1
Is 0 ^-5 / ℃).

(2) Impact resistance Charpy impact test method for hard plastics (JIS
K 7111), edgewise impact test piece
The Charpy impact strength was measured. The measurement temperature is 23 ℃
The unit is (Kj / m²). SI unit conversion: 1K
gf · cm / cm ²= 0.9807 Kj / m²

(3) Tensile strength Plastic tensile test method (JIS K 7113)
The tensile yield strength of the No. 1 test piece was measured in accordance with the above. The measurement temperature is 23 ° C., and the unit is (MPa). SI
Unit conversion: 1 Kgf / mm ² = 9.807 MPa

(Vicat Softening Temperature Test) The Vicat softening temperature was measured according to the Vicat softening temperature test method for plastics (JIS K 7206). 5Kg for measurement
A weight is used, and the unit is (° C).

[0105]

[Table 1]

[0106]

[Table 2]

[0107]

[Table 3]

[0108]

The polyvinyl chloride resin composition of the present invention is 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 monomer containing vinyl chloride as a main component. Resin 70 to 99 parts by weight (A) and chlorinated vinyl chloride resin 1 to 30 parts by weight (B)
Since 100 parts by weight of the vinyl chloride resin (A + B) of 10 to 60 parts by weight of needle-like or plate-like inorganic material is used, the molded product obtained from this polyvinyl chloride resin composition is an inorganic material-filled polyvinyl chloride resin. While maintaining the same coefficient of linear expansion and impact resistance as the system with an impact modifier added, the tensile strength and heat resistance are further improved. Rain gutters, housing materials such as window frame members, hard vinyl chloride pipes, It is suitable for use in pipeworking equipment such as joints, especially for applications that require linear expansion coefficient, impact resistance, and heat resistance.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 27:24) F term (reference) 4F071 AA24X AA33X AA77 AA79 AA79X AB26 AB30 AD01 AD05 AE17 AF14 AF23 AF54 AF61 AH03 BA01 BB03 BB04 BB05 BB06 4J002 BD182 BN111 BN121 BN211 DE186 DE286 DG046 DJ006 DJ046 DJ056 DK006 FA016 FA076 FD016 FD020 FD030 FD040 FD170 4J026 AA45 AA46 AC15 AC34 BA02 DB03 DA02 BB03 DA02 BB03 DA12 BB01 BA03

Claims (5)

[Claims] 1. An elastomer component of 1 to 30% by weight and a vinyl monomer containing vinyl chloride as a main component of 70 to 99% by weight.
Vinyl chloride resin obtained by graft-copolymerizing 70-
Vinyl chloride resin composition (A + B) comprising 99 parts by weight (A) and 1 to 30 parts by weight of chlorinated vinyl chloride resin (B)
100 parts by weight and 10 to 60 needle-like or plate-like inorganic substances
A polyvinyl chloride resin composition, characterized in that it comprises 1 part by weight. 2. 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., and a polyfunctional compound. Monomer 0.
The polyvinyl chloride resin composition according to claim 1, which is an acrylic copolymer composed of 1 to 10 parts by weight. 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 −60 ° C. as a main component. Acrylic copolymer 40 comprising 0.1 to 1 part by weight of a functional monomer
90% by weight, the glass transition temperature of the homopolymer is -55 ° C.
From a core-shell structure obtained by graft-copolymerizing 100 parts by weight of a radical-polymerizable monomer containing (meth) acrylate as a main component and having a temperature of 0 ° C. or more and 10 to 60% by weight of a mixed monomer of 1.5 to 10 parts by weight of a polyfunctional monomer. The polyvinyl chloride resin composition according to claim 1, which is a copolymer of 4. The polyvinyl chloride resin composition according to claim 1, wherein the acicular inorganic material is wollastonite. 5. A molded product made of the polyvinyl chloride resin composition according to claim 1.