JP2019019215A - Thermoplastic resin composition and molded article thereof - Google Patents

Abstract

To provide a thermoplastic resin composition from which a molded article excellent in flowability, rigidity, impact resistance and weather resistance is obtained, and a molded article thereof.SOLUTION: The thermoplastic resin composition contains: a graft copolymer (E) obtained by graft polymerization of one or more vinyl monomers with a composite rubbery polymer obtained by combining polyorganosiloxane and an alkyl(meth)acrylate polymer; and polymethyl methacrylate (F), wherein a volume average particle size of the composite rubbery polymer is 100-200 nm, and a ratio of the particles with a particle size of 300-500 nm in the total particles of the composite rubbery polymer is 5-25 vol%.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition and a molded article thereof.

  Improving the strength of resin materials typified by rigidity and impact resistance has extremely high industrial utility in the fields of automobiles, electrical / electronic devices, and various methods have been studied so far. For example, as a thermoplastic resin material from which a molded article having excellent rigidity can be obtained, a crystalline resin such as polybutylene terephthalate (PBT) resin or polyethylene terephthalate (PET) resin, an amorphous resin reinforced with glass filler (GF), etc. There is. Examples of the thermoplastic resin material from which a molded article having excellent impact resistance can be obtained include ABS resin (acrylonitrile-butadiene-styrene copolymer), high impact polystyrene (HIPS) resin, and modified polyphenylene ether (PPE) resin.

ABS resin is widely used as a representative example of a resin material imparted with excellent impact resistance by dispersing a rubber component having a low glass transition temperature (Tg) or a low elastic modulus in a resin matrix.
However, since ABS resin uses polybutadiene, which is a conjugated diene rubber, as a rubber component, it has a drawback that it is easily deteriorated by ultraviolet rays, and the resulting molded product is inferior in weather resistance. Further, in order to develop rigidity in a molded article of an amorphous resin such as ABS resin, it is necessary to add a reinforcing material such as GF.

In order to improve the weather resistance of the molded product, ASA resin (acrylonitrile-styrene-alkyl (meth) acrylate copolymer) is used. Since ASA resin uses a saturated rubber alkyl (meth) acrylate polymer as a rubber component, it has a feature of excellent weather resistance and can be used for vehicle exterior materials and outdoor electrical equipment. ing.
As a means for improving the impact resistance and weather resistance of a molded article, a resin using a composite rubber of polyorganosiloxane and an alkyl (meth) acrylate polymer as a rubber component (hereinafter also referred to as “SAS resin”) is also used. It has been proposed (see, for example, Patent Documents 1 to 5).
By the way, in order to obtain a complicated shape and a thin molded product with an automobile part, fluidity is required. As a thermoplastic resin composition capable of obtaining a molded article having high fluidity and excellent impact resistance and weather resistance, a copolymer comprising SAS resin, an aromatic alkenyl compound component and a vinyl cyanide compound as essential components And a polymer comprising a methacrylic acid ester component as an essential component has been proposed (see, for example, Patent Document 6).

JP-A-6-25492 JP-A-11-199642 Japanese Patent Laid-Open No. 11-228764 JP 2005-132987 A JP 2004-346189 A JP 11-35783 A

  Although the techniques described in Patent Documents 1 to 6 have any effect of improving impact resistance, fluidity, and weather resistance, the effect of improving the rigidity is insufficient, so that it can be applied to vehicle exterior materials and outdoor electrical equipment. The required performance cannot be fully satisfied.

  An object of the present invention is to provide a thermoplastic resin composition that is excellent in fluidity, and that can provide a molded article excellent in rigidity, impact resistance, and weather resistance, and a molded article thereof.

As a result of intensive studies, the present inventors have found that in a graft copolymer using a composite rubber-like polymer in which a polyorganosiloxane and an alkyl (meth) acrylate polymer are combined, the volume average particle diameter of the composite rubber-like polymer is It was found that the above problems can be solved by specifying the particle size distribution and combining with polymethyl methacrylate, and the present invention has been achieved.
That is, this invention includes the following aspects.

[1] A graft copolymer (E) in which one or more vinyl monomers are graft-polymerized to a composite rubber-like polymer in which a polyorganosiloxane and an alkyl (meth) acrylate polymer are combined; Acid methyl (F),
The volume average particle diameter of the composite rubber-like polymer is 100 to 200 nm, and the ratio of particles having a particle diameter of 300 to 500 nm in all the particles of the composite rubber-like polymer is 5 to 25% by volume. , A thermoplastic resin composition.
[2] The thermoplastic resin composition according to [1], wherein the composite rubber-like polymer has a gel content of 70 to 99% by mass.
[3] The thermoplastic resin composition according to [1] or [2], wherein the proportion of particles having a particle diameter of 300 to 500 nm in the total particles of the composite rubber-like polymer is 5 to 15% by volume.
[4] The 230 ° C. of polymethyl methacrylate (F), one of the thermoplastic resin composition of the melt volume flow rate under a load of 3.7kg is 5~25cm ^3/10 min [1] to [3] object.
[5] The polymethyl methacrylate (F) is, 230 ° C., and polymethyl methacrylate melt volume flow rate under a load of 3.7kg is 15~25cm ^3/10 min, 230 ° C., under a load 3.7kg either thermoplastic resin composition of the melt volume flow rate comprises a polymethyl methacrylate is 5 to 10 cm ^3/10 min (1) to (4).
[6] A molded article comprising the thermoplastic resin composition according to any one of [1] to [5].

The thermoplastic resin composition of the present invention is excellent in fluidity. Moreover, according to the thermoplastic resin composition of the present invention, a molded article having excellent rigidity, impact resistance and weather resistance can be obtained.
The molded article of the present invention is excellent in rigidity, impact resistance and weather resistance.

Hereinafter, the present invention will be described in detail.
In the following description, the “molded product” is formed by molding the thermoplastic resin composition of the present invention.
“˜” indicating a numerical range means that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.

"Thermoplastic resin composition"
The thermoplastic resin composition of the present invention contains a graft copolymer (E) and polymethyl methacrylate (F).
The graft copolymer (E) is a composite rubber-like polymer (C) in which a polyorganosiloxane (A) and an alkyl (meth) acrylate polymer (B) are combined, and one or more vinyl monomers. (D) is a copolymer obtained by graft polymerization.
The thermoplastic resin composition of the present invention further contains an additive in addition to the graft copolymer (E) and the polymethyl methacrylate (F), as necessary, within a range not impairing the effects of the present invention. May be.

<Polyorganosiloxane (A)>
The polyorganosiloxane (A) constituting the composite rubber-like polymer (C) is not particularly limited, but a polyorganosiloxane containing a vinyl polymerizable functional group (vinyl polymerizable functional group-containing polyorganosiloxane) is preferable, A polyorganosiloxane having a vinyl polymerizable functional group-containing siloxane unit and a dimethylsiloxane unit is more preferred.

Examples of the vinyl polymerizable functional group include a methacryloyloxyalkyl group, an acryloyloxyalkyl group, a vinyl group, and a vinyl-substituted phenyl group. Carbon number of the alkyl group in a methacryloyloxyalkyl group and acryloyloxyalkyl group may be 1-12, for example.
The vinyl polymerizable functional group-containing siloxane unit may have an organic group other than the vinyl polymerizable functional group. Examples of other organic groups include an alkyl group such as a methyl group and a phenyl group.

  The content of the vinyl polymerizable functional group-containing siloxane unit is preferably 0.3 to 3 mol% with respect to the total number of moles (100 mol%) of all units constituting the polyorganosiloxane (A). When the content of the vinyl polymerizable functional group-containing siloxane unit is within the above range, the polyorganosiloxane (A) and the alkyl (meth) acrylate polymer (B) are sufficiently complexed to form poly on the surface of the molded product. Organosiloxane (A) becomes difficult to bleed out. Therefore, the impact resistance of the molded product is further improved.

  As the polyorganosiloxane (A), since the color developability is further improved, the content of silicon atoms having three or more siloxane bonds is the total number of moles of all silicon atoms in the polyorganosiloxane (A) ( 100 mol%) is preferably 0 to 1 mol%.

  As a preferable embodiment of the polyorganosiloxane (A), 0.3 to 3 mol% of a vinyl polymerizable functional group-containing siloxane unit and 99.7 to 97 mol% of a dimethylsiloxane unit (however, a vinyl polymerizable functional group-containing siloxane unit) And a total of 100 mol% of dimethylsiloxane units), and the content of silicon atoms having 3 or more siloxane bonds is 1 mol% or less with respect to the total number of moles of all silicon atoms. Examples include siloxane.

The average particle diameter of the polyorganosiloxane (A) is not particularly limited, but is preferably 400 nm or less and more preferably 150 nm or less because the impact resistance is further improved. About a lower limit, 20 nm or more is preferable.
Here, the average particle diameter of the polyorganosiloxane (A) is a value calculated from a particle diameter distribution obtained by measuring a mass-based particle diameter distribution using a dynamic light scattering particle size distribution analyzer ( Mass average particle diameter).

(Production method of polyorganosiloxane (A))
The polyorganosiloxane (A) can be obtained, for example, by polymerizing a siloxane mixture containing a dimethylsiloxane oligomer and a vinyl polymerizable functional group-containing siloxane.

  As the dimethylsiloxane oligomer, a dimethylsiloxane ring having 3 or more members is preferable, and a dimethylsiloxane ring having 3 to 7 members is more preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These dimethylsiloxanes may be used alone or in combination of two or more.

The vinyl-polymerizable functional group-containing siloxane is not particularly limited as long as it contains a vinyl-polymerizable functional group and can be bonded to the dimethylsiloxane oligomer via a siloxane bond, but the reactivity with the dimethylsiloxane oligomer is not limited. In consideration, an alkoxysilane compound containing a vinyl polymerizable functional group is preferable.
Specific examples of alkoxysilane compounds containing vinyl polymerizable functional groups include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltri Methacryloyloxysiloxanes such as methoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane; tetramethyltetravinylcyclotetrasiloxane, p-vinylphenyldimethoxy Vinyl siloxanes such as methylsilane; and the like. These vinyl polymerizable functional group-containing siloxanes may be used alone or in combination of two or more.

The method for polymerizing the siloxane mixture is not particularly limited, but emulsion polymerization is preferred. Emulsion polymerization is usually performed using an emulsifier, water, and an acid catalyst.
As the emulsifier, an anionic emulsifier is preferable. Specific examples include sodium alkylbenzene sulfonate, sodium lauryl sulfonate, sodium polyoxyethylene nonylphenyl ether sulfate, and the like. Among these, sulfonic acid-based emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are preferable. These emulsifiers may be used alone or in combination of two or more.
The amount of the emulsifier used is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the siloxane mixture. If the usage-amount of an emulsifier is 0.05 mass part or more, the dispersion state of a siloxane mixture will be easy to be stabilized, and it will become easy to hold | maintain the emulsification state of a fine particle diameter. On the other hand, if the usage-amount of an emulsifier is 5 mass parts or less, the deterioration of the weather resistance resulting from an emulsifier can be suppressed.

Examples of the acid catalyst include organic acid catalysts such as sulfonic acids (eg, aliphatic sulfonic acid, aliphatic substituted benzene sulfonic acid, aliphatic substituted naphthalene sulfonic acid, etc.); inorganic acids such as mineral acids (eg, sulfuric acid, hydrochloric acid, nitric acid, etc.) A catalyst etc. are mentioned. These acid catalysts may be used alone or in combination of two or more.
Among these, aliphatic substituted benzenesulfonic acid is preferable, and n-dodecylbenzenesulfonic acid is particularly preferable in that it is excellent in the stabilizing action of the siloxane latex (a) described later. In addition, when n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, the influence of the color of the emulsifier used in the production of the polyorganosiloxane (A) on the color of the molded product can be reduced.
Although the addition amount of an acid catalyst should just be determined suitably, it is about 0.1-20 mass parts normally with respect to 100 mass parts of siloxane mixtures.

The acid catalyst may be mixed with the siloxane mixture, the emulsifier and water at the timing of mixing them, or the siloxane mixture, the emulsifier and water are mixed and emulsified to form a latex (siloxane latex (a)). (A) may be finely divided and then mixed with the finely divided siloxane latex (a).
Since it is easy to control the particle diameter of the resulting polyorganosiloxane (A), it is preferable that the siloxane latex (a) and the acid catalyst are mixed after the siloxane latex (a) is finely divided. In particular, it is preferable that the finely divided siloxane latex (a) is dropped into the acid catalyst aqueous solution at a constant rate.
When the acid catalyst is mixed at the timing of mixing the siloxane mixture, the emulsifier, and water, it is preferable to make the particles fine after mixing them.
The siloxane latex (a) can be formed into fine particles by using, for example, a homomixer or a homogenizer. A homomixer performs microparticulation with a shearing force generated by high-speed rotation. The homogenizer atomizes with a jet output from a high pressure generator.
Examples of the method of mixing the siloxane mixture, the emulsifier, water and the acid catalyst, and the method of mixing the finely divided siloxane latex (a) and the acid catalyst include mixing by high-speed stirring, mixing by a high-pressure emulsifier such as a homogenizer, etc. Is mentioned. Among these, a method using a homogenizer is preferable because the particle size distribution of the polyorganosiloxane (A) can be reduced.

The polymerization temperature is preferably 50 ° C. or higher, and preferably 80 ° C. or higher.
In addition, when dripping the micronized siloxane latex (a) into the acid catalyst aqueous solution, the temperature of the acid catalyst aqueous solution is preferably 50 ° C. or higher, and preferably 80 ° C. or higher.
The polymerization time is preferably 2 hours or longer, and more preferably 5 hours or longer when the acid catalyst is mixed at the timing of mixing the siloxane mixture, the emulsifier and water. On the other hand, when the finely divided siloxane latex (a) and the acid catalyst are mixed, it is preferable that the finely divided siloxane latex (a) is dropped into the acid catalyst aqueous solution and held for about 1 hour.
The polymerization is stopped by cooling the reaction solution and neutralizing the reaction solution with an alkaline substance such as sodium hydroxide, potassium hydroxide, sodium carbonate or the like so that the pH of the reaction solution at 25 ° C. is about 6-8. Can be done by.
As described above, a latex of polyorganosiloxane (A) is obtained.
The average particle diameter of the polyorganosiloxane (A) can be controlled by adjusting the composition of the siloxane mixture, the amount of the acid catalyst used (the content of the acid catalyst in the aqueous acid catalyst solution), the polymerization temperature, and the like. For example, the average particle size tends to increase as the amount of the acid catalyst used decreases, and the average particle size tends to decrease as the polymerization temperature increases.

<Alkyl (meth) acrylate polymer (B)>
The (meth) acrylate polymer (B) constituting the composite rubber-like polymer (C) is a polymer having an alkyl (meth) acrylate unit. “Alkyl (meth) acrylate” refers to alkyl acrylate or alkyl methacrylate.
The (meth) acrylate polymer (B) may further have a monomer (other monomer) unit other than the alkyl (meth) acrylate unit.

Carbon number of the alkyl group of alkyl (meth) acrylate may be 1-12, for example.
Examples of the alkyl (meth) acrylate include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate; hexyl methacrylate and 2-ethylhexyl methacrylate. And alkyl methacrylate esters such as n-lauryl methacrylate. These alkyl (meth) acrylates may be used individually by 1 type, and may use 2 or more types together. Among these, n-butyl acrylate is preferable because the impact resistance of the molded product is further improved.

  Other monomers are not particularly limited as long as they can be copolymerized with alkyl (meth) acrylate, but aromatic vinyl compounds (for example, styrene, α-methylstyrene, p-methylstyrene, etc.), vinyl cyanide compounds (For example, acrylonitrile, methacrylonitrile, etc.). These other monomers may be used individually by 1 type, and may use 2 or more types together.

  In the alkyl (meth) acrylate polymer (B), the content of the alkyl (meth) acrylate unit is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, based on the total mass of all monomer units. preferable.

The alkyl (meth) acrylate polymer (B) is obtained by polymerizing a monomer component containing at least one alkyl (meth) acrylate. This monomer component may contain other monomers.
The polymerization method of the monomer component is not particularly limited, and can be performed according to a known method.

<Composite rubbery polymer (C)>
The composite rubber-like polymer (C) is a composite rubber in which a polyorganosiloxane (A) and an alkyl (meth) acrylate polymer (B) are combined.

  The ratio of the polyorganosiloxane (A) to the alkyl (meth) acrylate polymer (B) in the composite rubber-like polymer (C) is not particularly limited, but the molded article has more excellent impact resistance and weather resistance. Therefore, when the total of the polyorganosiloxane (A) and the alkyl (meth) acrylate polymer (B) is 100% by mass, the ratio of the polyorganosiloxane (A) is 4 to 14% by mass. Preferably there is.

The composite rubber-like polymer (C) is granular and is present in the thermoplastic resin composition in a granular form.
The volume average particle diameter of the composite rubber-like polymer (C) is 100 to 200 nm, preferably 120 to 180 nm. When the volume average particle diameter is not less than the lower limit of the above range, the impact resistance of the molded product is excellent. When the volume average particle diameter is not more than the upper limit of the above range, the weather resistance of the molded article is excellent.
Here, the volume average particle size of the composite rubber-like polymer (C) is measured by measuring the volume-based particle size distribution of the composite rubber-like polymer (C) using a dynamic light scattering type particle size distribution analyzer. It is a value calculated from the obtained particle size distribution.

The ratio of the particle | grains whose particle diameter is 300-500 nm which occupies in all the particles in a composite rubber-like polymer (C) is 5-25 volume%. That is, the composite rubber-like polymer (C) has a particle size distribution (volume basis) in which particles having a particle size of 300 to 500 nm occupy a proportion of 5 to 25% by volume in all particles. When the proportion of particles having a particle diameter of 300 to 500 nm is 5% by volume or more, the impact resistance of the molded product is excellent, and when it is 25% by volume or less, the weather resistance of the molded product is excellent. Since the balance between impact resistance and weather resistance of the molded product becomes better, the proportion of particles having a particle size of 300 to 500 nm is preferably 5 to 15% by volume.
Further, the proportion of the particles having a particle diameter of more than 500 nm in the total particles in the composite rubber-like polymer (C) is preferably less than 1% by volume from the viewpoint that the weather resistance of the molded product becomes better, More preferably less than 0.1% by volume.
Here, the ratio of the particles having a particle diameter of 300 to 500 nm and the ratio of the particles having a particle diameter of more than 500 nm are respectively determined using the dynamic light scattering type particle size distribution measuring instrument. It is a value calculated from a particle size distribution obtained by measuring a volume-based particle size distribution.

The volume-based particle size distribution of the composite rubbery polymer (C) is a value for all the composite rubbery polymers (C) contained in the thermoplastic resin composition. Accordingly, the volume average particle diameter, the ratio of particles having a particle diameter of 300 to 500 nm, and the ratio of particles having a particle diameter of more than 500 nm are all included in the thermoplastic resin composition (C). The overall value.
When the number of graft copolymers (E) used in the thermoplastic resin composition is two or more, as long as the volume average particle size as a whole and the proportion of particles having a particle size of 300 to 500 nm are within the above range, Among the two or more types of graft copolymers (E), the graft copolymer in which the composite rubber-like polymer (C) has a volume average particle diameter or / and a ratio of particles having a particle diameter of 300 to 500 nm is outside the above range. The polymer (E) may be contained. In terms of impact resistance and weather resistance of the molded article, the graft rubber (E) has a volume average particle diameter of the composite rubber-like polymer (C) and a ratio of particles having a particle diameter of 300 to 500 nm within the above range. ) Is preferably contained.
The volume average particle diameter of the composite rubber-like polymer (C) and the proportion of particles having a particle diameter of 300 to 500 nm are the same as the volume average particle diameter and the particles of the composite rubber-like polymer (C) in the thermoplastic resin composition. It was confirmed by image analysis of an electron micrograph that the ratio of particles having a diameter of 300 to 500 nm was shown.

The gel content of the composite rubber-like polymer (C) is preferably 70 to 99% by mass. When the gel content is 70% by mass or more, the rigidity of the molded product is more excellent. When the gel content is 99% by mass or less, the impact resistance of the molded product is more excellent.
The gel content in the present invention is the composite rubber-like polymer (C) before immersion in acetone when the composite rubber-like polymer (C) is immersed in acetone and the insoluble matter not dissolved in acetone is dried. ) To the mass of the dried acetone-insoluble matter. In detail, it measures by the method as described in the Example mentioned later.

(Method for producing composite rubber-like polymer (C))
The production method of the composite rubber-like polymer (C) is not particularly limited, but a plurality of latexes each containing a polyorganosiloxane (A) and an alkyl (meth) acrylate polymer (B) are hetero-aggregated or co- enlarged. A method comprising: polymerizing a monomer component forming the other polymer in the presence of a latex containing one of the polyorganosiloxane (A) and the alkyl (meth) acrylate polymer (B) to form a composite. And the like.
Since the volume average particle size and particle size distribution of the composite rubber-like polymer (C) can be easily adjusted to be within the above-mentioned range, alkyl (meth) is present in the presence of the latex polyorganosiloxane (A). By mixing the monomer component containing one or more acrylates by radical polymerization to obtain a copolymer latex (radical polymerization step), the copolymer latex and the acid group-containing copolymer latex are mixed. A method having a step of enlarging the polymer latex (a hypertrophy step) is preferable. This method preferably further includes a step of adding a condensed acid salt to the copolymer latex (condensed acid salt adding step) after the radical polymerization step and before the enlargement step.

Radical polymerization process:
The radical polymerization step is a step of radical polymerization of a monomer component containing one or more alkyl (meth) acrylates in the presence of latex polyorganosiloxane (A).
The monomer component containing at least one alkyl (meth) acrylate may be added all at once to the latex polyorganosiloxane (A), or may be added continuously or intermittently.

When radically polymerizing a monomer component containing one or more alkyl (meth) acrylates, a graft crossing agent or a crosslinking agent may be used as necessary.
Examples of the grafting agent or cross-linking agent include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, diethylene methacrylate ethylene glycol diester, dimethacrylic acid propylene glycol diester, and dimethacrylic acid 1,3-butylene glycol diester. And 1,4-butylene glycol diester of dimethacrylic acid. These may be used individually by 1 type and may use 2 or more types together.

In radical polymerization, a radical polymerization agent and an emulsifier are usually used.
Examples of the radical polymerization initiator include peroxides, azo initiators, redox initiators in which an oxidizing agent and a reducing agent are combined. In these, a redox-type initiator is preferable and especially the sulfoxylate-type initiator which combined ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, sodium formaldehyde sulfoxylate, and hydroperoxide is preferable.
Although it does not restrict | limit especially as an emulsifier, since it is excellent in the stability of the latex at the time of radical polymerization and a polymerization rate can be raised, various carboxylic acids, such as sodium sarcosinate, fatty acid potassium, fatty acid sodium, alkenyl succinate dipotassium, rosin acid soap, etc. Salts are preferred. Of these, dipotassium alkenyl succinate is preferable because gas generation can be suppressed when the obtained graft copolymer (E) and the thermoplastic resin composition containing the graft copolymer (E) are molded at high temperature.
For example, the polymerization start temperature may be 40 to 70 ° C., and the time from the start to the end of the polymerization may be 0.5 to 3.0 hours.

Condensate addition process:
The condensed acid salt addition step is a step of adding a condensed acid salt to the copolymer latex obtained in the radical polymerization step. Prior to the enlargement process, by adding a condensation salt to the copolymer latex, it becomes possible to reduce the addition amount of the acid group-containing copolymer latex by making the enlargement easier to proceed, and the composite rubber It becomes easy to adjust the volume average particle size and particle size distribution of the polymer (C) within the above-described ranges.
As the condensed acid salt, for example, a salt of a condensed acid such as phosphoric acid or silicic acid and an alkali metal and / or alkaline earth metal is used. Among these, pyrophosphoric acid and alkali metal salts which are condensed acids of phosphoric acid are preferable, and sodium pyrophosphate or potassium pyrophosphate is particularly preferable.

The addition amount of the condensed acid salt may be adjusted so that the volume average particle size and the particle size distribution of the composite rubber-like polymer (C) are within the above-mentioned ranges, but usually it is obtained in the radical polymerization step. It is preferable to set it as 0.1-5 mass parts with respect to 100 mass parts of solid content of copolymer latex, and 0.3-3 mass parts is more preferable. If the amount of condensed acid salt is not less than the lower limit of the above range, the enlargement is sufficiently advanced, and if it is not more than the upper limit of the above range, the enlargement is sufficiently advanced, or the rubber latex is easily stabilized. , Generation of a large amount of agglomerates can be suppressed.
The condensed acid salt is preferably added to the copolymer latex all at once.

  The pH of the copolymer latex to which the condensed acid salt is added (mixture of copolymer latex and condensed acid salt) at 25 ° C. is preferably 7 or more. If the pH is 7 or more, enlargement is likely to proceed sufficiently. In order to make pH 7 or more, general alkali compounds, such as sodium hydroxide and potassium hydroxide, can be used.

Enlargement process:
The enlargement process is obtained in the radical polymerization process, and if necessary, the copolymer latex to which the condensation salt is added in the condensation salt addition process and the acid group-containing copolymer latex are mixed. This is a step of enlarging the copolymer latex. Thereby, the latex of a composite rubber-like polymer (C) is obtained.

The acid group-containing copolymer has an acid group-containing monomer unit and an alkyl (meth) acrylate unit. Other monomer units other than these may further be included as necessary.
As the acid group-containing monomer, an unsaturated compound having a carboxy group is preferable. Examples of the unsaturated compound having a carboxy group include (meth) acrylic acid, itaconic acid, crotonic acid and the like, and (meth) acrylic acid is particularly preferable. (Meth) acrylic acid refers to acrylic acid or methacrylic acid. An acid group containing monomer may be used individually by 1 type, and may use 2 or more types together.

  Examples of the alkyl (meth) acrylate include esters of (meth) acrylic acid and an alcohol having a linear or branched alkyl group having 1 to 12 carbon atoms, such as methyl acrylate, ethyl acrylate, and acrylic acid. Propyl, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-methacrylate Examples include butyl and 2-ethylhexyl methacrylate. Among these, alkyl (meth) acrylates having an alkyl group having 1 to 8 carbon atoms are particularly preferable. Alkyl (meth) acrylate may be used individually by 1 type, and may use 2 or more types together.

  The other monomer is a monomer copolymerizable with the acid group-containing monomer and the alkyl (meth) acrylate, and is a monomer other than the acid group-containing monomer and the alkyl (meth) acrylate. . Other monomers include aromatic vinyl compounds (eg, styrene, α-methylstyrene, p-methylstyrene, etc.), vinyl cyanide compounds (eg, acrylonitrile, methacrylonitrile, etc.), two or more polymerizable Examples include compounds having a functional group (for example, allyl methacrylate, polyethylene glycol ester dimethacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitic acid, etc.). Another monomer may be used individually by 1 type and may use 2 or more types together.

  As an acid group containing copolymer, content of an acid group containing monomer unit is 5-40 mass with respect to the total mass (100 mass%) of all the monomer units which comprise an acid group containing copolymer. %, A copolymer having an alkyl (meth) acrylate unit content of 60 to 95% by mass and another monomer unit content of 0 to 48% by mass is preferred, and the content of the acid group-containing monomer unit A copolymer having an amount of 8 to 30% by mass, an alkyl (meth) acrylate unit content of 70 to 92% by mass, and another monomer unit content of 0 to 30% by mass is more preferable. When the content of the acid group-containing monomer unit is not less than the lower limit and the content of the alkyl (meth) acrylate unit is not more than the upper limit, sufficient enlargement ability can be obtained. If the content of the acid group-containing monomer unit is not more than the above upper limit value and the content of the alkyl (meth) acrylate unit is not less than the above lower limit value, a large amount of coagulum is produced during the production of the acid group-containing copolymer latex. Can be suppressed. If the content of other monomer units is not more than the above upper limit value, the acid group-containing copolymer latex can have a sufficient enlargement ability.

  The acid group-containing copolymer latex polymerizes monomer components containing an acid group-containing monomer, an alkyl (meth) acrylate, and, if necessary, other monomers copolymerizable with these in water. Is obtained. As the polymerization method, a general emulsion polymerization method can be used.

Examples of emulsifiers used in emulsion polymerization include carboxylic acid-based emulsifiers such as oleic acid, palmitic acid, stearic acid, alkali metal salts of rosin acid, and alkali metal salts of alkenyl succinic acid; alkyl sulfate esters, sodium alkylbenzene sulfonates, Known emulsifiers such as anionic emulsifiers such as sodium alkylsulfosuccinate and sodium polyoxyethylene nonylphenyl ether sulfate may be mentioned. These emulsifiers may be used alone or in combination of two or more.
The emulsifier may be added all at once in the initial stage of polymerization, or may be added continuously or intermittently. Depending on the amount of the emulsifier and its method of use, the particle size of the acid group-containing copolymer latex may eventually affect the particle size of the enlarged composite rubber-like polymer (C) latex. It is preferable to select the method of use.

Examples of the polymerization initiator used for emulsion polymerization include a thermal decomposition type initiator and a redox type initiator. Examples of the thermal decomposition type initiator include potassium persulfate, sodium persulfate, and ammonium persulfate. Examples of the redox-type initiator include combinations of organic peroxides represented by cumene hydroperoxide, sodium formaldehyde sulfoxylate, iron salts, and the like. These polymerization initiators may be used alone or in combination of two or more.
In the case of emulsion polymerization, a chain transfer agent such as mercaptans (for example, t-dodecyl mercaptan, n-octyl mercaptan, etc.), terpinolene, α-methylstyrene dimer or the like is used to adjust the molecular weight or the pH is adjusted. Therefore, an electrolyte can be added as an alkali, an acid, or a thickener.

  The amount of acid group-containing copolymer latex added in the enlargement step (in terms of solid content) is adjusted so that the volume average particle size and particle size distribution of the composite rubber-like polymer (C) are within the above-described ranges. Usually, 0.1-5 mass parts is preferable with respect to 100 mass parts of solid content of the copolymer latex obtained by a radical polymerization process, and 0.3-3 mass parts is more preferable. If the addition amount of the acid group-containing copolymer latex is 0.1 parts by mass or more, the enlargement proceeds sufficiently. Moreover, it can suppress that agglomerates generate | occur | produce in large quantities. On the other hand, if the addition amount of the acid group-containing copolymer latex is 5 parts by mass or less, the pH of the enlarged latex can be suppressed from being lowered, and the latex is less likely to become unstable.

The acid group-containing copolymer latex may be added all at once to the copolymer latex, or may be added continuously or intermittently by dropping.
It is preferable to appropriately control stirring during enlargement. If the stirring is insufficient, the unexpanded rubbery polymer may remain due to local enlargement. On the other hand, if the stirring is performed excessively, the enlarged latex becomes unstable and a large amount of agglomerates may be generated.
Although the temperature in particular when performing enlargement is not restrict | limited, 20-90 degreeC is preferable and 30-80 degreeC is more preferable. If the temperature is outside this range, the enlargement may not proceed sufficiently.

  The composite rubber-like polymer (C) is enlarged using the acid group-containing copolymer latex as described above, and then a monomer component containing at least one alkyl (meth) acrylate is further added. You may manufacture by making it polymerize.

<Vinyl monomer (d)>
The vinyl monomer (d) is not particularly limited, but aromatic vinyl compounds, (meth) acrylic acid alkyl esters, vinyl cyanide compounds, and the like are preferable. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, and the like. Examples of (meth) acrylic acid alkyl esters include methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and t-butyl acrylate. Can be mentioned. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Among these, it is preferable to use styrene and acrylonitrile in combination since the impact resistance of the molded product is further improved.

<Graft copolymer (E)>
The graft copolymer (E) is a copolymer obtained by graft polymerizing one or more vinyl monomers (d) to the composite rubber-like polymer (C).
In the graft copolymer (E), it is difficult to specify how one or more vinyl monomers (d) are polymerized in the composite rubber-like polymer (C). That is, there is a situation (impossible / unpractical situation) in which the graft copolymer (E) cannot be directly specified by its structure or characteristics, or is almost impractical. Therefore, the graft copolymer (E) is more appropriately defined as “one or more vinyl monomers (d) are graft-polymerized to the composite rubber-like polymer (C)”.

  The mass ratio between the composite rubbery polymer (C) and the one or more vinyl monomers (d) is not particularly limited, but the balance between the impact resistance and the weather resistance of the molded product becomes better. Therefore, the composite rubber-like polymer (C) is preferably 10 to 80% by mass, and one or more vinyl monomers (d) are preferably 20 to 90% by mass, and the composite rubber-like polymer (C) Is preferably 30-70% by mass and at least one vinyl monomer (d) is 30-70% by mass (provided that the composite rubber-like polymer (C) and one or more vinyl monomers) The total amount with the monomer (d) is 100% by mass). With such a mass ratio, the fluidity of the thermoplastic resin composition and the impact resistance and weather resistance of the molded product become more excellent.

(Production method of graft copolymer (E))
The graft copolymer (E) is obtained by graft polymerization of one or more vinyl monomers (d) to the composite rubber-like polymer (C).
The method for carrying out the graft polymerization is not particularly limited, but emulsion polymerization is preferred because it can be controlled so that the reaction proceeds stably. Specifically, a method in which one or more vinyl monomers (d) are charged all at once to the latex of the composite rubber-like polymer (C) and then polymerized; the latex of the composite rubber-like polymer (C) A method in which a part of one or more vinyl monomers (d) is charged first, and the remainder is dropped into the polymerization system while polymerizing as needed; one or more vinyl compounds are added to the latex of the composite rubber-like polymer (C). A method of polymerizing at any time while dropping the whole amount of the monomer (d) can be mentioned, and these can be carried out in one step or in two or more steps. When carrying out by dividing into two or more stages, it is also possible to carry out by changing the kind and composition ratio of one or more kinds of vinyl monomers (d) in each stage.
In the emulsion polymerization, a radical polymerization initiator and an emulsifier are usually used. Examples of these radical polymerization initiators and emulsifiers include the radical polymerization initiators and emulsifiers exemplified above in the description of the method for producing the composite rubber-like polymer (C).
In the polymerization, various known chain transfer agents may be added in order to control the molecular weight and graft ratio of the obtained graft copolymer (E).
The polymerization conditions may be, for example, a polymerization start temperature of 60 to 90 ° C. and a time from the start of polymerization to the end of 2.0 to 5.0 hours.

The graft copolymer (E) obtained by emulsion polymerization is usually in a latex state.
As a method for recovering the graft copolymer (E) from the latex of the graft copolymer (E), for example, the latex of the graft copolymer (E) is poured into hot water in which a coagulant is dissolved. Examples thereof include a wet method of coagulating in a slurry state; a spray drying method of recovering the graft copolymer (E) semi-directly by spraying the latex of the graft copolymer (E) in a heated atmosphere.

  Examples of the coagulant used in the wet method include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid; metal salts such as calcium chloride, calcium acetate, and aluminum sulfate, and are selected according to the emulsifier used in the polymerization. . For example, when only a carboxylic acid soap such as fatty acid soap or rosin acid soap is used as an emulsifier, one or more of the above-described coagulants can be used. Further, when an emulsifier exhibiting a stable emulsifying power even in an acidic region such as sodium alkylbenzenesulfonate is used as the emulsifier, a metal salt is suitable as the coagulant.

When a wet method is used, a slurry-like graft copolymer (E) is obtained.
As a method for obtaining the dried graft copolymer (E) from the slurry-like graft copolymer (E), first, the remaining emulsifier residue is eluted and washed in water, and then this slurry is centrifuged or press-dehydrated. Examples include a method of drying with an air dryer after dehydrating with a machine; a method of simultaneously performing dehydration and drying with a press dehydrator or an extruder. By this method, a powder or particulate dry graft copolymer (E) is obtained.
Although it does not restrict | limit especially as washing | cleaning conditions, It is preferable to wash | clean on the conditions from which the amount of emulsifier residue contained in 100 mass% of graft copolymers (E) after drying becomes the range of 0.5-2 mass%. If the amount of the emulsifier residue in the graft copolymer (E) is 0.5% by mass or more, the fluidity of the obtained graft copolymer (E) and the thermoplastic resin composition containing the graft copolymer (E) tends to be further improved. . On the other hand, when the emulsifier residue in the graft copolymer (E) is 2% by mass or less, gas generation can be suppressed when the thermoplastic resin composition is molded at a high temperature. The amount of the emulsifier residue can be adjusted by, for example, the washing time.
A drying temperature may be 60-80 degreeC, for example.
The volume average particle size and volume-based particle size distribution of the composite rubber-like polymer (C) in the obtained graft copolymer (E) are the same as those of the composite rubber-like polymer used in the production of the graft copolymer (E). It is the same as the volume average particle size and volume-based particle size distribution of the composite rubber-like polymer (C) in the latex of the combined (C).
In addition, the graft copolymer (E) discharged | emitted from the press dehydrator and the extruder is not collect | recovered, but it is also possible to send directly to the extruder and molding machine which manufacture a resin composition, and to make a molded article.

<Polymethyl methacrylate (F)>
230 ° C. of polymethyl methacrylate (F), melt volume flow rate under a load of 3.7 kg (hereinafter, also referred to as "MVR".) Is preferably 5~25cm ^3/10 min, 7~20cm ^3/10 min Is more preferable. If the MVR of polymethyl methacrylate (F) is not less than the lower limit, the fluidity of the thermoplastic resin composition is more excellent, and if it is not more than the upper limit, the rigidity of the molded product is more excellent.
MVR is measured according to ISO 1133.
As polymethyl methacrylate (F), 1 type may be used independently and 2 or more types from which MVR differs may be used together.

Since the balance between the fluidity of the thermoplastic resin composition and the rigidity of the molded article becomes better, the following two types of polymethyl methacrylate (F-1) and (F -2) is preferably used in combination.
(F-1): 230 ℃ , polymethyl methacrylate MVR under a load of 3.7kg is 15~25cm ^3/10 min.
(F-2): 230 ℃ , polymethyl methacrylate MVR under a load of 3.7kg is 5 to 10 cm ^3/10 min.
(F-1) MVR of, 18~22cm ^3/10 min is preferred.
(F-2) MVR of, 5~8cm ^3/10 min is preferred.

  The mass ratio of the two types of polymethyl methacrylates (F-1) and (F-2) is not particularly limited, but since the balance between the rigidity and the fluidity of the molded product becomes better, ( When the total mass of (F-1) and (F-2) is 100% by mass, (F-1) is 20 to 60% by mass and (F-2) is 20 to 60% by mass. Preferably, (F-1) is 40 to 60% by mass, and (F-2) is 40 to 60% by mass.

<Additives>
Examples of the additive include various stabilizers such as an antioxidant and a light stabilizer, a lubricant, a plasticizer, a release agent, a dye, a pigment, an antistatic agent, and an inorganic filler.

<Content ratio of each component>
When the total mass of the graft copolymer (E) and polymethyl methacrylate (F) in the thermoplastic resin composition is 100 mass%, the content of the graft copolymer (E) is 20 to 50 mass. %, The polymethyl methacrylate (F) content is preferably 50 to 80% by mass, the graft copolymer (E) content is 25 to 40% by mass, and the polymethyl methacrylate (F) content is The amount is more preferably 60 to 75% by mass. When the content of the graft copolymer (E) is not less than the lower limit and the content of polymethyl methacrylate (F) is not more than the upper limit, the impact resistance is more excellent. When the content of the graft copolymer (E) is not more than the above upper limit value and the content of the polymethyl methacrylate (F) is not less than the above lower limit value, fluidity and rigidity are more excellent.

  The ratio of the total mass of the graft copolymer (E) and polymethyl methacrylate (F) to the total mass of the thermoplastic resin composition is preferably 70 to 100 mass%, more preferably 90 to 100 mass%.

<MVR of thermoplastic resin composition>
MVR at 220 ° C., load 10kg of the thermoplastic resin composition of the present invention is preferably 6.0~16.0cm ^3/10 min, 9.0~16.0cm ^3/10 min is more preferable. If MVR of a thermoplastic resin composition is more than the said lower limit, the fluidity | liquidity of a thermoplastic resin composition will be more excellent. If MVR of a thermoplastic resin composition is below the said upper limit, the moldability of a molded article will be more excellent.
The MVR of the thermoplastic resin composition can be adjusted by the MVR, content and molecular weight of polymethyl methacrylate (F).

<Method for producing thermoplastic resin composition>
The method for producing the thermoplastic resin composition of the present invention is not particularly limited. For example, the graft copolymer (E), polymethyl methacrylate (F), and additives as necessary are mixed and dispersed using a mixer such as a V-type blender or a Henschel mixer, and thus obtained. The mixture is melt kneaded using a melt kneader such as a screw extruder, Banbury mixer, pressure kneader, or mixing roll. Moreover, you may pelletize a melt-kneaded material using a pelletizer etc. as needed.

<Effect>
In the thermoplastic resin composition of the present invention described above, at least one composite rubbery polymer (C) in which the polyorganosiloxane (A) and the alkyl (meth) acrylate polymer (B) are combined is used. A graft copolymer (E) obtained by graft polymerization of the vinyl monomer (d) and polymethyl methacrylate (F), and the volume average particle diameter of the composite rubber-like polymer (C) is 100 to 100. Since the proportion of particles having a particle diameter of 300 to 500 nm in the total particle of the composite rubber-like polymer (C) is 200 to 500% by volume, the fluidity is excellent, and the rigidity, A molded article excellent in impact resistance and weather resistance can be obtained.

"Molding"
The molded article of the present invention consists of the thermoplastic resin composition of the present invention.
Since the molded article of the present invention uses the thermoplastic resin composition of the present invention, it is excellent in rigidity, impact resistance, and weather resistance.

The molded article of the present invention can be obtained by molding the thermoplastic resin composition of the present invention.
The molding method is not particularly limited, and a known molding method can be used. Examples thereof include an injection molding method, a press molding method, an extrusion molding method, a vacuum molding method, and a blow molding method.

  Examples of uses of molded products include vehicle parts such as pillars, door mirrors, radiator grills, spoilers, OA equipment, home appliance parts, building materials parts such as wall materials and window frames, and miscellaneous goods such as toys and stationery. A lamp is suitable.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to a following example. In the following examples, “%” and “part” are based on mass unless otherwise specified.
Various measurements and evaluation methods in Examples and Comparative Examples described below are as follows.

"Measurement / Evaluation"
<Measurement of particle size distribution and volume average particle size of composite rubber-like polymer (C)>
Using a Nanotrac particle size distribution meter ("UPA-EX150" manufactured by Nikkiso Co., Ltd.) and using pure water as a measurement solvent, the volume-based particle size distribution of the composite rubber-like polymer (C) latex is measured and obtained. From the obtained particle size distribution, the volume average particle size and the ratio of particles having a particle size of 300 to 500 nm were determined. These can each be regarded as the volume average particle diameter of the composite rubber-like polymer (C) in the thermoplastic resin composition and the ratio of particles having a particle diameter of 300 to 500 nm. Actually, the volume average particle diameter of the composite rubber-like polymer (C) and the ratio of the particles having a particle diameter of 300 to 500 nm are the same as the volume average particle of the composite rubber-like polymer (C) in the thermoplastic resin composition. It was confirmed by image analysis of an electron micrograph that the diameter and the ratio of particles having a particle diameter of 300 to 500 nm were shown.
In an example in which two types of graft copolymers (E) are used in combination, the volume average particle diameter and particle diameter of the composite rubber-like polymer (C) in the thermoplastic resin composition are 300 to 300 by image analysis using an electron microscope. The proportion of 500 nm particles was confirmed.

<Measurement of gel content>
0.5 g of a coagulated powder sample [D1] obtained by coagulating an aqueous or solvent dispersion of the composite rubber-like polymer (C) with calcium chloride, washing with methanol, and vacuum-drying for 24 hours in 100 mL of acetone The sample was added, stirred with a spatula, and immersed at 23 ° C. for 24 hours to obtain an acetone-containing sample. Next, the centrifuge cell [D2] is weighed, the whole amount of the acetone-containing sample is put into the centrifuge cell, ultracentrifuged at 1400 rpm for 4 hours, the supernatant is removed by decantation, and the remaining insoluble matter The centrifuge cell was vacuum dried at 23 ° C. for 24 hours. The mass of the dried product [D3] was measured, and the gel content of the composite rubber-like polymer (C) was determined from the following formula (1).
Gel content rate (%) = (Dry substance amount [D3] (g) −Centrifuge cell mass [D2] (g)) / Coagulated powder sample mass [D1] (g) (1)

<Measurement of MVR of polymethyl methacrylate (F)>
The MVR of polymethyl methacrylate was measured using a melt indexer (“F-F01” manufactured by Toyo Seiki Seisakusho Co., Ltd.) according to ISO 1133 at a cylinder temperature of 230 ° C. and a load of 3.7 kg.

<Rigidity evaluation>
In accordance with ISO 3167, a test piece (molded product) was prepared from the pellet-shaped thermoplastic resin composition by using an injection molding machine (“IS55FP-1.5A” manufactured by Toshiba Machine Co., Ltd.). The flexural modulus of this test piece was measured in an atmosphere of 23 ° C. according to ISO 178. The higher the flexural modulus, the better the rigidity.

<Evaluation of impact resistance>
In accordance with ISO 3167, a test piece (molded product) was prepared from the pellet-shaped thermoplastic resin composition by using an injection molding machine (“IS55FP-1.5A” manufactured by Toshiba Machine Co., Ltd.). The Charpy impact strength (notched) of this test piece was measured in an atmosphere of 23 ° C. according to ISO 179. The greater the Charpy impact strength, the better the impact resistance.

<Evaluation of fluidity>
The MVR of the pellet-shaped thermoplastic resin composition was measured using a melt indexer (“F-F01” manufactured by Toyo Seiki Seisakusho Co., Ltd.) in accordance with ISO 1133 at a cylinder temperature of 220 ° C. and a load of 10 kg. The larger the MVR, the better the fluidity.

<Evaluation of weather resistance>
From the pellet-shaped thermoplastic resin composition, using a 4-ounce injection molding machine manufactured by Nippon Steel Works, a cylinder set temperature of 260 ° C., a mold temperature of 60 ° C., and an injection rate of 20 g / second, a length of 100 mm, A plate-like molded product having a width of 100 mm and a thickness of 3 mm was produced.
Next, the surface of the obtained molded product was cut to a length of 45 mm and a width of 50 mm, and a sunshine weather meter (WEL-SUN-HCH-B manufactured by Suga Test Instruments Co., Ltd.) was used, in accordance with JIS D 0205 and JIS K 7350-4. The test was conducted for 1000 hours under the condition of 63 ° C. and rain.
The degree of color change (ΔE) of the molded product before and after the test was measured using a colorimeter (Minolta CM-508d D65 10 ° SCE method). The smaller ΔE, the better the weather resistance.

"Manufacture of polyorganosiloxane"
<Production Example 1: Production of polyorganosiloxane (A)>
98 parts of octamethylcyclotetrasiloxane and 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane mixture. To this was added an aqueous solution consisting of 0.67 parts of sodium dodecylbenzenesulfonate and 300 parts of ion-exchanged water, and the mixture was stirred at 10000 rpm for 2 minutes with a homomixer. Then, the homogenizer was charged with ^{2 at} a pressure of 300 kg / cm 2. Through circulation, a stable premixed organosiloxane latex was obtained.
Separately, 10 parts of dodecylbenzenesulfonic acid and 90 parts of ion-exchanged water were put into a reactor equipped with a reagent injection container, a cooling tube, a jacket heater, and a stirrer, and a 10% aqueous solution of dodecylbenzenesulfonic acid ( Acid catalyst aqueous solution) was prepared.
This acid catalyst aqueous solution was heated to 85 ° C., and in this state, the premixed organosiloxane latex was added dropwise to the acid catalyst aqueous solution over 2 hours. After the completion of the addition, the temperature was maintained for 3 hours, and then cooled to 40 ° C. or lower. Next, this reaction product was neutralized to pH 7.0 with a 10% aqueous sodium hydroxide solution to obtain a latex of polyorganosiloxane (A).
The obtained polyorganosiloxane (A) latex was dried at 180 ° C. for 30 minutes and the solid content was determined to be 18.2%. The average particle diameter based on mass of the polyorganosiloxane (A) was 30 nm.

"Production of acid group-containing copolymer latex"
<Production Example 2: Production of acid group-containing copolymer latex (K-1)>
In a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer, 200 parts of ion exchange water, 2 parts of potassium oleate, 4 parts of sodium dioctylsulfosuccinate, ferrous sulfate heptahydrate 0.003 Part, 0.009 part of ethylenediaminetetraacetic acid disodium salt and 0.3 part of sodium formaldehyde sulfoxylate were charged under a nitrogen stream, and the temperature was raised to 60 ° C. When the temperature reached 60 ° C., a mixture composed of 85 parts of n-butyl acrylate, 15 parts of methacrylic acid and 0.5 part of cumene hydroperoxide was continuously added dropwise over 120 minutes. After completion of the dropwise addition, ripening was further performed for 2 hours while maintaining the temperature at 60 ° C., the solid content was 33%, the polymerization conversion was 96%, and the acid group-containing copolymer had an acid group content of 120 nm. A copolymer latex (K-1) was obtained.

<Production Example 3: Production of acid group-containing copolymer latex (K-2)>
Similar to Production Example 2, except that potassium oleate is 1.5 parts, n-butyl acrylate is 88 parts, and methacrylic acid is 12 parts, solid content is 33%, polymerization conversion is 97%, acid An acid group-containing copolymer latex (K-2) having a volume average particle size of the group-containing copolymer of 60 nm was obtained.

"Production of graft copolymer"
<Production Example 4: Production of Graft Copolymer (E-1)>
In a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer, 5.0 parts of latex of polyorganosiloxane (A) in terms of solid content, 0.6 parts of dipotassium alkenyl succinate, 190 parts of ion exchange water was charged and mixed. Next, as a monomer constituting the alkyl (meth) acrylate polymer (B), 45.0 parts of n-butyl acrylate, 0.6 part of allyl methacrylate, 0.09 part of 1,3-butylene glycol dimethacrylate, A mixture consisting of 0.02 parts of t-butyl hydroperoxide was added. The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the internal temperature was raised to 60 ° C. When the internal temperature reached 60 ° C., from 0.000075 part of ferrous sulfate heptahydrate, 0.00023 part of ethylenediaminetetraacetic acid disodium salt, 0.2 part of sodium formaldehyde sulfoxylate, 10 parts of ion-exchanged water The resulting aqueous solution was added to initiate radical polymerization. After the polymerization exotherm is confirmed, the jacket temperature is set to 75 ° C., the polymerization is continued until the polymerization exotherm is not confirmed, and this state is maintained for another hour, and a composite rubber in which polyorganosiloxane and polybutyl acrylate rubber are combined. A latex was obtained (radical polymerization step). The obtained composite rubber had a volume average particle diameter of 90 nm.
After the liquid temperature inside the reactor dropped to 70 ° C., 0.20 part of 5% aqueous sodium pyrophosphate solution was added as a solid content (condensate addition step). Next, after controlling at an internal temperature of 70 ° C., 0.26 parts of acid group-containing copolymer latex (K-1) is added as a solid content, stirred for 30 minutes, enlarged, and a composite rubber-like polymer (C ) Latex was obtained (the enlargement process).
The obtained latex-like composite rubbery polymer (C) had a volume average particle size of 150 nm. Moreover, the ratio of the particle | grains whose particle diameter is 300-500 nm occupied in all the particles of a composite rubber-like polymer (C) was 15 volume%, and the gel content rate was 95 mass%.
To the latex of this composite rubber-like polymer (C), 0.001 part of ferrous sulfate heptahydrate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.3 part of sodium formaldehyde sulfoxylate, 10 parts of ion-exchanged water An aqueous solution consisting of parts was added. Subsequently, a mixed liquid composed of 8.8 parts of acrylonitrile, 26.2 parts of styrene, and 0.16 part of t-butyl hydroperoxide was dropped over 80 minutes to perform polymerization. After completion of the dropwise addition, after maintaining the temperature at 75 ° C. for 30 minutes, a mixture comprising 3.8 parts of acrylonitrile, 11.2 parts of styrene, 0.07 part of t-butyl hydroperoxide and 0.02 part of n-octyl mercaptan Was added dropwise over 20 minutes to polymerize. After completion of dropping, after maintaining the temperature at 75 ° C. for 30 minutes, 0.05 part of cumene hydroperoxide was added, and after maintaining the temperature at 75 ° C. for 30 minutes, the mixture was cooled, and a composite rubber polymer ( A latex of a silicone / acrylic composite rubber graft copolymer (E-1) obtained by graft polymerization of acrylonitrile and styrene on C) was obtained.
Subsequently, 150 parts of a 1% calcium acetate aqueous solution was heated to 60 ° C., and 100 parts of the latex of the graft copolymer (E-1) was gradually dropped into the solution to be solidified. Then, the precipitate was separated, dehydrated, washed and then dried to obtain a graft copolymer (E-1).

<Production Example 5: Production of graft copolymers (E-2) to (E-10)>
Table 1 shows the amounts of allyl methacrylate and 1,3-butylene glycol dimethacrylate used in the radical polymerization step, the amount of sodium pyrophosphate used in the enlargement step, and the type and amount of the acid group-containing copolymer latex. Except having changed as described above, graft copolymers (E-2) to (E-10) were obtained in the same manner as in Production Example 4.

<Production Example 6: Production of graft copolymer (E-11)>
In a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer, 6.0 parts of polyorganosiloxane latex (A) in terms of solid content, 0.1 part of sodium dodecylbenzenesulfonate, Then, 190 parts of ion-exchanged water was charged and mixed. Next, as a monomer constituting the alkyl (meth) acrylate polymer (B), 44.0 parts of n-butyl acrylate, 0.4 part of allyl methacrylate, 0.09 part of 1,3-butylene glycol dimethacrylate, A mixture consisting of 0.12 parts of t-butyl hydroperoxide was added. The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the internal temperature was raised to 60 ° C. When the internal temperature reached 60 ° C., from 0.000075 part of ferrous sulfate heptahydrate, 0.00023 part of ethylenediaminetetraacetic acid disodium salt, 0.2 part of sodium formaldehyde sulfoxylate, 10 parts of ion-exchanged water The resulting aqueous solution was added to initiate radical polymerization. After the polymerization exotherm is confirmed, the jacket temperature is set to 75 ° C., the polymerization is continued until the polymerization exotherm is not confirmed, and this state is maintained for another hour, and a composite rubber in which polyorganosiloxane and polybutyl acrylate rubber are combined. A latex was obtained (radical polymerization step). The obtained composite rubber had a volume average particle diameter of 90 nm.
An aqueous solution consisting of 0.2 part of sodium formaldehyde sulfoxylate and 10 parts of ion-exchanged water was added to the latex of the composite rubber-like polymer (C). Subsequently, a mixed liquid composed of 2.5 parts of acrylonitrile, 7.5 parts of styrene, and 0.1 part of t-butyl hydroperoxide was dropped over 20 minutes to be polymerized. After completion of the dropwise addition, the temperature was maintained at 75 ° C. for 30 minutes, and then a mixture composed of 10 parts of acrylonitrile, 30 parts of styrene and 0.2 part of t-butyl hydroperoxide was dropped over 80 minutes for polymerization. After completion of dropping, after maintaining the temperature at 75 ° C. for 30 minutes, 0.05 part of cumene hydroperoxide was added, and after maintaining the temperature at 75 ° C. for 30 minutes, the mixture was cooled, and a composite rubber polymer ( A latex of a silicone / acrylic composite rubber graft copolymer (E-11) obtained by graft polymerization of acrylonitrile and styrene on C) was obtained.
Subsequently, 150 parts of a 1% calcium acetate aqueous solution was heated to 60 ° C., and 100 parts of the latex of the graft copolymer (E-11) was gradually dropped into the solution to be solidified. Then, the precipitate was separated, dehydrated, washed and dried to obtain a graft copolymer (E-11).

The volume average particle diameter of the composite rubber-like polymer (C) used for the production of the graft copolymers (E-1) to (E-11) in each example, the particle diameter occupied in all the particles is 300 to 500 nm. Table 1 shows the ratio of certain particles and the gel content.
“Component (d)” in Table 1 is a vinyl monomer graft polymerized to the composite rubber-like polymer (C), “AN” is acrylonitrile, and “ST” is styrene.

"Polymethyl methacrylate (F)"
<Polymethyl methacrylate (F-1)>
Rayon "SVK" Co., Ltd.: using (MVR 20.0cm ^3/10 min) as polymethyl methacrylate (F-1).
<Polymethyl methacrylate (F-2)>
Rayon "VH5" Co., Ltd.: using (MVR 5.5cm ^3/10 min) as polymethyl methacrylate (F-2).
<Polymethyl methacrylate (F-3)>
Rayon "VHM" Co., Ltd.: using (MVR 3.1cm ^3/10 min) as polymethyl methacrylate (F-3).

"Examples 1 to 17 and Comparative Examples 1 to 8"
The types and amounts (parts) of the graft copolymer (E) and polymethyl methacrylate (F) shown in Table 2, 0.4 part of EBS-WAX (manufactured by Kao), ADK STAB LA-36 (manufactured by ADEKA Corporation) ) 0.4 part, Adeka Stub LA-63PK (manufactured by ADEKA Corporation) 0.4 part, and carbon black 0.8 part were mixed using a Henschel mixer. The obtained mixture was melt-kneaded at 250 ° C. using a screw type extruder (“TEX-28 type twin screw extruder” manufactured by Nippon Steel Co., Ltd.) and then pelletized by a pelletizer. A thermoplastic resin composition was obtained.
The fluidity of the obtained thermoplastic resin composition, the rigidity, impact resistance, and weather resistance of the molded product were evaluated as described above. These results are shown in Tables 2 and 3.

The “volume average particle diameter” in Tables 2 and 3 is the volume average particle diameter (nm) of the composite rubber-like polymer (C) used for the production of the graft copolymer (E).
“Particle ratio of 300 to 500 nm” is the ratio (volume) of particles having a particle diameter of 300 to 500 nm in all the particles of the composite rubber-like polymer (C) used for the production of the graft copolymer (E). %).
“Gel content” is the gel content (% by mass) of the composite rubber-like polymer (C) used for the production of the graft copolymer (E).

As shown in Tables 2 and 3, the thermoplastic resin compositions of Examples 1 to 17 are excellent in fluidity, and the molded articles obtained from the respective thermoplastic resin compositions have rigidity, impact resistance, and weather resistance. It was excellent.
On the other hand, the thermoplastic resin compositions of Comparative Examples 1 to 8 were inferior in any one or more of fluidity, molded product rigidity, impact resistance, and weather resistance.

  ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin composition which can obtain the molded article which is excellent in fluidity | liquidity and excellent in rigidity, impact resistance, and a weather resistance can be provided. In particular, the balance between the impact resistance and weather resistance of the molded product is higher than that of conventionally known thermoplastic resin compositions, and it is used for vehicle parts such as pillars, door mirrors, radiator grills, and spoilers, OA equipment, home appliance parts, The utility value for building materials such as wall materials and window frames, and miscellaneous goods such as toys and stationery is extremely high.

Claims (6)

A graft copolymer (E) in which one or more vinyl monomers are graft-polymerized to a composite rubber-like polymer in which a polyorganosiloxane and an alkyl (meth) acrylate polymer are combined, and polymethyl methacrylate ( F) and
The volume average particle diameter of the composite rubber-like polymer is 100 to 200 nm, and the ratio of particles having a particle diameter of 300 to 500 nm in all the particles of the composite rubber-like polymer is 5 to 25% by volume. , A thermoplastic resin composition.   The thermoplastic resin composition according to claim 1, wherein the composite rubber-like polymer has a gel content of 70 to 99% by mass.   3. The thermoplastic resin composition according to claim 1, wherein a ratio of particles having a particle diameter of 300 to 500 nm in all particles of the composite rubber-like polymer is 5 to 15% by volume. The 230 ° C. of polymethyl methacrylate (F), the thermoplastic resin composition according to any one of claims 1 to 3 melt volume flow rate under a load of 3.7kg is 5~25cm ^3/10 min . The polymethyl methacrylate (F) is, 230 ° C., and polymethyl methacrylate melt volume flow rate under a load of 3.7kg is 15~25cm ^3/10 min, 230 ° C., a melt volume under a load of 3.7kg flow rate thermoplastic resin composition according to claim 1 comprising a polymethyl methacrylate is 5 to 10 cm ^3/10 min.   The molded article which consists of a thermoplastic resin composition as described in any one of Claims 1-5.