JP2005330467A - Manufacturing method of graft polymerization powder, and thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a graft polymerization powder which maintains good powder handling ability and can give high impact resistance when a thermoplastic resin is added, and to provide a thermoplastic resin composition containing the graft polymerization powder. <P>SOLUTION: Aqueous dispersion of a polyorganosiloxane graft polymer (A) is obtained by coagulating the polyorganosiloxane graft polymer (A) in the aqueous dispersion and is made into a slurry. To this slurry, a hard inelastic polymer (B) having a glass transition temperature (Tg) of ≥40°C in an amount of 0.1-10 pts.mass with respect to 100 pts.mass of the polyorganosiloxane graft polymer (A) is added. The graft polymerization powder (C) is obtained by coating the polyorganosiloxane graft polymer (A) with the hard inelastic polymer (B). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a graft polymerized powder and a thermoplastic resin composition containing the graft polymerized powder obtained by the production method.

Conventionally, a molded body using a thermoplastic resin has been widely used in various fields. As a method for improving the impact resistance and the like, various methods have been proposed so far. For example, Patent Document 1 discloses a powder obtained by grafting an epoxy group-containing vinyl monomer to a polyester resin. A method of blending a polyorganosiloxane-based graft copolymer (grafted polymer powder) is described.
JP 2003-277450 A

  However, the graft polymerized powder described in Patent Document 1 is easily fused between the produced powders in the production process, and therefore, fluidity and blocking resistance, which are important indicators in handling powder products. There is a problem in handling, such as being easy to decrease. In addition, a molded product obtained by using a thermoplastic resin composition obtained by mixing such a graft polymerized powder with other thermoplastic resins may cause unevenness and poor appearance or develop physical properties such as impact resistance. There are problems such as variations in sex.

  The present invention has been made to solve the above-mentioned problems, and is a graft polymerized powder that retains good powder handling properties and can impart high impact resistance when added to a thermoplastic resin. And a thermoplastic resin composition containing the graft-polymerized powder.

That is, according to the first aspect of the present invention, an epoxy group-containing vinyl monomer or an epoxy group-containing vinyl monomer is added to a composite rubber composed of a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber in an aqueous medium. A graft polymerization step of obtaining an aqueous dispersion of the polyorganosiloxane-based graft polymer (A) by graft-polymerizing a vinyl-based monomer mixture composed of a monomer and other vinyl-based monomers;
A coagulation step of coagulating the polyorganosiloxane-based graft polymer (A) in the aqueous dispersion to make the aqueous dispersion a slurry;
0.1 to 10 parts by mass of hard inelastic polymer (B) having a glass transition temperature (Tg) of 40 ° C. or higher is added to 100 parts by mass of the polyorganosiloxane-based graft polymer (A). And a hard inelastic polymer addition step of coating the polyorganosiloxane graft polymer (A) with the hard inelastic polymer (B). This is a method for producing a graft polymerized powder (C) obtained by coating A) with a hard inelastic polymer (B).
Further, the second aspect of the present invention is a heat containing the graft polymerized powder (C) produced by the method of producing the graft polymerized powder (C) of the first aspect and other thermoplastic resin. It is a plastic resin composition.

  The graft polymerized powder (C) produced by the method for producing the graft polymerized powder (C) of the present invention maintains good powder handling properties and has high impact resistance when added to a thermoplastic resin. Since it can be imparted, it is suitable as an additive for adding a thermoplastic resin. Further, the thermoplastic resin composition containing the graft polymerized powder (C) has high impact resistance and is excellent in expression of various physical properties.

Hereinafter, the present invention will be described in more detail.
≪Method for producing graft polymerized powder (C) ≫
The production method of the present invention is a method for producing a graft polymer powder (C) obtained by coating a polyorganosiloxane-based graft polymer (A) with a hard inelastic polymer (B). It has the analysis process and a hard inelastic polymer addition process, It is characterized by the above-mentioned.

<Graft polymerization process>
In the graft polymerization process, an epoxy group-containing vinyl monomer, or an epoxy group-containing vinyl monomer and other vinyl-based materials are mixed with a composite rubber composed of a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber in an aqueous medium. In this step, an aqueous dispersion of the polyorganosiloxane-based graft polymer (A) is obtained by graft polymerization of the mixture with the monomer.

[Polyorganosiloxane rubber]
In the present invention, the polyorganosiloxane rubber includes an organosiloxane and a crosslinker for polyorganosiloxane rubber (hereinafter referred to as crosslinker (I)), and optionally a graft crossover agent for polyorganosiloxane rubber (hereinafter referred to as graft crossover agent (I). )] Obtained by emulsion polymerization and fine particles can be used.

  As the organosiloxane used for preparing the polyorganosiloxane rubber, a cyclic organosiloxane having 3 or more members is used, and those having 3 to 6 members are preferably used. Examples of such cyclic organosiloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenyl A cyclotetrasiloxane etc. can be mentioned, These may be used independently and may be used in mixture of 2 or more types.

  As the crosslinking agent (I) used for the preparation of the polyorganosiloxane rubber, trifunctional or tetrafunctional ones, that is, trialkoxyalkyl, arylsilane or tetraalkoxysilane are used, and specific examples include trimethoxymethyl. Examples thereof include silane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, and tetrabutoxysilane. As the crosslinking agent (I) used in the present invention, tetraalkoxysilane is preferable, and tetraethoxysilane is particularly preferably used in the above.

The graft crossing agent (I) optionally used in the preparation of the polyorganosiloxane rubber does not react when preparing the polyorganosiloxane rubber, and then in the presence of the polyorganosiloxane rubber for preparing the composite rubber. It is a siloxane having a functional group that reacts when polymerizing a polyalkyl (meth) acrylate described later or graft polymerizing an epoxy group-containing vinyl monomer or the like to a composite rubber.
Specific examples of the graft crossing agent (I) include the following formulas 1 to 4:
^{_{CH 2 = CR 2 -COO- (CH}} 2) p -SiR 1 n O (3-n) / 2 ( Equation 1)
^{_{CH 2 = CH-SiR 1 n}} O (3-n) / 2 ( Equation 2)
^{_{HS- (CH 2) p -SiR 1}} n O (3-n) / 2 ( Equation 3)
^{_{CH 2 = CR 2 -C 6 H}} 4 SiR 1 n O (3-n) / 2 ( equation 4)
(In each formula, R ¹ represents a methyl group, an ethyl group, a propyl group, or a phenyl group, R ² represents a hydrogen atom or a methyl group, n represents 0, 1 or 2, and p represents an integer of 1-6. The compound represented by this can be shown.

Among these, (meth) acryloyloxyalkylsiloxane capable of forming a unit represented by (Formula 1) has high grafting efficiency, and thus can efficiently form a graft chain. It is preferable because the impact resistance of the composition of the invention becomes more excellent. Among the (meth) acryloyloxyalkylsiloxanes, methacryloyloxyalkylsiloxanes are preferred, and specific examples include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ- Examples include methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethoxysilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane, and the like.
Examples of the vinyl siloxane capable of forming the unit represented by (Formula 2) include vinylmethyldimethoxysilane and vinyltrimethoxysilane.
Examples of the mercaptosiloxane that can form the unit represented by (Formula 3) include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyldiethoxyethylsilane.
Examples of the compound that can form the unit represented by (Formula 4) include p-vinylphenylmethyldimethoxysilane.

  The amount of the component derived from organosiloxane in the polyorganosiloxane rubber is preferably 60% by mass or more, more preferably 70% by mass or more. The amount of the component derived from the crosslinking agent (I) is preferably 0 to 30% by mass. The amount of the component derived from the graft crossing agent (I) is preferably 0.1 to 10% by mass.

  In producing the latex of the polyorganosiloxane rubber, a known production method such as the method described in US Pat. No. 2,891,920 or the method described in US Pat. No. 3,294,725 can be used. For example, a mixed solution of an organosiloxane, a crosslinking agent (I), and a graft crossing agent (I) (hereinafter referred to as an organosiloxane mixture) in the presence of a sulfonic acid-based emulsifier such as alkylbenzenesulfonic acid or alkylsulfonic acid, For example, a method of shearing and mixing with water using a homogenizer or the like to prepare an emulsion and then raising the temperature to allow the condensation reaction to proceed, or an organosiloxane emulsion in which the organosiloxane mixture, emulsifier and water are stirred to form an emulsified state In addition, a polyorganosiloxane rubber latex can be obtained by a method in which an acidic compound having no ability to form micelles such as sulfuric acid is mixed and the condensation reaction proceeds.

[Polyalkyl (meth) acrylate rubber]
The polyalkyl (meth) acrylate rubber used in the present invention includes the following alkyl (meth) acrylate, and a polyalkyl (meth) acrylate rubber cross-linking agent (hereinafter referred to as cross-linking agent (II)) and / or blended as required. Alternatively, it can be obtained by copolymerizing an acrylic rubber raw material mixture comprising a grafting agent for polyalkyl (meth) acrylate rubber (hereinafter referred to as grafting agent (II)).

  Alkyl (meth) acrylates include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and alkyls such as hexyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, and tridecyl methacrylate. Methacrylate is mentioned, and these can be used alone or in combination. Among these, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable.

The crosslinking agent (II) is a compound having two or more radically polymerizable double bonds in one molecule. As the crosslinking agent (II), ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Hexanediol di (meth) acrylate, butanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethyloltetra (meth) acrylate, allyl (meth) acrylate, divinylbenzene, And triallyl cyanurate.
The usage-amount of crosslinking agent (II) is 0-10 mass% in polyalkyl (meth) acrylate rubber.
Since the polyalkyl (meth) acrylate rubber is used as a composite rubber with polyorganosiloxane in the present invention, the crosslinking agent (II) is appropriately added. If the amount exceeds 10% by mass, the rubber tends to be too hard.

As the graft crossing agent (II), compounds having two types of unsaturated groups having different reactivities are used. Examples of such compounds include allyl methacrylate, triallyl cyanurate, triallyl isocyanate and the like. Can do. Both triallyl cyanurate and triallyl isocyanate appear to have the same reactivity of the three allyl groups, but the reactivity when the second and third allyl groups react after the first allyl group reacts. Since it differs from the reactivity when the first allyl group reacts, it can be regarded as having an unsaturated group with different reactivity. In the case of allyl methacrylate, of the two unsaturated groups, the less reactive one also reacts during the polymerization and acts as a crosslinking site, and since these all do not react during polymerization, The unsaturated group acts as a graft site during subsequent graft polymerization.
The amount of the graft crossing agent (II) used is preferably 0.01 to 10% by mass in the polyalkyl (meth) acrylate rubber. If it is less than 0.01% by mass, the effect as a graft crossing agent tends to be reduced, and if it exceeds 10% by mass, the performance as a rubber tends to be reduced.

  These crosslinking agents (II) and graft crossing agents (II) can be used alone or in combination of two or more, and a compound such as allyl methacrylate can be used as both.

[Composite rubber]
The composite rubber used in the present invention is composed of a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber. In the presence of the polyorganosiloxane rubber latex described above, an acrylic rubber raw material for the polyalkyl (meth) acrylate rubber It can be obtained by emulsion polymerization of the mixture.
The acrylic rubber raw material mixture may be added to the polyorganosiloxane rubber latex all at once or continuously.
As the polymerization proceeds, the polyalkyl (meth) acrylate rubber and the polyorganosiloxane rubber form a crosslinked network intertwined with each other at the interface between them, and further, due to the presence of the graft crossing agent (I), the polyorganosiloxane Grafting of the polyalkyl (meth) acrylate rubber to the rubber also occurs, resulting in a composite rubber latex that is substantially inseparable from each other.

The composition of the composite rubber used in the present invention is 1 to 99% by mass of polyorganosiloxane rubber and 99 to 1% by mass of polyalkyl (meth) acrylate rubber (polyorganosiloxane rubber component and polyalkyl (meth) acrylate rubber). The total amount of the component and the component is preferably 100% by mass), more preferably 5 to 95% by mass of the polyorganosiloxane rubber and 95 to 5% by mass of the polyalkyl (meth) acrylate rubber.
If the polyorganosiloxane rubber exceeds 99% by mass, the surface appearance of a molded article made of the resulting thermoplastic resin composition tends to deteriorate, and if the polyalkyl (meth) acrylate rubber component exceeds 99% by mass, it is obtained. The impact resistance of the resulting thermoplastic resin composition tends to decrease.

The composite rubber used in the present invention preferably has a mass average particle diameter in the range of 0.2 μm to 1.0 μm. A more preferable lower limit is 0.3 μm, and a more preferable upper limit is 0.7 μm. If the mass average particle diameter is less than 0.2 μm, the total surface area of the composite rubber when blended with a thermoplastic resin increases, so the amount of epoxy groups required for improving impact resistance increases, and the thermoplastic resin composition There is a tendency for the fluidity of the to decrease. On the other hand, when it exceeds 1.0 μm, the addition efficiency of the composite rubber with respect to the development of impact resistance tends to decrease.
The mass average particle size is, for example, 0.1 ml of latex diluted to about 3% solid content with distilled water as a sample, flow rate of 1.4 ml / min, pressure of about 2 using a CHDF2000 particle size distribution meter manufactured by MATEC USA. It can be measured using a capillary cartridge for particle separation and a carrier liquid under the conditions of .76 MPa (about 4000 psi) and a temperature of 35 ° C. The calibration curve for the mass average particle size can be prepared by measuring the particle size of a total of 13 points from 0.02 μm to 1.0 μm using, for example, a monodisperse polystyrene with a known particle size manufactured by DUKE, USA as the standard particle size substance. it can.

[Graft polymerization]
In the present invention, in the aqueous medium such as water, the above-mentioned composite rubber is added with the epoxy group-containing vinyl monomer, or the vinyl group comprising the epoxy group-containing vinyl monomer and other vinyl monomers. An aqueous dispersion of the polyorganosiloxane-based graft polymer (A) is obtained by graft polymerization of the monomer mixture.

Epoxy group-containing vinyl monomers include glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, allyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, glycidyl ether of polyalkylene glycol (meth) acrylate, glycidyl itaconate, etc. Among these, use of glycidyl methacrylate is more preferable. These may be used alone or in combination of two or more.
Ratio of monomer component derived from epoxy group-containing vinyl monomer among all monomer components constituting polyorganosiloxane graft polymer (A), that is, polyorganosiloxane graft polymer (A) The ratio of the epoxy group-containing vinyl monomer component to the whole needs to be in the range of 0.1 to 10% by mass. A more preferable lower limit is 0.5% by mass, and a more preferable upper limit is 8% by mass. If it is less than 0.1% by mass, the impact resistance tends to decrease, and if it exceeds 10% by mass, the dispersibility tends to decrease.

  Further, the other monomer contained in the vinyl monomer mixture is not particularly limited as long as it can be radically polymerized under the same conditions as the epoxy group-containing vinyl monomer, and is appropriate depending on the purpose. A monomer can be selected and used. For example, (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, etc. Acrylates, acrylic acid, methacrylic acid, maleic acid, itaconic acid and other unsaturated carboxylic acids, maleic anhydride, itaconic anhydride and other acid anhydrides, N-phenylmaleimide, N-cyclohexylmaleimide, Nt-butylmaleimide Maleimide derivatives such as, hydroxy group-containing monomers such as 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, diacetone acrylamide, dimethylamino Nitrogen-containing materials such as ethyl methacrylate, diene monomers such as butadiene, isoprene, and chloroprene, and styrene monomers such as styrene and α-methylstyrene are used, and these are used alone or in combination of two or more. be able to.

  The graft polymer portion composed of an epoxy group-containing vinyl monomer, or a vinyl monomer mixture composed of an epoxy group-containing vinyl monomer and another vinyl monomer, Alternatively, it can be produced by multistage polymerization. Depending on how the dispersibility of the graft polymer in the matrix, interfacial strength, and the like are set, it is possible to improve impact resistance by making the graft polymerization multistage. For example, when the graft polymer part contains a reactive monomer unit such as glycidyl methacrylate, as a method of maintaining good dispersibility while maintaining the reactivity of glycidyl methacrylate, it can be produced by multistage polymerization. It is an effective means. However, an unnecessarily large number of stages increases the number of manufacturing steps and decreases the productivity, so it is not preferable to increase more than necessary. Therefore, the polymerization is preferably 5 stages or less, more preferably 3 stages or less.

  As a polymerization method for producing the graft polymer part, general dropping polymerization can be used. However, when the first stage of the composite rubber is produced in the absence of an emulsifier, the polymerization rubber is used in the presence of the composite rubber. A method in which the components constituting the graft polymer portion are charged all at once and then a catalyst is added to perform polymerization is preferable. According to this method, the agglomerated particles are less likely to be fused during powder recovery. In the case of multistage polymerization, the second and subsequent stages may be charged all at once or by dropping.

  In graft polymerization, the amount of an epoxy group-containing vinyl monomer to be graft-polymerized on a composite rubber, or a vinyl monomer mixture composed of an epoxy group-containing vinyl monomer and other vinyl monomers is obtained. When the mass of the resulting polyorganosiloxane-based graft polymer (A) is 100 mass%, it is preferably 5 to 50 mass%, more preferably 10 to 30 mass%.

The polyorganosiloxane-based graft polymer (A) is composed of an epoxy group-containing vinyl monomer or an epoxy group-containing vinyl monomer and another vinyl monomer in the presence of the above-described composite rubber latex. The vinyl monomer mixture can be obtained by emulsion graft polymerization in one stage or multiple stages.
In graft polymerization, a component corresponding to a branch of the graft polymer (here, an epoxy group-containing vinyl monomer, or a vinyl monomer comprising an epoxy group-containing vinyl monomer and another vinyl monomer) So-called free polymer obtained by polymerizing only the branch component without grafting onto the trunk component (here, composite rubber) is obtained as a by-product, and is obtained as a mixture of the graft polymer and the free polymer. However, in the present invention, both are referred to as a graft polymer.

<Coagulation process>
The coagulation step is a step of coagulating the polyorganosiloxane-based graft polymer (A) in the aqueous dispersion obtained in the graft polymerization step to make the aqueous dispersion a slurry.

  The coagulation step can be performed, for example, as follows. That is, the aqueous dispersion of the polyorganosiloxane-based graft polymer (A) obtained in the graft polymerization step is brought into contact with the coagulant at 20 to 70 ° C., more preferably at 30 to 60 ° C., while stirring. It coagulates to make a slurry. At this time, if the coagulation step is carried out at a coagulation temperature of less than 20 ° C., the particle size obtained during the coagulation step becomes small, and there is a risk that the powder characteristics when powdered will be deteriorated. On the other hand, when the temperature exceeds 70 ° C., a lot of coarse powder having a particle diameter exceeding 1 mm is generated, which not only affects the powder recovery, but also has a problem in the molded product obtained when added to the thermoplastic resin. It also causes variations in physical properties such as impact resistance.

  Examples of the coagulant used in the coagulation step include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as formic acid and acetic acid, aluminum sulfate, magnesium sulfate, sodium chloride, calcium chloride, sodium sulfate and magnesium chloride. Inorganic salts, and organic salts such as sodium acetate and calcium acetate can be used, and these can be used alone or in combination.

<Hard inelastic polymer addition process>
In the hard inelastic polymer addition step, a hard inelastic polymer (B) having a glass transition temperature (Tg) of 40 ° C. or higher is added to the slurry obtained in the coagulation step, and a polyorganosiloxane graft polymer ( A) A step of adding 0.1 to 10 parts by mass with respect to 100 parts by mass and coating the polyorganosiloxane-based graft polymer (A) with the hard inelastic polymer (B).
By this process, the hard inelastic polymer (B) covers the periphery of the powder (polyorganosiloxane-based graft polymer (A)) coagulated in the coagulation process, and powder fluidity, blocking resistance, etc. A graft polymerized powder (C) having excellent powder characteristics can be produced.

The hard inelastic polymer (B) used in the hard inelastic polymer addition step is a polymer having no double bond in the molecule, and has a Tg of 40 ° C. or more, preferably Tg Is 50 ° C. or higher. In the hard inelastic polymer (B) having a Tg of less than 40 ° C., the hard inelastic polymer (B) is surrounded around the powder (polyorganosiloxane-based graft polymer (A)) coagulated in the coagulation step. Since the hard inelastic polymer (B) coagulates alone before covering, the powder characteristics of the polyorganosiloxane-based graft polymer (A) cannot be improved.
The composition of the hard inelastic polymer (B) is not particularly limited, but preferred monomers constituting it include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; methyl acrylate, ethyl acrylate, Examples thereof include acrylic acid esters such as butyl acrylate and 2-ethylhexyl acrylate; aromatic vinyls such as styrene and α-methylstyrene; and vinylcyan compounds such as acrylonitrile and methacrylonitrile. Particularly preferred are methyl methacrylate, ethyl acrylate, butyl acrylate and styrene.
The hard inelastic polymer (B) can be produced by emulsion polymerization of these monomers. Emulsifiers used for emulsion polymerization include anionic surfactants such as fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl phosphate esters, dialkyl sulfosuccinates, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters Well known ones such as nonionic surfactants such as sorbitan fatty acid ester and glycerin fatty acid ester, and cationic surfactants such as alkylamine salts can be used. Further, the hard inelastic polymer (B) may be a single-stage polymer or a multi-stage polymer as long as it has a Tg of 40 ° C. or higher.

  The addition amount (as solid content) of the hard inelastic polymer (B) is 0.1 to 10 parts by mass, preferably 0.5 to 100 parts by mass of the polyorganosiloxane graft polymer (A) in the slurry. -5 parts by mass. If the amount of addition of the hard inelastic polymer (B) is less than 0.1 parts by mass, the powder properties of the resulting graft polymerized powder cannot be sufficiently improved. Many fine powders consisting of the elastic polymer (B) are generated, which is not preferable.

  Moreover, it is preferable to perform a hard inelastic polymer addition process at the temperature within the range of 30-90 degreeC. If it is less than 30 degreeC, the fine particle with a particle diameter of 100 micrometers or less originating in a hard inelastic polymer (B) may generate | occur | produce. On the other hand, if the temperature exceeds 90 ° C., the powder characteristics of the obtained graft polymerized powder (C) may not be sufficiently improved.

  As a specific method of the hard inelastic polymer addition step, for example, a method of adding and mixing the slurry of the hard inelastic polymer (B) to the slurry obtained in the coagulation step, or the coagulation step Examples include a method in which the latex of the hard inelastic polymer (B) separately prepared is added to the slurry obtained in (1), and the latex of the hard inelastic polymer (B) is coagulated in the slurry. In particular, when the hard inelastic polymer addition step is performed by the latter method, the hard inelastic polymer (B) can efficiently and uniformly cover the periphery of the powder obtained in the coagulation step. In particular, a graft polymerized powder (C) having excellent powder characteristics can be obtained, which is preferable.

  In such a hard inelastic polymer addition process, the aqueous dispersion is coagulated in the coagulation process, and the hard inelastic polymer (B ) Is very important. That is, even when a latex or slurry of the hard inelastic polymer (B) is added to an aqueous dispersion that is not coagulated and is in a latex state, the graft polymerized powder (C) having excellent powder characteristics Can't get.

[Solidification process]
In the manufacturing method of this invention, it is preferable to perform the solidification process which heat-processes a slurry further after the said hard inelastic polymer addition process.
In the graft polymer powder (C) obtained in the hard inelastic polymer addition step, fine particles (polyorganosiloxane-based graft polymer (A)) are aggregated, and the periphery thereof is composed of the hard inelastic polymer (B). Although it has a coated structure, by performing such a solidification step, the fusion of the fine particles in the graft polymerized powder (C) is promoted, the particle density is improved, and the particle shape retention is enhanced.
In addition, since the hard inelastic polymer (B) is added to the slurry before the solidification step, the particles are not fused in the solidification step, and the hard inelastic polymer (B) is not added. The solidification step can be performed at a higher temperature.
In the solidification step, it is preferable to perform a heat treatment for 10 minutes or more in a temperature range of 80 ° C to 120 ° C.
The solidification step may be performed in a single step under a constant temperature condition, but if it is performed under a multi-stage condition in which the temperature is raised stepwise, a graft polymerized powder having more excellent powder characteristics can be produced.

  In the present invention, after the hard inelastic polymer addition step or the solidification step, the obtained powder is washed with water, dehydrated, and dried to obtain a graft polymerized powder (C) having excellent powder characteristics. be able to.

  The graft polymer powder (C) thus obtained preferably has an average particle size of 50 μm or more. When it is less than 50 μm, the powderiness at the time of use is poor and the handleability is poor.

Further, an inorganic filler can be further added to the graft polymerized powder (C) produced by the production method of the present invention. By combining the inorganic filler and the graft polymer, it becomes possible to further improve the handleability of the powder, and the graft polymer powder (C) that can express the physical properties described so far and the powder handleability in a well-balanced manner. Is obtained.
The inorganic filler is preferably added after the addition of the hard inelastic polymer (B) in the hard inelastic polymer addition step, or during the drying and packing of the powder.
The type and amount of the inorganic filler may be determined as required in the required application. Examples of the inorganic filler include carbonates such as heavy calcium carbonate, precipitated calcium carbonate and colloidal calcium carbonate, and titanium oxide. , Clay, talc, mica, silica, carbon black, graphite, glass beads, glass fiber, carbon fiber, and metal fiber. In addition, a filler that is water-soluble or suspended can also be used.

  According to the production method of the present invention, slurrying can be carried out while suppressing the generation of coarse powder, and then the periphery of the powder in the slurry is uniform and dense with the hard inelastic polymer (B). The graft polymerized powder (C) having excellent powder characteristics such as blocking resistance and good handling properties can be produced.

≪Thermoplastic resin composition≫
The thermoplastic resin composition of the present invention contains the graft polymerized powder (C) produced by the production method of the present invention and other thermoplastic resins.

  In the thermoplastic resin composition of the present invention, the blended amount of the graft polymerized powder (C) is preferably 3 to 50% by mass, more preferably 5 to 30% by mass, based on the total solid content of the thermoplastic resin composition. . If the blending amount is less than 3% by mass or exceeds 30% by mass, the impact resistance modification effect of the thermoplastic resin composition tends to be lowered.

<Other thermoplastic resins>
Although there is no restriction | limiting in particular as another thermoplastic resin, The thing which has as a main component 1 or more types of thermoplastic resins chosen from a polyester resin, a polyamide resin, a polyarylene sulfide resin, and polyolefin resin is preferable.

The polyester resin used in the present invention includes terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, α, β-bis (4-carboxyphenoxy) ethane, and adipic acid as resin constituents. , One or more of dicarboxylic acids such as sebacic acid, azelaic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid or their ester forming derivatives, and ethylene glycol, propylene glycol, butanediol, pentane Diol, neopentyl glycol, hexanediol, octanediol, decanediol, cyclohexanedimethanol, hydroquinone, bisphenol A, 2,2-bis (4'-hydroxyethoxyphenyl) Polyester resin obtained by polycondensation reaction from glycols selected from one or more of lopan, xylene glycol, polyethylene ether glycol, polytetramethylene ether glycol, aliphatic polyester oligomers having both hydroxyl groups at the ends Yes, it may be either homopolyester or copolyester.
As comonomer components for composing the copolyester, in addition to the above, hydroxycarboxylic acids such as glycolic acid, hydroxy acid, hydroxybenzoic acid, hydroxyphenylacetic acid, naphthylglycolic acid, propiolactone, butyrolactone, caprolactone, valerolactone Lactone compounds such as can also be used.
In addition, it has a branched or cross-linked structure using a multifunctional ester forming component such as trimethylolpropane, trimethylolethane, pentaerythritol, trimellitic acid, trimesic acid, and pyromellitic acid as long as thermoplasticity can be maintained. Polyester may be used.
In addition, aromatic nuclei such as dibromoterephthalic acid, tetrabromoterephthalic acid, tetrachloroterephthalic acid, 1,4-dimethyloltetrabromobenzene, tetrabromobisphenol A, tetrabromobisphenol A ethylene or propionoxycide adduct A polyester copolymer having a halogen compound as a substitution machine and having a halogen using a compound having an ester-forming group is also included.
A polyester elastomer constituting a block copolymer of a high melting point hard segment and a low melting point soft segment can also be used. Examples of the polyester elastomer include a block copolymer of a hard segment mainly composed of an alkylene terephthalate unit and a soft segment made of an aliphatic polyester or polyether.
These polyester resins can be used alone or in combination of two or more.
Particularly preferred polyester resins are polybutylene terephthalate, polyethylene terephthalate and copolymers having these as main repeating units, and the comonomer component forming the copolymer is particularly preferably isophthalic acid, bisphenol A, 2, 2 -Bis (β-hydroxyethoxyphenyl) propane, 2,2-bis (β-hydroxyethoxytetrabromophenyl) propane and the like.

The polyamide resin used in the present invention is not particularly limited, and means all polymers capable of being melt-polymerized and melt-molded composed of amino acid lactam or diamine and dicarboxylic acid. Specific examples of the polyamide resin used in the present invention include the following resins.
(1) A polycondensation product of an organic dicarboxylic acid having 4 to 12 carbon atoms and an organic diamine having 2 to 13 carbon atoms, for example, polyhexamethylene adipamide which is a polycondensation product of hexamethylenediamine and adipic acid [6, 6 nylon], polyhexamethylene azelamide [6,9 nylon] which is a polycondensate of hexamethylene diamine and azelaic acid, polyhexamethylene sebaca which is a polycondensate of hexamethylene diamine and sebacic acid [6,10 nylon], polyhexamethylene dodecanoamide [6,12 nylon] which is a polycondensate of hexamethylenediamine and dodecanedioic acid, polycondensation of bis-p-aminocyclohexylmethane and dodecanedioic acid Polybis (4-aminocyclohexyl) methane dodecane,
(2) ω-amino acid polycondensate, for example, polyundecanamide [11 nylon] which is a polycondensate of ω-aminoundecanoic acid,
(3) Ring-opening polymer of lactam, for example, polycapramide [6 nylon] which is a ring-opening polymer of ε-aminocaprolactam, ring-opening polymer of ε-aminolaurolactam, polylauric lactam [12 nylon], etc. .
Of these, polyhexamethylene adipamide (6,6 nylon), polyhexamethylene azelamide (6,9 nylon), and polycaproamide (6 nylon) are preferably used.
In the present invention, a polyamide resin produced from, for example, adipic acid, isophthalic acid and hexamethylenediamine can also be used, and two or more kinds such as a mixture of 6 nylon and 6,6 nylon can be used. It is also possible to use a blend in which the polyamide resin is blended.

The polyamide resin (1) can be prepared, for example, by polycondensing an equimolar amount of an organic dicarboxylic acid having 4 to 12 carbon atoms and an organic diamine having 2 to 13 carbon atoms. In addition, if necessary, the organic dicarboxylic acid can be used in a larger amount than the organic diamine so that the carboxy group in the polyamide resin is in excess of the amino group. The organic dicarboxylic acid can be used in a smaller amount than the organic diamine so as to be in excess of the group. Specific examples of the organic dicarboxylic acid include adipic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid and the like. Specific examples of the organic diamine include hexamethylene diamine and octamethylene diamine. The polyamide resin (1) may be prepared from a derivative capable of producing a carboxylic acid such as an ester or an acid chloride and a derivative capable of producing an amine such as an amine salt in the same manner as the above method. it can.
The polyamide resin (2) can be prepared, for example, by heating and polycondensing an ω-amino acid in the presence of a small amount of water. In many cases, a small amount of a viscosity stabilizer such as acetic acid is added.
The polyamide resin (3) can be prepared, for example, by heating lactam in the presence of a small amount of water to cause ring-opening polymerization. In many cases, a small amount of a viscosity stabilizer such as acetic acid is added.

The polyarylene sulfide resin used in the present invention, the repeating units: wherein the general formula (Ar-S), Ar (but, X is _{-SO 2 -, - CO -,} - O-, or lower alkyl An alkylene group having 1 to 5 carbon atoms which may have a side chain.) And those having 1 to 8 substituents such as halogen and methyl groups on these aromatic rings That's it. ] As a main structural unit, may be composed of only a straight chain structure, and may have a crosslinked structure as long as it has melt processability.

The polyolefin resin used in the present invention includes, for example, a homopolymer or copolymer of an olefin monomer obtained by radical polymerization, ionic polymerization, etc., a dominant amount of an olefin monomer and a subordinate amount of a vinyl monomer. And those having as a main component a copolymer of an olefin monomer and a diene monomer, and the like are used alone or in combination of two or more. As the polymerization catalyst, a known catalyst such as a Ziegler catalyst, a chromium catalyst, or a metallocene catalyst is used. Examples of the olefin monomer herein include ethylene, propylene, butene-1, hexene-1, decene-1, octene-1, 4-methyl-pentene-1, and ethylene and propylene are particularly preferable.
Specific examples of homopolymers or copolymers of the above olefinic monomers include low density polyethylene, ultra low density polyethylene, ultra low density polyethylene, linear low density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, polypropylene. , Ethylene-propylene copolymer, polymethylpentene, polybutene and the like. Moreover, these olefin polymers are used individually or in combination of 2 or more types. Among these, a polyolefin resin mainly containing one or a mixture of two or more selected from the group consisting of polyethylene, polypropylene, and ethylene-propylene copolymer is particularly preferable.

The thermoplastic resin composition of the present invention may further contain a filler as necessary. By blending the filler, rigidity and heat resistance are improved, workability such as prevention of adhesion to the roll surface in calendaring and the like is improved, and cost reduction can be achieved.
Fillers include calcium carbonate, talc, glass fiber, carbon fiber, magnesium carbonate, mica, kaolin, calcium sulfate, barium sulfate, titanium white, white carbon, carbon black, ammonium hydroxide, magnesium hydroxide, aluminum hydroxide, etc. Is mentioned. Among these, calcium carbonate and talc are preferable.
The blending amount of the filler is preferably 0.1 to 400 parts by mass with respect to 100 parts by mass of the thermoplastic resin (the total amount of the graft polymerized powder (C) and other thermoplastic resins). Preferably it is 1-350 mass parts, More preferably, it is 1-300 mass parts. When the blending amount of the filler is less than 0.1 parts by mass, the effect of improving the rigidity is not sufficient, and when it is more than 400 parts by mass, the surface property tends to decrease.

The thermoplastic resin composition of the present invention may further contain additives such as stabilizers, lubricants, and flame retardants as necessary.
Stabilizers include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl). Phenol stabilizers such as -4-hydroxyphenyl) propionate], phosphorus stabilizers such as tris (monononylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, and dilauryl thiodipro Sulfur stabilizers such as pionate can be mentioned.
Lubricants include sodium, calcium or magnesium salts of lauric acid, palmitic acid, oleic acid or stearic acid.
Flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diisopropylphenyl phosphate, tris (chloroethyl) phosphate , Phosphate compounds such as alkoxy-substituted bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, polyphosphate such as trioxybenzene triphosphate, tetrabromobisphenol A, decabromodiphenyl oxide, hexabromocyclododecane, octabromodiphenyl ether, Bistribromophenoxye , Ethylenebistetrabromophthalimide, tribromophenol, various halogenated epoxy oligomers obtained by the reaction of halogenated bisphenol A and epihalohydrin, carbonate oligomers containing halogenated bisphenol A, halogenated polystyrene, chlorinated Examples include halogen-containing compounds such as polyolefin and polyvinyl chloride, metal hydroxides, metal oxides, sulfamic acid compounds, and the like.

The thermoplastic resin composition of the present invention is polytetrafluoroethylene (F) having a fibril-forming ability (hereinafter sometimes referred to as polytetrafluoroethylene (F)) in order to further improve the flame retardancy or impact strength. It may contain.
Polytetrafluoroethylene (F) is classified as type 3 in the ASTM standard.
Polytetrafluoroethylene (F) further preferably has a primary particle diameter in the range of 0.05 to 10 μm, and preferably has a secondary particle diameter of 30 to 1000 μm. Such polytetrafluoroethylene (F) has a melting and dripping prevention performance during the combustion test of the test piece in the UL standard vertical combustion test. Such polytetrafluoroethylene (F) is, for example, Lubron from Asahi Glass Co., Ltd. It is commercially available as CD-1 or as Polyflon from Daikin Chemical Industries, Ltd. and can be easily obtained.
As polytetrafluoroethylene (F), the thing of the form of aqueous dispersion can be used besides the usual solid form.

Moreover, as polytetrafluoroethylene (F), in order to improve the dispersibility in a thermoplastic resin composition and to obtain further favorable flame retardancy and mechanical properties, it contains polytetrafluoroethylene of the following form: It is also possible to use powder.
First, a co-agglomerated mixture of a polytetrafluoroethylene dispersion and a vinyl polymer dispersion may be mentioned. Specifically, in Japanese Patent Application Laid-Open No. 60-258263, a polytetrafluoroethylene dispersion liquid having an average particle size of 0.05 to 5 μm and a vinyl (co) polymer dispersion liquid are mixed, and polytetrafluoroethylene larger than 30 μm. A method for obtaining a polytetrafluoroethylene-containing powder by solidifying the contained particles without purification and drying the coagulated product is described, and the use of such a polytetrafluoroethylene-containing powder is possible.
Secondly, there can be mentioned a mixture of a polytetrafluoroethylene dispersion and dried polymer particles, and various kinds of such polymer particles can be used. More preferably, polycarbonate resin powder or ABS resin powder is used. It is what was used. Regarding such a mixture, JP-A-4-272957 describes a mixture of a polytetrafluoroethylene dispersion and an ABS resin powder, and such a method can be used.
Thirdly, a polytetrafluoroethylene mixed powder obtained by simultaneously removing the respective media from the mixture of the polytetrafluoroethylene dispersion and the thermoplastic resin solution can be mentioned. A mixture from which the medium has been removed by use can be mentioned, and such a mixture is described in JP-A No. 08-188653.
Fourthly, a polytetrafluoroethylene mixture obtained by polymerizing another vinyl monomer in a polytetrafluoroethylene dispersion can be mentioned, and such a mixture is disclosed in JP-A-9-95583. A method for obtaining a polytetrafluoroethylene mixed powder by supplying styrene and acrylonitrile into a polytetrafluoroethylene latex is specifically described, and such a mixed powder can be used.
Fifth, after mixing the polytetrafluoroethylene dispersion and the polymer particle dispersion, a method of polymerizing an ethylenically unsaturated monomer in the mixed dispersion can be mentioned. And a polytetrafluoroethylene mixed powder which can be finely dispersed in polytetrafluoroethylene. The details of the mixed powder are described in JP-A-11-29679, that is, in a dispersion obtained by mixing a polytetrafluoroethylene dispersion having a particle diameter of 0.05 to 1.0 μm and a polymer particle dispersion. A preferred example is a polytetrafluoroethylene mixed powder obtained by emulsion polymerization of a monomer having an ethylenically unsaturated bond, and then pulverized by coagulation or spray drying.

Here, as the polymer particles, polypropylene, polyethylene, polystyrene, HIPS, AS resin, ABS resin, MBS resin, MABS resin, ASA resin, polyalkyl (meth) acrylate, block copolymer composed of styrene and butadiene, and hydrogenation thereof. Copolymer, block copolymer of styrene and isoprene, and hydrogenated copolymer thereof, acrylonitrile-butadiene copolymer, ethylene-propylene random copolymer and block copolymer, ethylene-butene random copolymer Copolymers and block copolymers, copolymers of ethylene and α-olefin, copolymers of ethylene-unsaturated carboxylic acid esters such as ethylene-butyl acrylate, acrylate-butadiene copolymers, polyorganosiloxanes and polymers. Examples include composite rubbers containing alkyl (meth) acrylates, and copolymers obtained by grafting vinyl monomers such as styrene, acrylonitrile, and polyalkyl methacrylates to such composite rubbers. Among them, polyalkyl (meth) Acrylate, polystyrene, AS resin, ABS resin and ASA resin are preferred.
On the other hand, ethylenically unsaturated monomers include styrene, p-methylstyrene, o-methylstyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene, α-methylstyrene and the like. Body: Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, acrylic acid Acrylic ester monomers such as cyclohexyl and cyclohexyl methacrylate; Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; Vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; Vinyl acetate and vinyl butyrate Cal of etc Nsan vinyl monomer, ethylene, propylene, olefin monomers such as isobutylene; butadiene, may be selected isoprene, from such diene monomer dimethyl butadiene. These monomers can be used alone or in admixture of two or more.

  The thermoplastic resin composition of the present invention is excellent in impact resistance and dispersibility.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in more detail, this invention is not restrict | limited by these Examples. In each description, “part” and “%” all indicate “part by mass” and “% by mass”. Evaluation in Examples and Comparative Examples was performed according to the following method.

(1) Solid content concentration: Determined by drying the particle dispersion at 170 ° C. for 30 minutes.
(2) Particle size distribution in latex, mass average particle size: 0.1 ml of latex diluted to about 3% solid content with distilled water was used as a sample, and a flow rate of 1. using a CHDF2000 type particle size distribution meter manufactured by MATEC USA. The measurement was performed using a capillary cartridge for particle separation and a neutral carrier solution under the conditions of 4 ml / min, a pressure of about 2.76 MPa (about 4000 psi), and a temperature of 35 ° C. A calibration curve for the particle size was prepared by measuring a total of 13 particle sizes from 0.02 μm to 1.0 μm using monodisperse polystyrene with a known particle size manufactured by DUKE, USA as the standard particle size material.
(3) Average particle diameter (μm) of graft polymerized powder: The average particle diameter of the graft polymerized powder was determined by a sieving method.
(4) Powder flowability of graft polymerized powder: 50 g of resin powder was put into a bulk specific gravity measuring instrument used in JIS K-6721, and the state where the damper was removed was visually observed. The symbols in the table indicate the following contents.
○: Good ×: Poor (5) Izod impact strength of thermoplastic resin composition: Measured at 23 ° C. with a thickness of 3.2 mm and a notch according to ASTM D256 using a test piece obtained by injection molding.
(6) Bending strength and flexural modulus of thermoplastic resin composition: Using a test piece obtained by injection molding, measurement was performed under conditions of speed: 3 mm / min and distance between chucks: 100 mm in accordance with JIS K7171.
(7) Thermal deformation temperature (HDT) of the thermoplastic resin composition: Using a test piece obtained by injection molding, it was measured according to JIS K7191 under a load of 0.45 MPa.
(8) Dispersion state of the thermoplastic resin composition: A 0.8 mm-thick molded piece is prepared by injection molding, and the dispersion state of the graft polymer powder (C) when transmitted through light is visually observed and dispersed. Sex was evaluated.
○: Good ×: Bad

Reference Example 1 <Production of Polyorganosiloxane Graft Polymer (A-1)>
In a mixed solution of 97.5 parts of octamethylcyclotetrasiloxane (hereinafter referred to as D4), 2 parts of tetraethoxysilane as a crosslinking agent, and 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane as a grafting agent, dodecylbenzenesulfone 150 parts of distilled water in which 1 part of sodium acid was dissolved was added and stirred at 10,000 rpm for 2 minutes with a homomixer, and then passed twice through a homogenizer at a pressure of 20 MPa to obtain a stable premixed organosiloxane latex.
On the other hand, 251 parts of the organosiloxane latex was charged into a separable flask equipped with a condenser and a stirring blade, and 50 parts of a 0.4 mass% sulfuric acid aqueous solution was added thereto. While this mixed liquid was heated to 80 ° C., the temperature was maintained for 7 hours to polymerize octamethylcyclotetrasiloxane. The resulting reaction was then cooled and held at room temperature for 12 hours, then neutralized with 5% aqueous sodium hydroxide. The latex (L-1) thus obtained had a solid content concentration of 29.3%, a particle size distribution showing a single peak, and a mass average particle size of 350 nm.
27.3 parts of silicone latex (L-1) was sampled, placed in a separable flask equipped with a stirring blade, 167.7 parts of distilled water was added, the atmosphere was replaced with nitrogen, and the temperature was raised to 50 ° C. -A mixed solution of 74 parts of butyl acrylate, 0.4 part of allyl methacrylate and 0.4 part of diisopropylbenzene hydroperoxide was added. Next, a liquid mixture of 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.2 part of Rongalite and 5 parts of distilled water was added to start radical polymerization. Holding for a time, a silicone / acrylic composite rubber latex (S-1) was obtained. The solid content concentration of S-1 was 29.8%, the particle size distribution showed a single peak, and the mass average particle size was 650 nm.
A mixed liquid of 2 parts of glycidyl methacrylate, 6 parts of methyl methacrylate and 0.5 part of diisopropylbenzene hydroperoxide was dropped into 275.2 parts of composite rubber latex (S-1) over 12 minutes, and the internal temperature was 50 ° C. for 1 hour. After the first stage graft polymerization was performed, a mixed solution of 10 parts of methyl methacrylate and 0.5 part of diisopropylbenzene hydroperoxide was added dropwise over 15 minutes, and the inner temperature was maintained at 50 ° C. for 1 hour. The second stage graft polymerization was performed to complete the graft polymerization onto the composite rubber to obtain a latex of the polyorganosiloxane-based graft polymer (A-1). The latex solid content concentration was 33.3%, the particle size distribution showed a single peak, and the mass average particle size was 660 nm.

Reference Example 2 <Production of Polyorganosiloxane Graft Polymer (A-2)>
The same procedure as in Reference Example 1 except that the first stage monomer to be graft polymerized to the composite rubber latex (S-1) was 8 parts glycidyl methacrylate and the second stage monomer was 10 parts methyl methacrylate. A polyorganosiloxane-based graft polymer (A-2) latex was obtained.

Reference Example 3 <Production of Polyorganosiloxane Graft Polymer (A-3)>
Reference Example, except that the first stage monomer grafted onto the composite rubber latex (S-1) was 8 parts glycidyl methacrylate, the second stage monomer was 4 parts glycidyl methacrylate, and 6 parts methyl methacrylate. 1 to obtain a polyorganosiloxane-based graft polymer (A-3) latex.

Reference Example 4 <Production of Polyorganosiloxane Graft Polymer (A-4)>
A polyorganosiloxane-based graft polymer (A-4) latex was prepared in the same manner as in Reference Example 1, except that 18 parts of methyl methacrylate was used as the first-stage monomer for graft polymerization to the composite rubber latex (S-1). Obtained.

Reference Example 5 <Production of Hard Inelastic Polymer Latex (B-1)>
In a reaction vessel equipped with a stirrer, a cooler, a thermocouple, and a nitrogen inlet, 300 parts of deionized water, 1 part of sodium dioctylsulfosuccinate, 0.2 part of ammonium persulfate, 80 parts of methyl methacrylate, 20 parts of butyl acrylate, n -A mixture consisting of 0.2 parts of octyl mercaptan was charged, the inside of the container was replaced with nitrogen, the temperature of the reaction container was raised to 65 ° C with stirring, the mixture was heated and stirred for 2 hours to polymerize, and a hard inelastic polymer (B-1) A latex was obtained. Tg of the hard inelastic polymer (B-1) was 56.2 ° C.

Reference Example 6 <Production of Hard Inelastic Polymer Latex (B-2)>
In a reaction vessel equipped with a stirrer, a cooler, a thermocouple, and a nitrogen inlet, 300 parts of deionized water, 1 part of sodium dioctylsulfosuccinate, 0.2 part of ammonium persulfate, 70 parts of methyl methacrylate, 30 parts of butyl acrylate, n -A mixture consisting of 0.2 parts of octyl mercaptan was charged, the inside of the container was replaced with nitrogen, the temperature of the reaction container was raised to 65 ° C with stirring, the mixture was heated and stirred for 2 hours to polymerize, and a hard inelastic polymer (B-2) Latex was obtained. The Tg of the hard inelastic polymer (B-2) was 36.2 ° C.

Reference Example 7 <Production of polytetrafluoroethylene-containing mixed powder (F-1)>
Cumene hydroxy peroxide 0.3 part was dissolved in a mixed solution of 60 parts dodecyl methacrylate, 35 parts methyl methacrylate and 5 parts methyl acrylate. To this was added a mixed solution of 2.0 parts of sodium dodecylbenzenesulfonate and 300 parts of distilled water, stirred for 5 minutes at 10,000 rpm with a homomixer, and then passed twice through a homogenizer at a pressure of 20 MPa for stable preliminary dispersion. A liquid was obtained. This was charged into a flask equipped with a stirrer, a cooler, a thermocouple, a nitrogen inlet, and a reagent dropping device, and heated to 70 ° C. in a water bath under a nitrogen stream. Dissolve 0.0004 parts of ferrous sulfate, 0.0012 parts of disodium ethylenediaminetetraacetate and 0.2 parts of sodium formaldehydesulfoxylate in 5 parts of distilled water, add to the contents, start polymerization, and hold for 3 hours As a result, a polymer particle dispersion (hereinafter F-1-1) was obtained. The solid content concentration of F-1-1 was 25.2%, the particle size distribution showed a single peak, and the mass average particle size was 180 nm.
On the other hand, Asahi Glass Co., Ltd. full-on AD938 was used as a polytetrafluoroethylene particle dispersion, and the following operation was performed. The solid content concentration of AD938 is 63.0% and contains 5% polyoxyethylene alkyl ether with respect to polytetrafluoroethylene. The particle size distribution of AD938 showed a single peak, and the mass average particle size was 280 nm. 116.7 parts of distilled water was added to 83.3 parts of AD938 to obtain a polytetrafluoroethylene particle dispersion F-1-2 having a solid content of 26.2%. F-1-2 contains 25% polytetrafluoroethylene particles and 1.2% polyoxyethylene alkyl ether.
Next, 120 parts of F-1-2 (30 parts of polytetrafluoroethylene) and 199.2 parts of F-1-1 (50 parts of dodecyl methacrylate / methyl methacrylate copolymer) were mixed with a stirring blade, a condenser, The mixture was placed in a separable flask equipped with a thermocouple and a nitrogen inlet, and stirred for 1 hour under a nitrogen stream. Thereafter, the system was heated to 80 ° C. and stirred for 1 hour, then 0.001 part of iron (II) sulfate, 0.003 part of disodium ethylenediaminetetraacetate, 0.24 part of Rongalite salt, 60.8 distilled water. A mixture of 19 parts of methyl methacrylate, 1 part of methyl acrylate and 0.4 part of tertiary butyl peroxide was added dropwise over 1 hour, and the internal temperature was maintained at 80 ° C. for 1 hour after completion of the addition. The radical polymerization was completed. Through the series of operations, no solid separation was observed, and a uniform dispersion was obtained. This particle dispersion was put into 600 parts of hot water of 90 ° C. containing 5 parts of calcium acetate, solids were separated, filtered and dried to obtain 99 parts of mixed powder F-1.

Reference Example 8 <Production of polytetrafluoroethylene-containing mixed powder (F-2)>
In a separable flask equipped with a stirring blade, 200 parts of the hard inelastic polymer (B-1) latex of Reference Example 5 and 200 parts of the polytetrafluoroethylene aqueous dispersion (F-1-2) of Reference Example 7 were placed. The mixture was stirred for 10 minutes. This dispersion was added to 600 parts of 90 ° C. hot water containing 5 parts of calcium acetate, the solid matter was separated, filtered and dried to obtain 100 parts of mixed powder F-2.

[Examples 1 to 3, Comparative Examples 1 to 8]
Each of the polyorganosiloxane-based graft polymers (A-1) to (A-4) latex obtained in the reference example was coagulated with the apparatus shown in FIG.
The apparatus of FIG. 1 is an apparatus in which four overflow-type stirring tanks equipped with stirring blades are connected in series. The 1st tank 1 was equipped with the 1st metering pump 5 and the 2nd metering pump 6, and the coagulation process was performed here. The second tank 2 is equipped with a third metering pump 7 where a hard inelastic polymer addition step was performed. And in the 3rd tank 3 and the 4th tank 4, the solidification process was performed.
After continuous operation using this apparatus and becoming a steady state, the slurry is sampled from the fourth tank 4, washed with water, dehydrated, and dried to obtain graft polymerized powders (C-1 to C-11). It was.
At this time, the temperature of the first tank 1 to the fourth tank 4 is adjusted so that the first tank 1: 40 ° C., the second tank 2: 60 ° C., the third tank 3 to the fourth tank 4: 90 ° C. did. Moreover, the residence time in the 1st tank 1-the 4th tank 4 was 20 minutes, respectively.
From the first metering pump 5, a calcium 0.75% aqueous solution as a coagulant is supplied to the first tank, and from the second metering pump 6, polyorganosiloxane-based graft polymer (A-1) to (A-4) Each latex was supplied to the 1st tank 1 with the compounding quantity shown in Table 1. The flow rates of the aqueous calcium acetate solution and the polyorganosiloxane graft polymers (A-1) to (A-4) latex were adjusted to be the same. From the 3rd metering pump 7, the hard inelastic polymer latex (B-1) or (B-2) obtained by the reference example was added to the 2nd tank 2 with the compounding quantity shown in Table 1.

About the obtained graft polymerization powder (C-1 to C-11), the mass average particle diameter was measured and the powder fluidity was evaluated. The results are shown in Table 1.
As is apparent from Table 1, the graft polymer powder (C-1 to C-3) to which the hard inelastic polymer (B-1) having a Tg of 40 ° C. or higher is added has excellent powder characteristics. there were.
On the other hand, the graft polymer powder (C-5 to C-7) to which the hard inelastic polymer (B-1) or (B-2) was not added, or the hard inelastic polymer (B-2) having a low Tg. ) To which the graft polymerized powder (C-8 to C-10) was added had poor fluidity. The graft polymerized powder (C-11) to which 20 parts of the hard inelastic polymer (B-1) was added was excellent in fluidity but poor in powdering.

[Examples 4 to 9, Comparative Examples 9 to 14]
Any one of the graft polymer powders (C-1 to C-5, C-8) obtained in Examples 1 to 3 and Comparative Examples 1 to 2 and 5 and the following BF-E (comparison) The following PBT1 as other thermoplastic resins, and polytetrafluoroethylene-containing mixed powders (F-1) and (F-2) obtained in Reference Examples 7 and 8 as polytetrafluoroethylene and (F-3) below Are blended in the proportions shown in Table 2, and are extruded at a barrel temperature of 240 ° C. and a screw rotation speed of 200 rpm by a co-directional twin-screw extruder (PCM-30 manufactured by Ikegai Co., Ltd.) Adjusted. Next, test specimens for measuring physical properties were prepared with an injection molding machine, and Izod impact strength, bending strength, bending elastic modulus, HDT, and dispersion state were evaluated. The results are shown in Table 2.
-PBT1: Polybutylene terephthalate resin (Tuffpet PBT, N1000 manufactured by Mitsubishi Rayon Co., Ltd.)
BF-E: ethylene-glycidyl methacrylate copolymer (Sumitomo Chemical Co., Ltd. Bond First E)
F-3: Polytetrafluoroethylene powder (Asahi Glass Co., Ltd. CD-1)

As is apparent from Table 2, the thermoplastic resin compositions of Examples 4 to 6 using the graft polymerized powders (C-1 to C-3) of Examples 1 to 3 had high Izod impact strength. Moreover, bending strength and bending elastic modulus were also high. Moreover, it is also excellent in dispersibility, and therefore excellent in impact resistance.
Further, the thermoplastic resin compositions of Examples 7 to 9 to which polytetrafluoroethylene was further added had the added number of graft polymer powders compared to Examples 4 to 6 to which polytetrafluoroethylene was not added. Even lower, it showed high impact strength. Moreover, HDT was also higher than Examples 4-6.
On the other hand, the thermoplastic resin compositions of Comparative Examples 9-11 using the graft copolymers (C-4, C-5, C-8) of Comparative Examples 1-2, 4 have Izod impact strength and dispersibility. One or both were inferior. For this reason, the stability of impact resistance is also lacking.
Further, the thermoplastic resin composition of Comparative Example 12 having the same composition except that BF-E was added in place of the graft polymerized powders (C-1 to C-3) in Examples 4 to 6 was used in Examples 4 to 4. Compared to 6, bending strength and flexural modulus were low. A thermoplastic resin composition having a low flexural strength or flexural modulus has a low strength when bent by impact, and has poor impact resistance.
Further, in the composition of Comparative Example 12, the thermoplastic resin composition of Comparative Example 13 in which the blending amount of BF-E was decreased, although the bending strength and the bending elastic modulus were good, the Izod impact strength was significantly reduced. .
Further, the thermoplastic resin composition of Comparative Example 14 having the same composition except that BF-E was added instead of the graft polymerized powder (C-2) in Example 8 was compared with Example 8 in terms of Izod impact strength. And the flexural modulus was low.

[Examples 10 to 13, Comparative Examples 15 to 18]
Any one of the graft polymerized powders (C-1 to C-4) obtained in Examples 1 to 3 and Comparative Example 1 and BF-E (comparative), and the following PBT2 as other thermoplastic resin Were extruded at a barrel temperature of 240 ° C. and a screw rotation speed of 200 rpm using a same-direction twin-screw extruder (PCM-30 manufactured by Ikegai Co., Ltd.) to prepare pellets. Next, test specimens for measuring physical properties were prepared with an injection molding machine, and Izod impact strength, bending strength, bending elastic modulus, and HDT were evaluated. The results are shown in Table 3.
・ PBT2: Polybutylene terephthalate resin (Tuffpet PBT manufactured by Mitsubishi Rayon Co., Ltd., G1030 (containing 30% GF))

As is apparent from Table 3, the thermoplastic resin compositions of Examples 10 to 13 using the graft polymerized powders (C-1 to C-3) of Examples 1 to 3 are Izod impact strength, bending strength and The bending elastic modulus was good.
On the other hand, the thermoplastic resin compositions of Comparative Examples 15 and 16 using the graft copolymer (C-4) of Comparative Example 1 were compared with Examples 10 to 13 in terms of bending strength, bending elastic modulus, and HDT. Showed equivalent properties, but the Izod impact strength was low.
Further, the thermoplastic resin compositions of Comparative Examples 17 and 18 to which BF-E was added showed comparable properties with respect to flexural strength, flexural modulus, and HDT compared with Examples 10 to 13, but Izod Impact strength was low.

[Examples 14 to 17, Comparative Examples 19 to 22]
Any one of the graft polymerized powders (C-1 to C-4) obtained in Examples 1 to 3 and Comparative Example 1 and BF-E (comparative), and the following PA66 as other thermoplastic resin Were extruded at a barrel temperature of 260 ° C. and a screw rotation speed of 200 rpm using a same-direction twin-screw extruder (PCM-30 manufactured by Ikegai Co., Ltd.) to prepare pellets. Next, test specimens for measuring physical properties were prepared with an injection molding machine, and Izod impact strength, bending strength, bending elastic modulus, and HDT were evaluated. The results are shown in Table 4.
PA66: 66 nylon resin (Zytel 101L manufactured by DuPont)

As is clear from Table 4, the thermoplastic resin compositions of Examples 14 to 17 using the graft polymerized powders (C-1 to C-3) of Examples 1 to 3 were found to have Izod impact strength, bending strength, and The bending elastic modulus was good.
On the other hand, the thermoplastic resin compositions of Comparative Examples 19 and 20 using the graft copolymer (C-4) of Comparative Example 1 were compared with Examples 14 to 17 in terms of bending strength, bending elastic modulus, and HDT. Showed equivalent properties, but the Izod impact strength was significantly lower.
Moreover, the thermoplastic resin composition of Comparative Example 21 having the same composition except that BF-E was added instead of the graft polymerized powder (C-2) in Example 17 was compared with Example 17 in terms of Izod impact strength. Was significantly lower. Moreover, bending strength and bending elastic modulus were also low.
Further, the thermoplastic resin composition of Comparative Example 22 having the same composition except that BF-E was added in place of the graft polymerized powders (C-1 to C-3) in Examples 14 to 16, Examples 14 to Compared to 16, the Izod impact strength was significantly reduced. Moreover, bending strength and bending elastic modulus were also low.

It is the schematic of the apparatus used in the Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... 1st tank, 2 ... 2nd tank, 3 ... 3rd tank, 4 ... 4th tank, 5 ... 1st metering pump, 6 ... 2nd metering pump, 7 ... 3rd metering pump

Claims (2)

In an aqueous medium, an epoxy group-containing vinyl monomer or an epoxy group-containing vinyl monomer and other vinyl monomers are added to a composite rubber composed of a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber. A graft polymerization step of obtaining an aqueous dispersion of the polyorganosiloxane graft polymer (A) by graft polymerization of a vinyl monomer mixture comprising:
A coagulation step of coagulating the polyorganosiloxane-based graft polymer (A) in the aqueous dispersion to make the aqueous dispersion a slurry;
0.1 to 10 parts by mass of hard inelastic polymer (B) having a glass transition temperature (Tg) of 40 ° C. or higher is added to 100 parts by mass of the polyorganosiloxane-based graft polymer (A). And a hard inelastic polymer addition step of coating the polyorganosiloxane graft polymer (A) with the hard inelastic polymer (B). A method for producing a graft polymerized powder (C) obtained by coating A) with a hard inelastic polymer (B). The thermoplastic resin composition containing the graft polymerization powder (C) manufactured by the manufacturing method of the graft polymerization powder (C) of Claim 1, and another thermoplastic resin.

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