JP2002322331A - Vinyl chloride-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vinyl chloride-based resin composition excellent in impact resistance, weatherability, processability, color development for a colored product and surface appearance. SOLUTION: This vinyl chloride-based resin composition is obtained by blending (A) a polyvinyl chloride-based resin with (B) a graft copolymer obtained by graft polymerizing a vinyl monomer to a polyalkyl (meth)acrylate rubber and (C) a chlorinated polyolefin and/or a vinyl ester-ethylene copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition, and more particularly to a vinyl chloride resin composition, which has good workability without impairing impact resistance and weather resistance, and has excellent coloring properties in a color product. The present invention relates to a vinyl chloride resin composition having a molded surface appearance.

[0002]

2. Description of the Related Art Vinyl chloride resins are inexpensive and have many excellent chemical and physical properties. Therefore, they are most widely produced among synthetic resins and used for a wide range of applications. However, a molded article made of a vinyl chloride resin alone has a major drawback of being brittle against impact. Many techniques have been improved to overcome this shortcoming.

For example, Japanese Patent Application Laid-Open No. 6-41380 discloses an attempt to improve impact resistance, weather resistance and the like by blending a chlorinated vinyl chloride resin and a chlorinated polyethylene resin with a vinyl chloride resin. However, in this method, the improvement in impact resistance is still insufficient.

[0004] The most effective method for improving the impact resistance of a vinyl chloride resin is a graft obtained by graft-polymerizing a monomer such as styrene, acrylonitrile or methyl methacrylate onto a rubber-like elastomer (elastic body). This is a method of blending a copolymer with a vinyl chloride resin. There have been many proposals for such a method (for example, Japanese Patent Publication No. 56-22339, Japanese Patent Publication No. Sho 5-5).
7-26536, JP-B-60-27689, and the like. However, the graft copolymers described in these publications also
Improvement of impact resistance and weather resistance at low temperature is still insufficient.

As a technique for further improving this, Japanese Patent Application Laid-Open No. 1-279954 and the like disclose a technique in which a vinyl-based monomer is graft-polymerized to a specific composite rubber comprising a polyorganosiloxane and a polyalkyl (meth) acrylate. A technique for blending a graft copolymer with a vinyl chloride resin is disclosed. According to this technique, excellent impact resistance, particularly impact resistance and weather resistance at low temperatures, which could not be obtained conventionally, can be obtained. However, when this graft copolymer is added to a vinyl chloride resin, kneading of the vinyl chloride resin is excessively promoted, and the appearance of the obtained molded article tends to be deteriorated.

Further, JP-A-10-17745 discloses a graft copolymer obtained by graft-polymerizing a vinyl monomer onto a composite rubber comprising a polyorganosiloxane and a polyalkyl (meth) acrylate, a chlorinated polyolefin, It is described that impact resistance, weather resistance, surface appearance, and the like are improved by mixing a vinyl chloride resin with a vinyl ester-ethylene copolymer in a specific amount. However, in this technique, there is room for further improvement in terms of the color developing property of a color product, workability, and the like.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior arts. That is, an object of the present invention is to provide a vinyl chloride resin composition which is excellent in impact resistance, weather resistance, workability, and coloring properties of a colored product, and has a good surface appearance of a molded article obtained. .

[0008]

SUMMARY OF THE INVENTION The present invention relates to a graft obtained by graft-polymerizing a vinyl chloride resin (A) with one or more vinyl monomers onto a polyalkyl (meth) acrylate rubber. A vinyl chloride resin composition comprising a copolymer (B) and a chlorinated polyolefin and / or vinyl ester-ethylene copolymer (C).

In the present invention, "(meth) acrylate" means acrylate and / or methacrylate.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The average degree of polymerization of the vinyl chloride resin (A) used in the present invention is preferably from 700 to 1700. When the average degree of polymerization is 700 or more, impact resistance and heat resistance are improved, and when it is 1700 or less, processability tends to be good. In particular, the average degree of polymerization is more preferably from 800 to 1300.

Examples of the vinyl chloride resin (A) include vinyl chloride homopolymer, vinyl acetate-vinyl chloride copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate-vinyl chloride copolymer and the like. No. Among these, vinyl chloride homopolymerization is particularly preferred.

The graft copolymer (B) used in the present invention
Is a graft copolymer obtained by graft-polymerizing one or more vinyl monomers onto a polyalkyl (meth) acrylate rubber.

The monomers used to obtain the polyalkyl (meth) acrylate rubber of the graft copolymer (B) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
Octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, methoxytripropylene glycol (meth) acrylate, 4-hydroxybutyl (meth)
Alkyl (meth) acrylates such as acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate are exemplified. These alkyl (meth) acrylates can be used alone or in combination of two or more.

Further, a polyalkyl (meth) acrylate rubber may be formed by copolymerizing these alkyl (meth) acrylates with other vinyl monomers. The other vinyl monomer is not particularly limited, for example,
Aromatic alkenyl compounds such as styrene, α-methylstyrene, and vinyl toluene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; methacrylic acid-modified silicone; and fluorine-containing vinyl compounds.
The amount of other vinyl monomers used is polyalkyl (meth)
The content is preferably 30% by mass or less in the monomer used to obtain the acrylate rubber.

The polyalkyl (meth) acrylate rubber of the graft copolymer (B) is preferably obtained by using two or more polyalkyl (meth) acrylate components having mutually different glass transition temperatures. Each polyalkyl (meth) acrylate component constituting the polyalkyl (meth) acrylate rubber is obtained by using a monomer having two or more unsaturated bonds in a molecule in a range of 20% by mass or less. It is preferred that

The monomer having two or more unsaturated bonds in the molecule functions as a cross-linking agent or a graft cross-linking agent. Examples of the crosslinking agent include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, divinylbenzene, and a polyfunctional methacryl group-modified silicone. Examples of the graft crosslinking agent include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Allyl methacrylate can also be used as a crosslinking agent. These cross-linking agents and graft crossing agents are used alone or in combination of two or more.

For example, glass transition temperatures different from each other 2
A polyalkyl (meth) acrylate component (B1-1) having one alkyl (meth) acrylate as a main component and another alkyl (meth) acrylate as a main component using a kind of polyalkyl (meth) acrylate component A polyalkyl (meth) acrylate rubber (B1) comprising a polyalkyl (meth) acrylate component (B1-2);
R), an acrylic rubber-based graft copolymer (B) obtained by graft-polymerizing one or more vinyl monomers.
1) is preferred.

In obtaining the acrylic rubber-based graft copolymer (B1), it is also preferable to use a compound containing a sulfonic acid or sulfate group and having a benzene ring skeleton or a salt thereof.

The two or more kinds of polyalkyl (meth) acrylate components having different glass transition temperatures can be obtained by using the above-mentioned various (meth) acrylates. For example, from the group consisting of 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, lauryl methacrylate and stearyl methacrylate as constituents of the polyalkyl (meth) acrylate component (B1-1). A glass derived from a polyalkyl (meth) acrylate component (B1-1), using at least one selected material and using n-butyl acrylate as a component of the polyalkyl (meth) acrylate component (B1-2). Transition temperature (Tg
1) is a polyalkyl (meth) acrylate component (B1
-2) It is preferable from the viewpoint of impact resistance to lower the glass transition temperature (Tg2). In particular, the use of at least one selected from the group consisting of 2-ethylhexyl acrylate, lauryl methacrylate, and stearyl methacrylate as a component of the polyalkyl (meth) acrylate component (B1-1) has an impact resistance, particularly It is more preferable in terms of impact resistance at low temperatures.

The polyalkyl (meth) acrylate rubber constituting the graft copolymer (B) preferably has two or more glass transition temperatures at 10 ° C. or lower. Further, it is preferable that at least one glass transition temperature is lower than the glass transition temperature of the n-butyl acrylate homopolymer. When the glass transition temperature of the polyalkyl (meth) acrylate rubber is such, the graft copolymer (B) can impart more excellent impact resistance.
The glass transition temperature is a value measured as a Tan δ transition point using a dynamic mechanical property analyzer (hereinafter, referred to as “DMA”).

In general, a polymer obtained from a monomer has an inherent glass transition temperature, and one transition point is observed in a homopolymer or a random copolymer of a plurality of components, but a mixture of a plurality of polymers or In the complexed polymer, a plurality of unique transition points are observed. For example, in a composite polymer composed of two components, two transition points are observed. In this case, DM
Two peaks are observed in the Tan δ curve measured by A, but when there is a bias in the composition ratio or when the transition point is close, the respective peaks approach each other and may be observed as a peak having a shoulder portion. is there. However, even in such a case, since it is different from a simple one-peak curve seen in the case of a homopolymer, it can be distinguished as two peaks.

The glass transition temperature of n-butyl acrylate homopolymer varies depending on the presence or absence of a crosslinked structure and the degree of crosslinking. Therefore, the expression “below the glass transition temperature of n-butyl acrylate homopolymer” as used herein means that, when there is a component in which n-butyl acrylate is used, the glass transition temperature of this component alone and Comparing the glass transition temperature of one component alone, it means that the glass transition temperature of the other component is lower than the glass transition temperature of the component in which n-butyl acrylate is used. When not used, the monomer of each component is replaced with n-butyl acrylate, and when a cross-linking agent or a graft cross-linking agent is used, the molar fraction between these and the monomer to be cross-linked is determined. When the glass transition temperatures of the polymers obtained by polymerization are set to be equal to each other, the above conditions are satisfied.

The average particle size of the polyalkyl (meth) acrylate rubber of the graft copolymer (B) is 0.05 to 5%.
It is preferably in the range of 1.0 μm. If the average particle size is 0.05 μm or more, the impact resistance is improved and the average particle size is 1.0 μm.
If it is less than m, the impact resistance tends to be improved and the appearance of the molded surface tends to be good. In addition, polyalkyl (meth)
In all the acrylate rubber particles, 70% by mass or more of the particles have a particle size in the range of 0.05 μm to 0.4 μm, and the particle size distribution has at least two peaks based on the number or mass. It preferably has a bidisperse distribution. By having such a bidisperse particle diameter, the impact resistance can be further improved.

In order to produce a polyalkyl (meth) acrylate rubber having such an average particle size, an emulsion polymerization method is generally preferably used. Further, the rubber prepared by emulsion polymerization can be graft-polymerized with a vinyl monomer. This rubber preferably has a gel content of 80% by mass or more as measured by extraction with toluene at 90 ° C. for 12 hours.

The vinyl monomer to be graft-polymerized to the polyalkyl (meth) acrylate rubber to obtain the graft copolymer (B) includes, for example, aromatic alkenyl such as styrene, α-methylstyrene, vinyltoluene and the like. Various vinyl monomers such as compounds; alkyl methacrylates such as methyl methacrylate and 2-ethylhexyl methacrylate; alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; . These can be used alone or in combination of two or more. Of these, alkyl methacrylate is preferred, and methyl methacrylate is particularly preferred.

The ratio of the polyalkyl (meth) acrylate rubber to the vinyl monomer in the graft copolymer (B) is based on the total mass of the graft copolymer (B). The amount of rubber is 1
0-95 mass% is preferred, and 40-90 mass% is more preferred. The amount of the vinyl monomer is preferably from 5 to 90% by mass, more preferably from 10 to 60% by mass. When the amount of the vinyl monomer is 5% by mass or more, the dispersion of the graft copolymer (B) in the resin composition becomes sufficient, and when the amount is 90% by mass or less, the impact strength developability tends to be improved. is there.

The graft copolymer (B) is obtained, for example, by adding a vinyl monomer to a polyalkyl (meth) acrylate rubber latex and polymerizing it in one or more stages by a radical polymerization technique. The latex of the graft copolymer (B) obtained by this polymerization is preferably poured into hot water in which a metal salt such as calcium chloride or magnesium sulfate or an acid such as sulfuric acid or hydrochloric acid is dissolved and coagulated. After separation, the graft copolymer (B) can be recovered as a powder.

The average particle size of the graft copolymer (B) is as follows:
It is preferably from 0.05 μm to 1.0 μm. In particular,
70% by mass or more of the entire particles of the graft copolymer (B) are present in a particle size range of 0.05 μm to 0.4 μm,
The particle size distribution preferably has a bidisperse distribution having at least two peaks based on the number or mass.

The graft copolymer (B) is blended with the vinyl chloride resin (A) as an impact modifier or the like. The amount of the graft copolymer (B) is preferably 1 to 20 parts by mass per 100 parts by mass of the vinyl chloride resin. When the amount is 1 part by mass or more, the impact resistance is improved, and when the amount is 20 parts by mass or less, processability is improved and a good molded surface appearance tends to be obtained. The amount is more preferably 2 to 15 parts by mass, and particularly preferably 2 to 10 parts by mass.

The chlorinated polyolefin (C) used in the present invention is, for example, chlorinated polyolefin powder in an aqueous suspension or chlorinated by dissolving polyethylene in an organic solvent. In particular, those obtained by chlorinating polyolefin powder in an aqueous suspension are preferable.

The polyolefin used as a raw material of the chlorinated polyolefin (C) is, for example, a homopolymer of ethylene, or ethylene and 40% by mass or less (preferably 20% by mass or less) having 12 or less carbon atoms (preferably 20% by mass or less). 3-8)
Is a copolymer obtained by copolymerizing an α-olefin of the formula (1). Specific examples of the α-olefin include propylene, 1-butene, 1-hexene, 4-methyl-1
-Pentene and the like. Among them, homopolymers of ethylene are particularly preferable.

The chlorine content of the chlorinated polyolefin (C) is preferably 30 to 40% by mass. This chlorine content is 3
When the content is 0% by mass or more, the compatibility with the vinyl chloride resin (A) is good, and the impact resistance is improved. In addition, the chlorine content is 4
If it is 0% by mass or less, the hardness does not increase too much, the molding processability is excellent, a good molded surface appearance is obtained, and the impact resistance tends to be improved. The chlorine content is 30 to 35% by mass.
Is more preferred.

The vinyl ester-ethylene copolymer (C) used in the present invention is, for example, a vinyl ester of a lower fatty acid and ethylene, preferably in a mass ratio of 30:70 to 70:70.
It is obtained by copolymerization within the range of 80:20 by an aqueous suspension polymerization method or an emulsion polymerization method. In particular, those obtained by copolymerization by an aqueous suspension polymerization method are preferable. Examples of the lower fatty acid vinyl ester include vinyl acetate, vinyl formate, vinyl propionate, and vinyl butyrate. Particularly, vinyl acetate is preferred.

Vinyl ester-ethylene copolymer (C)
Is a block copolymer in which polyethylene constitutes a hard segment and vinyl ester constitutes a soft segment. The mass ratio of vinyl ester to ethylene is preferably in the range of 30:70 to 80:20, more preferably 55:45 to 70:30,
55: 45-60: 40 is more preferred. When the ethylene content is 30% by mass or more, the processability is improved, and when the ethylene content is 45% by mass or less, the compatibility with the vinyl chloride resin (A) is excellent, and a good molded surface appearance tends to be obtained.

In the present invention, the chlorinated polyolefin and / or vinyl ester-ethylene copolymer (C)
Is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and particularly preferably 0.5 to 12 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A). . When the amount is within these preferred ranges, the processability tends to be improved and a good molded surface appearance tends to be obtained. These preferred ranges apply to both the amount when only one of the chlorinated polyolefin and the vinyl ester-ethylene copolymer is blended, and the total amount when both are blended.

The graft copolymer (B), the chlorinated polyolefin and / or the vinyl ester-ethylene copolymer (C) are compounded into the vinyl chloride resin (A) by various conventionally known mixing methods. Can do it.
Specifically, it can be compounded using, for example, a Henschel mixer, a Banbury mixer, a mixing roll, a calender roll, an extruder, or the like.

The vinyl chloride resin composition of the present invention contains the above-mentioned components (A) to (C) as main components. If necessary, a stabilizer, a lubricant, an inorganic filler, a pigment, Various additives such as an ultraviolet stabilizer can be added.

As the stabilizer, any known stabilizer which can be used for a vinyl chloride resin can be used without any particular limitation. Specific examples thereof include organic tin stabilizers such as dioctyltin mercaptide, dibutyltin mercaptide, dioctyltin malate, dibutyltin malate, octyltin laurate; metal soap stabilizers such as zinc stearate and calcium stearate; Lead-based stabilizers such as lead stearate, dibasic lead stearate, tribasic lead sulfate, and dibasic lead (phosphite); and the like. These can be used alone or in combination of two or more. Examples of the lubricant include polyethylene wax, ester wax of fatty acid and polyhydric alcohol, acrylic polymer lubricant and the like. Examples of the inorganic filler include calcium carbonate, titanium oxide, and talc.

The method for molding the vinyl chloride resin composition of the present invention is not particularly limited. For example, it can be molded by any method such as extrusion molding, injection molding, and calendar molding. The molding temperature is usually 170-210 ° C.

The vinyl chloride resin composition of the present invention can be used in various applications, and particularly, a flat plate, a pipe, a window frame,
It is very useful as a material for producing a profile extruded product used for a drainage mass or the like.

[0041]

The present invention will be described in more detail with reference to the following examples. In the following description, “parts” represents parts by mass.

<Production Example 1: Acrylic graft copolymer (1)> 99.5 parts of 2-ethylhexyl acrylate and 0.5 part of allyl methacrylate were mixed (meth)
100 parts of an acrylate monomer mixture were obtained. 100 parts of this monomer mixture was mixed with sodium alkyldiphenyl ether disulfonate (trade name Perex S, manufactured by Kao Corporation).
S-H, hereinafter "Pelex SS-H" hereinafter) was added to distilled water 195 parts was dissolved 1 part of a solid content, and pre-stirred at 10,000rpm with a homomixer and then a pressure of 300 kg / cm ² by a homogenizer Then, the mixture was emulsified and dispersed by stirring to obtain a (meth) acrylate emulsion. This emulsion was transferred to a separable flask equipped with a condenser and a stirring blade, heated while purging with nitrogen and mixing and stirring, and when the temperature in the kettle reached 50 ° C, 0.5 part of tert-butyl hydroperoxide was added. Thereafter, a mixed solution of 0.0002 part of ferrous sulfate, 0.006 part of disodium ethylenediaminetetraacetate, 0.26 part of Rongalit and 5 parts of distilled water was added.
At the same time, the jacket was set at 55 ° C. and left for 5 hours to complete the polymerization, and the acrylic rubber component (B1-1)
Latex was obtained. The polymerization rate of this latex is 99.
9%. This latex was coagulated and dried with ethanol to obtain a solid, which was extracted with toluene at 90 ° C. for 12 hours, and the gel content was measured to be 93.7% by mass.

The acrylic rubber component (B1-1)
Perex SS-H at 7.0% solids
The latex was collected so that the solid content of poly-2-ethylhexyl acrylate containing allyl methacrylate was 10 parts, put into a separable flask equipped with a stirrer, and the amount of distilled water in the system was 195 parts. Distilled water was added so as to obtain. At this time, 0.8 part of Perex SS-H is present as a solid content in the latex. Then, n containing 1.56 parts of allyl methacrylate
-A mixture of 78 parts of butyl acrylate and 0.32 parts of tert-butyl hydroperoxide was charged.
After stirring for minutes, the mixture was permeated into the acrylic rubber (A1) component particles. After further stirring for 10 minutes, the atmosphere in the vessel was replaced with nitrogen, the temperature in the kettle was raised to 50 ° C., and ferrous sulfate 0.0
02 parts, ethylenediaminetetraacetic acid disodium salt 0.0
A mixture of 0.6 part, 0.26 parts of Rongalite and 5 parts of distilled water was charged to initiate radical polymerization. At that time, the jacket was set at 60 ° C. Then the temperature in the pot is 70 ℃
, The polymerization is completed, and a polyalkyl (meth) acrylate rubber (B1) comprising an acrylic rubber component (B1-1) and an acrylic rubber component (B1-2) is held.
A latex of R) was obtained. A part of this latex was collected, and a polyalkyl (meth) acrylate rubber (B1
The sample was used for measurement of the particle size distribution of R). Table 1 shows the measurement results of the particle size distribution. This latex was dried to obtain a solid, which was extracted with toluene at 90 ° C. for 12 hours, and the gel content was measured to be 98.3%.

A mixture of 0.06 parts of tert-butyl hydroperoxide and 12 parts of methyl methacrylate (hereinafter referred to as “MMA”) was added to a latex of the polyalkyl (meth) acrylate rubber (B1R) at a temperature of 70 ° C. ° C
For 15 minutes, then cover the jacket with 70
C. and maintained for 4 hours to complete the graft polymerization of MMA onto the polyalkyl (meth) acrylate rubber (B1R). The conversion of MMA was 99.4%. The obtained latex of the acrylic rubber-based graft copolymer (1) was dropped into 200 parts of hot water of 1.5% by mass of aluminum sulfate, coagulated, separated, washed, dried at 75 ° C. for 16 hours, and powdered. Acrylic rubber-based graft copolymer (1)
I got Table 1 shows the glass transition temperature of the acrylic rubber-based graft copolymer (1). The glass transition temperature measured here is a value derived from a polyalkyl (meth) acrylate rubber.

<Production Example 2: Acrylic graft copolymer (2)> An acrylic rubber component (B1) was produced in the same manner as in Production Example 1 except that dipotassium alkenyl succinate was used instead of Perex SS-H. -1) latex was obtained. The polymerization rate of the latex of the acrylic rubber component (B1-1) was 99.9%, and the gel content was 92.4% by mass.

Subsequently, without using Perex SS-H,
Polymerization of acrylic rubber component (B1-2) was performed in the same manner as in Production Example 1 except that 0.5 parts of polyoxyethylene ether sulfate was added after infiltrating each component for acrylic rubber component (B1-2). And the acrylic rubber (B1-
1) A latex of a polyalkyl (meth) acrylate rubber (B1R) comprising a component and an acrylic rubber component (B1-2) was obtained. A part of this latex was collected, and the particle size distribution of the polyalkyl (meth) acrylate rubber (B1R) was measured. The gel content was 98.3% by mass.

Subsequently, in the same manner as in Production Example 1, MMA
Was carried out to obtain a latex of a powdery acrylic rubber-based graft copolymer (2). The conversion of MMA was 99.4%. Further, a powdery acrylic rubber-based graft copolymer (2) was obtained in the same manner as in Production Example 1 except that calcium chloride was used instead of aluminum sulfate. Table 1 shows the glass transition temperature of the acrylic rubber-based graft copolymer (2).

<Production Example 3: Acrylic rubber-based graft copolymer (3)> Into a separable flask equipped with a stirrer, 295 parts of distilled water and 1.0 part of potassium tallowate were added, and further, boric acid 0.4 was added. Part, anhydrous sodium carbonate (0.04 part), and stirred for 10 minutes. The mixture was replaced with nitrogen, and a mixed liquid of 83.3 parts of n-butyl acrylate, 1.7 parts of allyl methacrylate and 0.4 part of tert-butyl hydroperoxide was added. And stirred for 30 minutes. Next, when the temperature in the pot is 50
When the temperature reached ℃, a mixed solution comprising 0.0002 parts of ferrous sulfate, 0.006 parts of disodium ethylenediaminetetraacetate, 0.26 parts of Rongalite and 5 parts of distilled water was charged to initiate radical polymerization. At that time, the jacket was set at 60 ° C., and the temperature in the kettle was maintained at 70 ° C., and the polymerization was completed, and the polyalkyl (meth) acrylate rubber (B1R) consisting only of the acrylic rubber component (B1-2) was obtained.
Latex was obtained. A part of this latex was collected, and the particle diameter of the polyalkyl (meth) acrylate rubber (B1R) was measured in the same manner as in Production Example 1.
Was the monodispersion having a peak as a peak. The gel content was 97.3%.

A mixture of 0.06 parts of tert-butyl hydroperoxide and 15 parts of MMA was added dropwise to the latex of the polyalkyl (meth) acrylate rubber (B1R) at 70 ° C. for 15 minutes in a kettle. The jacket was set at 70 ° C. and maintained for 4 hours to complete the graft polymerization of MMA onto the polyalkyl (meth) acrylate rubber (B1R). MMA polymerization rate is 97.2%
Met. The obtained latex of the graft copolymer (3) was dropped into 200 parts of hot water containing 1.0% of aluminum sulfate, coagulated, separated, washed, and dried at 75 ° C. for 16 hours to obtain a powdery acrylic rubber. A graft copolymer (3) was obtained.
Table 1 shows the glass transition temperature of the acrylic rubber-based graft copolymer (3).

[Measurement of Particle Size Distribution of Polyalkyl (meth) acrylate Rubber] The particle size distribution measurement in Production Examples 1 to 3 was performed by diluting the obtained latex with distilled water as a sample, manufactured by MATEC, USA. The measurement was performed using a CHDF2000 type particle size distribution meter. The measurement condition is MATEC
Performed under standard conditions recommended by the company. That is, using a dedicated capillary cartridge for particle separation and a carrier liquid, the liquid is almost neutral, the flow rate is 1.4 ml / min, the pressure is about 4000 psi, the temperature is maintained at 35 ° C., and the concentration is diluted to about 3%. 0.1 ml of a latex sample was used for the measurement. As the standard particle size substance, monodisperse polystyrene having a known particle size manufactured by DUKE, USA is used in an amount of from 0.02 μm to 0.8 μm.
A total of 12 points were used within the range of m.

[Measurement of Glass Transition Temperature of Polyalkyl (meth) acrylate Rubber] In the measurement of glass transition temperature in Production Examples 1 to 3, 70 parts of the obtained acrylic rubber-based graft copolymer and 30 parts of polymethyl methacrylate were used. 25 together
Pelletize with a 25mmφ single screw extruder at 0 ° C,
Using a press set at 0 ° C., a plate prepared to a thickness of 3 mm was cut out to a width of about 10 mm and a length of about 12 mm, and the TA Ins
The temperature was measured with a measuring instrument of type DMA 983 manufactured by truments at a heating rate of 2 ° C./min, and the temperature corresponding to the transition point of the obtained Tanshin line was determined as the glass transition temperature.

<Examples 1 to 6 and Comparative Examples 1 to 4> A dibasic lead phosphate (4.2 parts) was added to 100 parts of the vinyl chloride homopolymer (PVC) having an average degree of polymerization of 1000 as the component (A).
Part, 0.35 part of calcium stearate, polyethylene wax (manufactured by Mitsui Petrochemical Industries, Ltd., Hi-Wax)
400P) 0.2 parts, ester wax (Loxiol G-60, manufactured by Henkel Hakusui Co., Ltd.) 1.0 part, calcium carbonate 5.0 parts and titanium oxide 2.5 parts, carbon black (Mitsubishi Chemical Corporation) 960B) was prepared to prepare a common compounding composition.

With respect to this common composition, Production Examples 1 to
Acrylic graft copolymers (1) to (3) as component (B) obtained in Step 3, silicone / acrylic rubber-based modifier (METABLEN S2001, manufactured by Mitsubishi Rayon Co., Ltd.): Table 2
In the table, “M1”) and MBS resin (manufactured by Mitsubishi Rayon Co., Ltd., Metablen C323: In Table 2, “M1”
2)), 35% by mass of chlorine content as component (C)
Chlorinated polyolefin (Eraslen 351A, manufactured by Showa Denko KK, referred to as "CPE" in Table 2), a vinyl acetate-ethylene copolymer having a mass ratio of vinyl acetate to ethylene of 55:45 (Nippon Gohsei Chemical Industry Co., Ltd.) Co., Ltd., Soabrene BH, referred to as “EVA” in Table 2) were added in the amounts shown in Table 1 and mixed with a Henschel mixer to obtain various vinyl chloride resin compositions.

Then, using the vinyl chloride resin composition, a sheet having a thickness of about 1.1 mm was prepared with an extruder having a screw diameter of 30 mm (cylinder temperature 190 ° C.), and the following evaluations were made. Table 2 shows the results. (1) Impact resistance: Three sheets having a thickness of 1.1 mm were stacked and pressed to produce a laminated sheet having a thickness of 3 mm. Next, the impact strength of the laminated sheet at 23 ° C. and −10 ° C. was measured according to JIS K-7110. (2) Weather resistance: Using a sunshine weather meter manufactured by Suga Test Instruments Co., Ltd., a black panel temperature of 63 ° C.
The impact strength at 23 ° C. was measured for a test piece of the sheet irradiated for 2,000 hours under conditions of rainfall of 12 minutes during a 60-minute cycle. (3) Appearance of Forming Surface (Molding Processability) The surface appearance of the obtained 1.1 mm thick sheet was visually observed and judged according to the following criteria. 1 ... Good (with surface gloss) 2 ... Surface gloss, but some surface roughness is confirmed 3 ... No surface gloss and the entire surface is rough (4) Color developability The obtained thickness 1.1 mm The surface appearance of the sheet was visually observed and judged according to the following criteria. 1 ... good 2 ... somewhat good 3 ... poor

[0055]

[Table 1]

[0056]

[Table 2]

From the results in Table 2, it can be seen that the vinyl chloride resin composition of the present invention is excellent in weather resistance, surface appearance, coloring and impact resistance, and particularly uses the graft copolymers (1) and (2). When it was found, the impact resistance was higher.

[0058]

The vinyl chloride resin composition of the present invention is excellent in the impact resistance, weather resistance and surface appearance of the obtained molded article. Therefore, for example, without impairing impact resistance and weather resistance, a plate, a pipe, a window frame, a drainage mass, and other deformed extruded products having excellent workability and coloring property in a colored product and having a good molded surface appearance can be used. It is very useful as a resin material for manufacturing.

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Claims (1)

[Claims] 1. A graft copolymer (B) obtained by graft-polymerizing one or more vinyl monomers to a polyalkyl (meth) acrylate rubber on a vinyl chloride resin (A), and , Chlorinated polyolefin and / or
Or a vinyl chloride resin composition containing a vinyl ester-ethylene copolymer (C).