JP2001278927A - Fine particle of graft copolymer and thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide fine particles of graft copolymer having an excellent moldability without reducing an improving effect of impact resistance against a thermoplastic resin. SOLUTION: The fine particles are obtained by graft-polymerizing a vinylic monomer in the presence of a composite rubber composed of a silicone rubber and an acrylic rubber, wherein the chlorine content is 60-4,000 ppm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite rubber comprising a silicone rubber and an acrylic rubber, which has good molding processability when blended with a thermoplastic resin and is molded, and has good impact resistance. Of a graft copolymer obtained by polymerizing a vinyl monomer in the presence of a copolymer, and a thermoplastic resin having excellent processability and impact resistance obtained by blending the powder. Composition.

[0002]

2. Description of the Related Art It has been widely practiced to improve the impact resistance by blending a graft copolymer containing a rubber component with a thermoplastic resin.

It is said that the use of a rubber component having as low a glass transition temperature (Tg) as possible is advantageous for exhibiting impact resistance. In fact, Tg is-
A resin containing a graft copolymer containing a polybutadiene rubber component having a lower Tg of about -80 ° C. than a resin containing a graft copolymer containing a polybutyl acrylate rubber component at about 50 ° C., such as methyl methacrylate / The addition of a butadiene / styrene copolymer (MBS resin) is more effective in improving impact resistance.

In terms of the low Tg of rubber, polyorganosiloxane (hereinafter also referred to as silicone) rubber, for example, polydimethylsiloxane rubber has a Tg of -120 ° C.
Since it is before and after, if a graft copolymer containing a silicone rubber component can be used, higher impact resistance can be expected as compared with a product containing a polybutadiene rubber component. From such a background, in recent years, studies on improving the impact resistance of a thermoplastic resin using a graft copolymer of silicone rubber or a composite rubber containing silicone rubber have been widely performed.

For example, JP-A-4-100812 discloses that a vinyl-based monomer is grafted onto a composite rubber having a structure in which a silicone rubber component and a polyalkyl (meth) acrylate component are entangled so that they cannot be separated from each other. The use of a polymerized graft copolymer is described. WO 97/10283 describes the use of a graft copolymer obtained by graft-polymerizing a vinyl monomer onto a composite rubber obtained by grafting a crosslinked silicone on a crosslinked acrylic rubber. Also, JP-A-11-100
No. 481 describes that a graft copolymer obtained by graft-polymerizing a vinyl monomer to a composite rubber obtained by coagulating and coagulating silicone rubber particles and acrylic rubber particles is used.

[0006]

However, when the above-mentioned graft copolymer is used, the impact resistance is more advantageous than that of the graft copolymer using an acrylic rubber, but a silicone component having a high lubricity is used. Therefore, when it is blended with a thermoplastic resin and molded, there is a problem that molding processability is poor.

[0007]

Means for Solving the Problems As a result of intensive studies on the above-mentioned problems, the present inventors have found that a vinyl-based monomer is graft-polymerized on a composite rubber composed of a silicone-based rubber and an acrylic-based rubber. In the graft copolymer powder obtained from the obtained graft copolymer, when chlorine is present in a specific amount, the processability at the time of molding by blending with a thermoplastic resin is good,
Further, they have found that a graft copolymer powder having an excellent effect of improving the impact resistance of a thermoplastic resin can be obtained, thereby completing the present invention.

That is, the present invention relates to a graft copolymer powder obtained by polymerizing a vinyl monomer in the presence of a composite rubber comprising a silicone rubber and an acrylic rubber, Chlorine content in powder is 60-40
A graft copolymer powder having a content of 00 ppm (claim 1),
2. The graft copolymer powder according to claim 1, wherein the silicone content in the composite rubber is 1 to 90% (representing weight%; the same applies hereinafter), and the graft copolymer is composite rubber 4.
3. A graft copolymer obtained by polymerizing 2 to 60% of a vinyl monomer in the presence of 0 to 98%.
The graft copolymer powder according to claim 3, wherein the vinyl monomer is an aromatic vinyl monomer, a vinyl cyanide monomer,
The graft copolymer powder according to claim 1, which is (meth) acrylic acid or a (meth) acrylic acid ester (claim 4), and the graft copolymer powder 1 according to claim 1
To 95 parts (parts by weight; the same applies hereinafter) and thermoplastic resin 5
To 99 parts of a thermoplastic resin composition (Claim 5) in which the total amount is 100 parts, and the thermoplastic resin is made of polyvinyl chloride, chlorinated polyvinyl chloride, polystyrene, styrene-acrylonitrile. Polymer, styrene-acrylonitrile-N-phenylmaleimide copolymer, α-methylstyrene-acrylonitrile copolymer,
The thermoplastic resin composition according to claim 5, which is polymethyl methacrylate, methyl methacrylate-styrene copolymer, polycarbonate, polyamide, polyester or polyphenylene ether (claim 6).

[0009]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a graft copolymer powder (hereinafter, referred to as "powder") obtained by polymerizing a vinyl monomer in the presence of a composite rubber comprising a silicone rubber and an acrylic rubber.
Which is also referred to as a graft copolymer powder), wherein the chlorine content in the graft copolymer powder is 60 to 4000 ppm.

[0010] The silicone rubber in the present invention is a polyorganosiloxane rubber having rubber elasticity, that is, a normal silicone rubber, and one of the silicone rubbers.
20%, preferably 1% to 10% of an organic polymer containing no silicone (polyorganosiloxane) segment (for example, butyl acrylate polymer rubber, butadiene polymer rubber, styrene polymer, styrene-butyl acrylate copolymer) And a modified silicone rubber substituted with the same. Further, the modified silicone rubber is a modified silicone rubber obtained by chemically bonding the silicone rubber and an organic polymer containing no silicone segment, and a modified silicone rubber having an entanglement between the silicone rubber and the organic polymer containing no silicone segment. A modified silicone rubber or the like simply coexisting without entanglement between the silicone rubber and the organic polymer containing no silicone segment. In the present invention, the term "acrylic" in the acrylic rubber means that the proportion of (meth) acrylic monomer units in units constituting the rubber is 50% or more, more preferably 60% or more.

The chlorine in the graft copolymer powder is as follows:
It includes chlorine itself, chlorine brought in from chlorine compounds such as calcium chloride, magnesium chloride and sodium chloride. In particular, calcium chloride, magnesium chloride,
Chlorine derived from a metal chloride such as sodium chloride is preferred because of its high effect.

The chlorine content of the graft copolymer powder is 60
4,000 ppm, preferably 100-3000 ppm.
ppm, particularly preferably 150 to 2000 ppm
It is. If the chlorine content is too small, the moldability tends to be poor, and if it is too large, the impact resistance and gloss tend to be poor, although moldability is improved.

The chlorine content is measured, for example, by placing a graft copolymer powder in a glass tube, heating and burning the gas, collecting the generated gas in a hydrogen peroxide solution, and measuring this by an ion chromatography method. It is required by

The graft copolymer having a chlorine content according to the present invention is prepared by, for example, adding a metal chloride such as calcium chloride, magnesium chloride or sodium chloride to a chlorine-free graft copolymer so as to have the above-mentioned chlorine content. It is obtained by adding. For example, when the graft copolymer is obtained by an emulsion polymerization technique, the obtained graft copolymer latex is coagulated with a coagulant containing chlorine such as calcium chloride, magnesium chloride, and sodium chloride, and the obtained coagulated product is washed. The degree can be adjusted so that the chlorine content in the powder obtained after drying falls within the range of the present invention. If the latex is coagulated using a coagulant that does not contain chlorine such as magnesium sulfate, sulfuric acid, phosphoric acid, or acetic acid as a coagulant, the dehydrated resin obtained by washing and dewatering can be converted into calcium chloride, magnesium chloride, or chloride. It can be obtained by adding a chlorine-containing compound such as sodium to adjust the chlorine content in the powder obtained after drying so as to fall within the range of the present invention.

[0015] The graft copolymer powder may be formed by using a wire mesh having a hole size of 16 mesh by 60% or more of the whole powder.
Furthermore, passing 70% or more, especially 80% or more,
It is preferable in terms of good impact resistance.

Specific examples of the silicone rubber include:
Dimethyl siloxane rubber, modified silicone rubber having a chemical bond between butyl acrylate rubber and dimethyl siloxane rubber, modified silicone rubber having entanglement between butyl acrylate rubber and dimethyl siloxane rubber,
Modified silicone rubber that simply coexists without entanglement between butyl acrylate rubber and dimethyl siloxane rubber, modified silicone rubber having a chemical bond between styrene-butyl acrylate copolymer and dimethyl siloxane rubber, styrene Modified silicone rubber that has entanglement between butyl acrylate copolymer and dimethylsiloxane rubber, modified silicone rubber that simply coexists without entanglement between styrene-butyl acrylate copolymer and dimethylsiloxane rubber, etc. Is raised.

Specific examples of the acrylic rubber include butyl acrylate polymer rubber, butyl acrylate- (meth) acrylate 2-ethylhexyl copolymer rubber, butyl acrylate-butadiene copolymer rubber, butyl acrylate -Styrene copolymer rubber.

The composite rubber comprising the silicone rubber and the acrylic rubber includes a composite rubber having a chemical bond between the silicone rubber and the acrylic rubber, and a composite rubber having a chemical bond between the silicone rubber and the acrylic rubber. A composite rubber having an entanglement, a composite rubber in which the silicone rubber and the acrylic rubber simply coexist without being entangled or the like.

The content of silicone (polyorganosiloxane) in the composite rubber comprising the silicone rubber and the acrylic rubber is 1 to 3 from the viewpoint of impact resistance-cost balance.
90% is preferable, 1 to 50% is more preferable, and 1 to 2
0% is particularly preferred. The average particle size of the composite rubber comprising the silicone rubber and the acrylic rubber is preferably from 50 to 800 nm, more preferably from 100 to 700 nm, from the viewpoint of obtaining better impact resistance.

The average particle size of the rubber can be determined by a light scattering method or observation with an electron microscope.

The coefficient of variation {(standard deviation / average particle size) × 100 (%)} of the particle size distribution of the composite rubber is preferably 60% or less, more preferably 50%, from the viewpoint of good impact resistance. % Or less.

The solvent-insoluble content (gel content: the weight fraction of the toluene-insoluble content when the sample is immersed in toluene at room temperature for 24 hours and centrifuged at 12,000 rpm for 1 hour, the same applies hereinafter) contained in the composite rubber is as follows: It is preferably at least 70%, more preferably at least 80%, from the viewpoint of better impact resistance. The upper limit is 100%.

The graft copolymer is obtained by polymerizing a vinyl monomer in the presence of a composite rubber comprising a silicone rubber and an acrylic rubber, and its graft ratio (grafted vinyl monomer The ratio of the amount of the rubber component to the amount of the rubber component in the methyl ethyl ketone insoluble when the graft copolymer was immersed in methyl ethyl ketone for 48 hours at room temperature and centrifuged at 12,000 rpm for 1 hour. (% To weight) is 2 to 100% from the viewpoint of good impact resistance.
Is preferable, 8 to 40% is more preferable, and 10 to 25%
Is particularly preferred.

The composite rubber comprising the silicone rubber and the acrylic rubber is used, for example, to form (1) an acrylic rubber such as a (meth) acrylate monomer in the presence of a silicone rubber latex produced by emulsion polymerization. (E.g., JP-A No. 4-10)
No. 0812), (2) A method of emulsion-polymerizing a component forming a silicone rubber such as an organosiloxane in the presence of an acrylic rubber latex produced by emulsion polymerization (for example, a method described in WO97 / 10283) Japanese Patent Application Laid-Open No. H11-100481, which discloses that a mixed latex obtained by mixing a silicone rubber latex produced by emulsion polymerization and an acrylic rubber latex produced by emulsion polymerization is coagulated and co-enlarged. It can be manufactured by methods,
The method of (3) for coagulating and coagulating is preferred from the viewpoint of good impact resistance and productivity.

The composite rubber obtained by coagulating and coagulating the mixed latex is such that a large number of particles of the silicone rubber particles in the silicone rubber latex and a large number of the acrylic rubber particles in the acrylic rubber latex are stuck together. It is included in the state where it was.

When a composite rubber is obtained by coagulation and co-enlargement, unagglomerated particles may be present, but it is preferable to reduce the amount to 40% or less in order to develop impact resistance.

The graft copolymer of the present invention is obtained, for example, by subjecting the composite rubber latex obtained by the above method to emulsion graft polymerization of a vinyl monomer with a radical polymerization initiator and, if necessary, a chain transfer agent. It is manufactured by

The vinyl monomer is used for enhancing the compatibility with the thermoplastic resin to be blended with the obtained graft copolymer and for uniformly dispersing the graft copolymer in the resin. is there.

Specific examples of the vinyl monomer include aromatic vinyl monomers such as styrene, α-methylstyrene and paramethylstyrene, and vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. Methacrylic acid monomer, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, methacrylic acid ester monomer such as hydroxyethyl methacrylate, acrylic acid monomer, methyl acrylate, butyl acrylate, And acrylate monomers such as glycidyl acrylate and hydroxyethyl acrylate. These may be used alone or in combination of two or more.

In order to obtain the graft copolymer of the present invention, 40 to 98% of the composite rubber, more preferably 70 to 92%, especially 80
About 90% to 60% to 2% of the vinyl monomer,
Furthermore, 30 to 8%, especially 20 to 10%, the total amount is 10
The polymerization is preferably performed so as to be 0%. If the amount of the vinyl monomer is too large, the content of the rubber component tends to be too small to exhibit sufficient impact resistance, and if too small, the monomer to be grafted is too small. Is small, and when blended with a thermoplastic resin, the compatibility with the thermoplastic resin which is a matrix resin becomes poor, and the impact resistance also tends to decrease.

In the polymerization of the vinyl monomer into the composite rubber, the portion corresponding to the branch of the graft copolymer (here,
A so-called free polymer, which is obtained by polymerizing a vinyl-based monomer) solely with a branch component without grafting to a trunk component (here, a composite rubber), is also produced as a by-product. Although obtained as a mixture, in the present invention, both are collectively referred to as a graft copolymer.

In the production of the graft copolymer, a radical polymerization initiator and, if necessary, a chain transfer agent are used, but these are not particularly limited as long as they are generally used in radical polymerization.

Specific examples of the radical polymerization initiator include cumene hydroperoxide, t-butyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, di-t-butyl peroxide, t-butylperoxylau. Organic peroxides such as sodium peroxylate, lauroyl peroxide, succinic peroxide, cyclohexane non peroxide, acetylacetone peroxide, inorganic peroxides such as potassium persulfate and ammonium persulfate, 2,2'-azobisisobutyronitrile And azo compounds such as 2,2'-azobis-2,4-dimethylvaleronitrile. Of these, organic peroxides and inorganic peroxides are particularly preferred because of their high reactivity. In particular, succinic peroxide, cyclohexane nonperoxide, acetylacetone peroxide, potassium persulfate or ammonium persulfate, when used for graft polymerization, hardly allow the polymer component of the graft to enter the inside of the composite rubber, which is advantageous in impact resistance. When the above-mentioned organic peroxide or inorganic peroxide is used, ferrous sulfate / glucose / sodium pyrophosphate, ferrous sulfate / dextrose / sodium pyrophosphate, or A mixture such as ferrous sulfate / sodium formaldehyde sulfoxylate / ethylenediamine acetate can be used in combination as a reducing agent. The combined use of a reducing agent is particularly preferred because the polymerization temperature can be lowered.

The amount of these radical polymerization initiators used is
Usually, 0.1 part is used for 100 parts of the monomer mixture used.
005 to 10 parts, more preferably 0.01 to 5 parts, and particularly preferably 0.02 to 2 parts.

If the amount of the radical polymerization initiator is too small, the polymerization rate tends to be low, and the production efficiency tends to be poor. If the amount is too large, the molecular weight of the obtained polymer decreases. , Impact resistance or powder properties tend to be low.

Specific examples of the chain transfer agent include t-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, n-hexyl mercaptan and the like.

The chain transfer agent is an optional component. When used, the amount of the chain transfer agent is preferably 0.001 to 5 parts with respect to 100 parts of the monomer (mixture) from the viewpoint of the development of impact resistance. Thus, a latex of a graft copolymer obtained by graft-polymerizing a vinyl-based monomer to a composite rubber comprising a silicone-based rubber and an acrylic-based rubber using an emulsion polymerization technique can be obtained.

As described above, the graft copolymer powder of the present invention is obtained, for example, by washing a coagulated product obtained by coagulating the above graft copolymer latex with a metal chloride such as calcium chloride, magnesium chloride, and the like, after drying. A method for adjusting the chlorine content in the obtained powder so as to fall within the range of the present invention or a coagulant containing no chlorine such as magnesium sulfate, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, etc. The latex is coagulated, washed, and dehydrated by adding water to a dehydrated resin obtained by adding an aqueous solution of a metal chloride salt such as calcium chloride or magnesium chloride to obtain a chlorine content in the powder obtained after drying. It can be obtained by a method of adjusting so as to fall within the scope of the present invention.

The graft copolymer powder can be blended with a thermoplastic resin to improve the impact resistance of the thermoplastic resin, and the thermoplastic resin composition obtained by blending has good moldability. .

Specific examples of the thermoplastic resin include polyvinyl chloride, chlorinated polyvinyl chloride, polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-N-phenylmaleimide copolymer, α-methylstyrene-acrylonitrile. Examples include copolymers, polymethyl methacrylate, methyl methacrylate-styrene copolymer, polycarbonate, polyamide, polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polyphenylene ether. These may be used alone or in combination of two or more.

The mixing ratio of the thermoplastic resin to the graft copolymer powder is 1 to 95 parts, preferably 3 to 90 parts, and 5 to 99 parts of the thermoplastic resin, more preferably 10 to 95 parts of the graft copolymer powder.
It is preferable to mix 97 parts with the total amount of 100 parts from the viewpoint of good impact resistance and surface rigidity.

The blending of the graft copolymer powder and the thermoplastic resin powder is carried out by mixing with a Henschel mixer, a ribbon blender or the like, and then melt-kneading with a roll, an extruder, a kneader or the like. it can.

At this time, commonly used compounding agents, ie, plasticizer, stabilizer, lubricant, ultraviolet absorber, antioxidant,
Flame retardants, pigments, glass fibers, fillers, polymer processing aids,
A polymer lubricant or the like can be blended.

As the molding method of the obtained thermoplastic resin composition, a molding method used for molding a usual thermoplastic resin composition, for example, an injection molding method, an extrusion molding method, a blow molding method, a calender molding method, etc. Can be applied.

[0045]

EXAMPLES Next, the present invention will be specifically described based on examples, but the present invention is not limited to only these.

The evaluations in the following Examples and Comparative Examples were performed according to the following methods. [Solid Concentration of Latex (Residue from Heated Drying) and Polymerization Conversion] A sample of the latex after the reaction was dried with a hot air dryer at 120 ° C. for 1 hour to obtain a solids concentration (residue after heated drying).
To obtain (solid content / prepared monomer content) × 100 (%)
Was calculated. [Average particle size and particle size distribution] Average particle size and particle size distribution of latex: Lead & Northlap Instruments (LEE) was used as a measuring device.
Using MICROTRAC UPA manufactured by D & NORTHRUP INSTRUMENTS, the number average particle diameter (nm) and the coefficient of variation of the particle diameter distribution {(standard deviation / number average particle diameter) × 100 (%)} were measured by a light scattering method. [Solvent insoluble content (gel content)] The latex was dried at 50 ° C for 75 hours, and then dried at room temperature under reduced pressure for 8 hours to obtain a measurement sample. The sample was immersed in toluene at room temperature for 24 hours, centrifuged at 12,000 rpm for 60 minutes, and the weight fraction of toluene insoluble in the sample was calculated. [Graft ratio] 1 g of the graft copolymer was immersed in 80 ml of methyl ethyl ketone for 48 hours at room temperature, and 12,000 r.
The insoluble content (w) of the graft copolymer was determined by centrifugation at pm for 60 minutes, and the graft ratio was calculated by the following equation.

{(W-1 × fraction of used rubber component in graft copolymer) / (1 × fraction of used rubber component in graft copolymer)} × 100 (%) [chlorine content] The polymer powder was placed in a glass tube, heated and burned, and the generated gas was collected in a 0.3% aqueous hydrogen peroxide solution. The collected liquid was removed with a Yokogawa Ion Chromatography Analyzer IC7000 (column: ICS-A23, guard column: ICS-A2G) manufactured by Yokogawa Analytical Systems Co., Ltd., and a 3 mmol / l aqueous sodium carbonate solution was removed as an eluent. The amount of chlorine was determined by using a 15 mmol / l sulfuric acid aqueous solution as the liquid and measuring at a flow rate of 1.0 ml / min and a measurement temperature of 40 ° C. [Molding processability] The obtained molded body (30 × 30 × 3 mm) was treated with methyl ethyl ketone (20 m).
1 for 8 hours, and the state of collapse was visually evaluated. A well-kneaded product is less likely to collapse and has good moldability. Judgment was made based on the following criteria. ：: Almost no collapse. Δ: Partially collapsed. ×: Disintegrated as a whole. [Impact resistance] According to Annex 1 of JIS-K7111,
No. 1 EA test piece (however, test piece size 80 × 10 × 3
mm) at 23 ° C.

Examples 1-4 and Comparative Examples 1-2 [Production of Composite Rubber Graft Copolymer Powder (G-1 to G'-2) Composed of Silicone Rubber and Acrylic Rubber] (1) Silicone rubber Manufacture of rubber latex (S-1) In a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer, amount of components (parts) pure water 189 sodium dodecylbenzenesulfonate (SDBS) 1.5 was charged. Next, the temperature was raised to 70 ° C. while replacing the system with nitrogen, and 1 part of pure water and 0.01% of potassium persulfate (KPS) were added.
After the addition of a mixture, a mixed solution consisting of styrene (ST) 1.1 butyl acrylate (BA) 0.9 was added all at once, and the mixture was stirred for 1 hour to complete the polymerization. And a latex of ST-BA copolymer.
The polymerization conversion was 99%. The solid content of the obtained latex was 1.0%, and the number average particle diameter was 0.01 μm. The coefficient of variation at this time was 38%. S
The toluene-insoluble content of the T-BA copolymer was 0%.

Separately, a mixture comprising the following components was stirred with a homomixer at 10,000 rpm for 5 minutes to prepare an emulsion of a silicone rubber-forming component.

Component Amount (parts) Pure water 70 SDBS 0.5 Octamethylcyclotetrasiloxane 94 Vinyltriethoxysilane 4 Then, a latex containing an ST-BA copolymer is added to 80
℃, dodecylbenzenesulfonic acid (DBS
A) 2 parts of pure water and 18 parts of pure water were added to adjust the pH of the system to 1.5, then the emulsion of the silicone rubber-forming component was added all at once, followed by stirring for 5 hours, and then cooled to 25 ° C. For 20 hours. Thereafter, the pH was adjusted to 8.4 with sodium hydroxide to terminate the polymerization, and a silicone rubber latex (S-1) was obtained. The polymerization conversion of the silicone rubber-forming component was 87%. The latex obtained (S
-1) a solid content of 24%, an average particle diameter of 65 nm,
The coefficient of variation of the particle size distribution was 38%, and the gel content was 61%. The silicone rubber in the silicone rubber latex is composed of 98% of the silicone component and 2% of the ST-BA copolymer component based on the charged amount and the conversion. (2) Production of acrylic rubber latex (Ac-1) In a 5-necked flask equipped with a stirrer, reflux condenser, nitrogen blowing port, monomer addition port, and thermometer, component amount (parts) pure water 280 olein Sodium acid 1.3 Sodium formaldehyde sulfoxylate (SFS) 0.4 Disodium ethylenediaminetetraacetate (EDTA) 0.01 Ferrous sulfate 0.002 was charged all at once.

The system was heated to 40 ° C. under a nitrogen stream while stirring, and after reaching 40 ° C., the component amount (parts) BA 4 allyl methacrylate (AlMA) 0.04 cumene hydroperoxide (CHP) 01 was added at once and stirring was continued at 40 ° C. for 1 hour. Thereafter, the following mixture was added dropwise over 6 hours, and after the addition, the mixture was stirred for 1 hour to complete the polymerization.

Component Amount (parts) BA 96 AlMA 0.96 CHP 0.16 The polymerization conversion was 99%. The latex obtained is p
H is 8.2, solid content concentration is 26%, average particle size is 50n
m, the gel content was 95%. (3) Production of acid group-containing copolymer latex (enlarger) A 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer. Water 200 Dioctyl sodium sulfosuccinate 0.6 SFS 0.4 EDTA 0.01 Ferrous sulfate 0.002

The system was heated to 65 ° C. under a nitrogen stream while stirring. After reaching 65 ° C., the component amount (parts) of the first-stage monomer mixture consisting of butyl methacrylate (BMA) 5 butyl acrylate (BA) 20 t-dodecylmercaptan (t-DM) 0.1 CHP 0.05 It was dropped continuously. After the completion of the dropwise addition, the second-stage monomer mixture composed of the components (parts) BMA 60 methacrylic acid 15 t-DM 0.2 CHP 0.15 was continuously added dropwise. The dropping rates of the first-stage and second-stage monomer mixtures were continuously and uniformly dropped over 5 hours. Two hours after the start of the dropwise addition, 0.6 part of sodium dioctylsulfosuccinate was added. After the completion of the dropwise addition, stirring was continued at 65 ° C. for 1 hour to terminate the polymerization, thereby obtaining an acid group-containing copolymer latex. The polymerization conversion was 98%. The obtained latex had a solid content of 33%, an average particle size of 100 nm, a coefficient of variation in particle size distribution of 20%, and a gel content of 0%. (4) Composite rubber graft copolymer powder (G-1 to G'-
2) Production Silicone rubber latex (S-1) and acrylic rubber latex (Ac-1) in amounts shown in Table 1 (solid content)
After mixing and stirring for 30 minutes, the temperature was raised to 60 ° C. 60
° C, the pH was adjusted to 1 by adding sodium hydroxide to the system.
After adjusting to 0, 3.5 parts (solid content) of the acid group-containing copolymer latex produced in (3) was added. Stirring 4
The coagulation enlargement was terminated for 5 minutes. Table 1 shows the average particle size of the obtained composite rubber latex, the variation coefficient of the particle size distribution, and the silicone content in the composite rubber calculated based on the charged amount.

In a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer, components (parts) pure water 290 composite rubber (solid content) 85 sodium oleate 3 were charged all together.

The system was heated to 70 ° C. under a nitrogen stream while stirring. After reaching 70 ° C., 0.05 parts of KPS was added, followed by 15 parts of methyl methacrylate (MMA) in 1 part.
It was dropped continuously over time. After dropping, add 1
After stirring was continued for a period of time, the polymerization was terminated, and a latex of a composite rubber graft copolymer was obtained. Table 1 shows the polymerization conversion, the average particle size, and the graft ratio of the graft copolymer.

To the obtained latex (solid content: 100 parts), 300 parts of a 1% calcium chloride aqueous solution was added and coagulated to prepare a coagulated slurry. The solidified slurry was heated to 80 ° C. while stirring, and then dehydrated to obtain a dehydrated resin. 1000 parts of pure water was added to the obtained dehydrated resin, followed by stirring to wash the resin, and then a dehydrated resin was obtained. To the obtained dehydrated resin (solid content: 100 parts), a 2.5% calcium chloride aqueous solution was added in the amount shown in Table 1 in solid content and thoroughly blended, followed by drying and drying of the graft copolymer powder (G-1). ~ G-
4, G'-1 to G'-2). Table 1 shows the chlorine content in the obtained powder.

[0057]

[Table 1] Table 1 shows that graft copolymer powders having various chlorine contents were obtained.

Examples 5 to 7 and Comparative Examples 3 and 4 7.5 parts of the graft copolymer powders obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were respectively blended with the following compositions. Then, the mixture was mixed with a mixer to prepare a thermoplastic resin composition.

Component Amount (parts) Vinyl chloride resin 99 Methyl methacrylate resin 1 Lead dibasic phosphite 3 Lead stearate 0.8 Calcium stearate 0.3 Fatty acid ester 0.2 Fatty acid alcohol dibasic ester 0.8 Bisphenol A 0.16 Calcium carbonate 3 Titanium dioxide 4 The vinyl chloride resin is 75% of Kanevinyl S1001 manufactured by Kaneka Chemical Industry Co., Ltd., and is Kanevinyl S10.
A mixed resin consisting of 25% of 03 was used. Methyl methacrylate resin manufactured by Kanegafuchi Chemical Industry Co., Ltd .: Kaneace PA
-20 was used.

The obtained thermoplastic resin composition was extruded using a twin-screw extruder under the conditions of a temperature below the resin inlet, 195 ° C., an intermediate temperature of the extruder at 180 ° C., and a resin outlet temperature of 190 ° C. Thus, a flat plate having a thickness of 3 mm was formed. Table 2 shows the results obtained by cutting out a Charpy test piece and a test piece for evaluating formability from this flat plate.

[0061]

[Table 2] Table 2 shows that the thermoplastic resin composition blended with the graft copolymer powder of the present invention has excellent moldability and impact resistance.

[0062]

According to the present invention, it is possible to obtain a graft copolymer powder having good molding processability when blended with a thermoplastic resin and molding, and excellent impact resistance of the obtained molded article.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4J002 AA01X BC03X BC04X BC06X BC07X BC09X BD04X BD18X BG06X BH02X BN21W BN22W CF00X CG00X CH07X CL00X 4J026 AA17 AA43 AA45 AA68 AB44 AC15 AC18 DB30 BA04 DA07 DB15 DB16 DB26 EA04 FA03 GA01 GA06 GA09

Claims (6)

[Claims] 1. A graft copolymer powder obtained by polymerizing a vinyl monomer in the presence of a composite rubber comprising a silicone rubber and an acrylic rubber, wherein the graft copolymer powder A graft copolymer powder having a chlorine content of 60 to 4000 ppm. 2. The silicone rubber in the composite rubber has a content of 1 to 9
The graft copolymer powder according to claim 1, which is 0% by weight. 3. The graft copolymer according to claim 1, wherein the composite rubber is 40 to 9
The graft copolymer powder according to claim 1 or 2, which is a graft copolymer obtained by polymerizing 2 to 60% by weight of a vinyl monomer in the presence of 8% by weight. 4. The graft according to claim 1, wherein the vinyl monomer is an aromatic vinyl monomer, a vinyl cyanide monomer, (meth) acrylic acid or (meth) acrylate. Copolymer powder. 5. The graft copolymer powder 1 according to claim 1,
95 parts by weight and 5 to 99 parts by weight of the thermoplastic resin have a total amount of 1
A thermoplastic resin composition formulated to be 00 parts by weight. 6. The thermoplastic resin is polyvinyl chloride, chlorinated polyvinyl chloride, polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-N-phenylmaleimide copolymer, α-methylstyrene-acrylonitrile copolymer. The thermoplastic resin composition according to claim 5, which is selected from the group consisting of polymethyl methacrylate, methyl methacrylate-styrene copolymer, polycarbonate, polyamide, polyester and polyphenylene ether.