JP7276484B2 - Thermoplastic resin composition and molded article thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a water repellency-imparting agent capable of imparting water repellency to a resin molded article to maintain its antifouling property over a long period of time, a thermoplastic resin composition containing this water repellency-imparting agent, and a molded article thereof. .
The present invention also relates to a thermoplastic resin molded article having excellent water repellency and durability.

BACKGROUND ART In order to prevent dirt from adhering to a resin molded product due to limescale, hot water scale, and muddy water, and to facilitate removal of the adhered dirt, the surface of the resin molded product is imparted with water repellency.

Conventionally, as a method of imparting water repellency to a resin molded product, there is a method of applying a water repellent coating agent to the surface of the resin molded product to form a water repellent coating layer, or attaching a water repellent film. .
However, such a method increases the number of steps after molding the resin molded product, increases the production cost, and makes it impossible to obtain the desired antifouling effect due to abrasion of the water-repellent coating layer and peeling of the water-repellent film over time.

In view of such problems, it has been proposed to add a water repellent component such as silicone oil to the resin composition in order to impart water repellency to the resin composition itself for molding the resin molded product (Patent Document 1). ).

JP 2010-77270 A

In the technique of Patent Document 1, the silicone oil or the like blended in the resin composition bleeds onto the surface of the resin molded product, and the water repellent effect is lost due to degreasing treatment or the like.
Moreover, it cannot be said that sufficient water repellency is obtained with the technique of Patent Document 1, and further improvement in water repellency is desired. For example, in Patent Document 1, the effect of imparting water repellency is evaluated by the sliding angle of water. However, in order to obtain a sufficient antifouling effect, a higher water repellency with a sliding angle of 10° or less is desired.

An object of the present invention is to provide a water repellency-imparting agent having a remarkably high water-repellency-imparting effect and an excellent water repellency-sustaining effect, a thermoplastic resin composition containing this water repellency-imparting agent, and a molded article thereof. and

Another object of the present invention is to provide a thermoplastic resin molded article which is remarkably excellent in water repellency and excellent in durability of water repellency.

The present inventor also found that the above object can be achieved by a graft copolymer (B) using a composite rubbery polymer (A) of a silicone-based rubbery polymer (S) and a (meth)acrylic acid alkyl ester. Found it.

The present inventor also found that a molded article having a surface Si content within a predetermined range as measured by a specific fluorescent X-ray analysis can achieve the above object.

The gist of the present invention is as follows.

[1] A graft copolymer obtained by graft-polymerizing a vinyl compound (b) to a composite rubbery polymer (A) obtained by combining a (meth)acrylic acid ester with a silicone-based rubbery polymer (S). (B) a water repellent agent.

[2] The proportion of the silicone rubbery polymer (S) in the total 100% by mass of the silicone rubbery polymer (S) and (meth)acrylic acid ester used in the production of the composite rubbery polymer (A) is The water repellency imparting agent according to [1], which is 10 to 65% by mass.

[3] The vinyl compound (b) contains aromatic vinyl and vinyl cyanide, and the vinyl compound (b) is 70 to 10% by mass with respect to the composite rubbery polymer (A) of 30 to 90% by mass. (where the total of the composite rubbery polymer (A) and the vinyl compound (b) is 100% by mass). The water repellency imparting agent according to [1] or [2].

[4] A thermoplastic resin composition containing the water repellency imparting agent according to any one of [1] to [3].

[5] The content of the composite rubbery polymer (A) is 10 to 50% by mass relative to 100% by mass of the resin component in the composition, and the content of the silicone-based rubbery polymer (S) is 2 to 5% by mass. The thermoplastic resin composition according to [4], which is 30% by mass.

[6] The thermoplastic resin composition according to [4] or [5], further comprising a lubricant (E).

[7] The thermoplastic resin composition according to [6], wherein the content of the lubricant (E) is 0.2 to 10 parts by mass with respect to 100 parts by mass of the resin component in the composition.

[8] The thermoplastic resin composition according to [6] or [7], wherein the lubricant (E) is an acid amide lubricant.

[9] The thermoplastic resin composition according to any one of [4] to [8], which has a surface Si content of 50 to 400 cps as measured by the following fluorescent X-ray analysis.
<Fluorescent X-ray analysis>
The surface of the test piece obtained by molding the thermoplastic resin composition was subjected to measurement time of 100 seconds, sample chamber atmosphere He purge, collimator 0.5 × 0.5 mm, excitation voltage 50 kv, tube current 100 μA. Fluorescent X-ray analysis is performed under the conditions, and the Si detection intensity of 1.60 to 1.88 keV is taken as the surface Si amount.

[10] A molded article obtained by molding the thermoplastic resin composition according to any one of [4] to [9].

[11] A molded article obtained by molding a thermoplastic resin composition, the molded article having a surface Si content of 50 to 400 cps as measured by the following fluorescent X-ray analysis.
<Fluorescent X-ray analysis>
Fluorescent X-ray analysis was performed on the surface of the molded product under the following conditions: measurement time 100 seconds, sample chamber atmosphere He purge, collimator 0.5×0.5 mm, excitation voltage 50 kv, tube current 100 μA. The Si detection intensity of ~1.88 keV is defined as the surface Si amount.

[12] The molded article according to [10] or [11], whose surface has a water contact angle of 90° or more and a water sliding angle of 20° or less.

[13] The thermoplastic resin composition comprises a composite rubbery polymer (A) obtained by combining a silicone rubbery polymer (S) with a (meth)acrylic acid ester, and a vinyl compound (b) grafted onto the composite rubbery polymer (A). The molded article according to [11] or [12], which contains a water repellency-imparting agent comprising a graft copolymer (B) obtained by polymerization.

[14] The molded article according to any one of [10] to [13], which is a vehicle member, building material, exterior member, household appliance housing, office equipment or air conditioner housing.

According to the water repellency-imparting agent of the present invention and the thermoplastic resin composition containing this water repellency-imparting agent, the water repellency is excellent and its durability is excellent, and the adhesion of dirt such as water scale and muddy water is prevented for a long period of time. It is possible to provide a thermoplastic resin molded article excellent in antifouling properties, from which adhering stains can be easily removed.
Moreover, the water repellency-imparting agent of the present invention can impart good water repellency to the thermoplastic resin molded article obtained without significantly impairing the molding appearance.

The graft copolymer (B) constituting the water repellency-imparting agent of the present invention is a composite rubbery polymer (A ), it also has the effect of being excellent in blocking property, and is excellent in handleability.

According to the present invention, a thermoplastic having excellent antifouling properties, which is excellent in water repellency and durability, prevents the adhesion of dirt such as water scale and muddy water for a long period of time, and can easily remove the adhered dirt. A resin molded product can be provided.

Embodiments of the present invention will be described in detail below.

As used herein, the term "unit" refers to a structural portion derived from a monomer compound (monomer) before polymerization. For example, a "(meth)acrylic acid ester unit" refers to a "structural portion derived from a (meth)acrylic acid ester". The content ratio of each monomer unit in the polymer corresponds to the content ratio of the monomer in the monomer mixture used to produce the polymer.
"(Meth)acrylic acid" means one or both of "acrylic acid" and "methacrylic acid". The same applies to "(meth)acrylate".
A "molded article" means an article obtained by molding a thermoplastic resin composition.

The volume average particle size of the silicone-based rubbery polymer (S), the composite rubbery polymer (A), and the graft copolymer (B) according to the present invention is measured by the method described in Examples below. is the value

[Water repellency imparting agent]
The water repellency-imparting agent of the present invention is obtained by graft polymerizing a vinyl compound (b) to a composite rubbery polymer (A) obtained by combining a (meth)acrylic acid ester with a silicone rubbery polymer (S). It consists of a graft copolymer (B) consisting of

[Composite rubbery polymer (A)]
First, the composite rubbery polymer (A) which is the rubber component of the graft copolymer (B) which is the water repellency-imparting agent of the present invention (hereinafter referred to as "composite rubbery polymer (A) of the present invention") ) will be explained.

The composite rubbery polymer (A) of the present invention is produced using a silicone rubbery polymer (S), a (meth)acrylic acid ester, a cross-linking agent and, if necessary, other vinyl compounds.

<Silicone rubbery polymer (S)>
The silicone-based rubbery polymer (S) constituting the composite rubbery polymer (A) of the present invention is not particularly limited, but polyorganosiloxane having a vinyl polymerizable functional group is preferred. In particular, siloxane containing a vinyl polymerizable functional group (vinyl polymerizable functional group-containing siloxane) unit 0.3 to 3 mol% and dimethylsiloxane unit 97 to 99.7 mol%, 3 or more siloxane Polyorganosiloxanes containing 1 mol % or less of silicon atoms with bonds based on all silicon atoms in the polydimethylsiloxane are preferred.

Examples of the dimethylsiloxane constituting the polyorganosiloxane include dimethylsiloxane-based cyclic bodies having three or more membered rings. Among them, 3- to 7-membered rings are preferred. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like. These can be used alone or in combination of two or more.

The vinyl-polymerizable functional group-containing siloxane is not limited as long as it contains a vinyl-polymerizable functional group and can bond with dimethylsiloxane via a siloxane bond. However, considering the reactivity with dimethylsiloxane, Various alkoxysilane compounds containing vinyl polymerizable functional groups are preferred. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, ∂-methacryloyloxybutyldiethoxymethylsilane and other methacryloyloxysiloxanes; tetramethyltetravinylcyclotetrasiloxane and other vinylsiloxanes; p-vinylphenyldimethoxymethylsilane, γ-mercaptopropyl and mercaptosiloxanes such as dimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane. These vinyl polymerizable functional group-containing siloxanes can be used singly or in combination of two or more.

The silicone-based rubbery polymer (S) may contain siloxane-based cross-linking agent units as a constituent component, if necessary.

Examples of siloxane-based cross-linking agents include tri- or tetra-functional silane-based cross-linking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane. These can be used singly or in combination of two or more.

The method for producing the silicone-based rubbery polymer (S) is not limited. For example, it can be produced by the following method.

First, a siloxane-based cross-linking agent is added, if necessary, to a siloxane mixture composed of dimethylsiloxane and vinyl-polymerizable functional group-containing siloxane, followed by emulsification with an emulsifier and water to obtain a siloxane mixture aqueous dispersion.
Next, the siloxane mixture aqueous dispersion is microparticulated by using a homomixer that microparticulates by shearing force generated by high-speed rotation, a homogenizer that micronizes by the ejection force of a high-pressure generator, or the like. Here, it is preferable to use a high-pressure emulsifying device such as a homogenizer, because the distribution of the particle size of the silicone-based rubbery polymer (S) is narrowed.
Next, the micronized siloxane mixture aqueous dispersion is added to an acid aqueous solution containing an acid catalyst and polymerized at a high temperature.
Then, the reaction solution is cooled and further neutralized with an alkaline substance such as caustic soda, caustic potash, sodium carbonate or the like to terminate the polymerization, thereby obtaining a silicone rubbery polymer (S) dispersed in an aqueous dispersion.

An anionic emulsifier is preferable as the emulsifier used in the production of the silicone rubbery polymer (S). Examples of anionic emulsifiers include sodium alkylbenzene sulfonate and sodium polyoxyethylene nonylphenyl ether sulfate. Among these, sulfonic acid-based emulsifiers such as sodium alkylbenzenesulfonate and sodium laurylsulfonate are preferred. One emulsifier may be used alone, or two or more emulsifiers may be used in combination. The emulsifier is used in the range of about 0.05 to 5 parts by mass with respect to 100 parts by mass (as solid content) of the siloxane mixture.

Acid catalysts used for polymerization include sulfonic acids such as aliphatic sulfonic acids, aliphatic-substituted benzenesulfonic acids and aliphatic-substituted naphthalenesulfonic acids, and mineral acids such as sulfuric acid, hydrochloric acid and nitric acid. Acid catalysts can be used singly or in combination of two or more. Among these, aliphatic-substituted benzenesulfonic acid is preferred, and n-dodecylbenzenesulfonic acid is particularly preferred, because of its excellent stabilizing effect on the aqueous dispersion of the silicone-based rubbery polymer (S). When n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used as an acid catalyst in combination, the emulsifier used in the aqueous dispersion of the silicone rubbery polymer (S) does not affect the color developability of the thermoplastic resin composition. You can limit the impact as much as possible.

The silicone-based rubbery polymer (S) is produced as a latex containing the silicone-based rubbery polymer (S) by emulsion polymerization as described above.
Usually, the silicone rubbery polymer (S) concentration (solid content concentration) of this silicone rubbery polymer (S) latex is about 10 to 40% by mass.

The volume average particle size of the silicone rubbery polymer (S) is preferably 1 to 100 nm, more preferably 10 to 90 nm, particularly preferably 30 to 70 nm. A silicone-based rubbery polymer with a volume average particle size of less than 1 nm is difficult to produce, and a volume average particle size of more than 100 nm results in poor molded appearance of the thermoplastic resin molded article obtained using it.

The particle size distribution of the silicone-based rubbery polymer (S) is not particularly limited, but it preferably has a single particle size so that it can be uniformly dispersed in the composite rubbery polymer (A).

As a method for controlling the volume average particle size of the silicone-based rubbery polymer (S), for example, the method described in JP-A-5-279434 can be employed.

Only one type of the silicone-based rubbery polymer (S) may be used, or two or more types may be used in combination.

<(Meth) acrylic acid ester>
Examples of (meth)acrylic acid esters constituting the composite rubbery polymer (A) of the present invention include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. , alkyl acrylates having 1 to 22 carbon atoms in the alkyl group such as benzyl acrylate; alkyl methacrylates having 1 to 22 carbon atoms in the alkyl group such as hexyl methacrylate, 2-ethylhexyl methacrylate, and n-dodecyl methacrylate esters. The water repellency, impact resistance and gloss of the thermoplastic resin molded article obtained by blending the water repellency imparting agent comprising the graft copolymer (B) using the composite rubbery polymer (A) obtained are improved. , (meth)acrylate, n-butyl acrylate is preferred. (Meth)acrylic acid esters may be used alone or in combination of two or more.

<Ratio of silicone-based rubbery polymer (S)/(meth)acrylic acid ester>
The proportion of the silicone rubbery polymer (S) in the total 100% by mass of the silicone rubbery polymer (S) and (meth)acrylic acid ester used in the production of the composite rubbery polymer (A) of the present invention is 10. to 65% by mass, and the ratio of (meth)acrylic acid ester is preferably 90 to 35% by mass. Acrylic acid ester: more preferably 88 to 45% by mass, silicone rubbery polymer (S): 15 to 55% by mass, and (meth)acrylic acid ester: 85 to 45% by mass. preferable. If the amount of the silicone-based rubbery polymer (S) is less than the above range, the water-repellent effect of the silicone-based rubbery polymer (S) cannot be sufficiently obtained. Even if the amount of the silicone-based rubbery polymer (S) exceeds the above range, the details of the reason are not clear, but the water repellency imparted by the water repellency imparting agent using the composite rubbery polymer (A) of the present invention The imparted effect tends to rather decrease.

<Crosslinking agent>
In the production of the composite rubbery polymer (A) of the present invention, preferably (meth)acrylic acid ester is used to introduce a crosslinked structure into the (meth)acrylic acid ester unit portion obtained from the (meth)acrylic acid ester described above. A cross-linking agent is used with the acid ester. In the case of a crosslinked rubbery polymer (A) obtained using a crosslinking agent, a graft for grafting the crosslinked portion to the vinyl compound (b) described later used in the production of the graft copolymer (B). It also functions as a crossover point.

Examples of cross-linking agents include allyl (meth)acrylate, butylene di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1, 4-butylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, polyester di(meth)acrylate, polyurethane di(meth)acrylate, polybutadiene Di(meth)acrylate, divinylbenzene, trivinylbenzene, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, diallyldimethylammonium chloride, polyglycerin poly(meth)acrylate, and the like. be done. These may be used individually by 1 type, and may use 2 or more types together.

The amount of the cross-linking agent to be used is not particularly limited, but the ratio of the cross-linking agent is 0.1 to 5.0 parts per 100 parts by mass of the silicone rubber polymer (S) and the (meth)acrylic acid ester. It is preferably in an amount of 0 parts by weight, particularly 0.2 to 4.0 parts by weight. If the ratio of the cross-linking agent is within the above range, a thermoplastic resin composition containing a water repellency imparting agent comprising a graft copolymer (B) using the obtained composite rubbery polymer (A) is used. The molded product obtained by this method has excellent impact resistance.

<Other vinyl compounds>
In the production of the composite rubbery polymer (A) of the present invention, vinyl compounds other than the (meth)acrylic acid ester may be used as necessary. Other vinyl compounds are not particularly limited as long as they can be copolymerized with (meth)acrylic acid esters and cross-linking agents. For example, aromatic vinyl such as styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, pt-butylstyrene, ethylstyrene; vinyl cyanide such as acrylonitrile, methacrylonitrile; -Cyclohexylmaleimide, N-phenylmaleimide and other maleimides, and maleic anhydride. These may be used individually by 1 type, and may be used in mixture of 2 or more types.

When other vinyl compounds are used in the production of the composite rubbery polymer (A) of the present invention, the amount of the other vinyl compounds used is 100 in total for the silicone-based rubbery polymer (S) and the (meth)acrylic acid ester. It is preferable to use so that the ratio of other vinyl compounds to parts by mass is 30 parts by mass or less, particularly 20 parts by mass or less, and particularly 10 parts by mass or less.

<Method for producing composite rubbery polymer (A)>
The composite rubbery polymer (A) of the present invention can be produced by polymerizing a (meth)acrylic acid ester in the presence of the silicone rubbery polymer (S).
In the production of the composite rubbery polymer (A) of the present invention, rubber components and various additives other than the silicone-based rubbery polymer (S) mentioned later can be added to the polymerization system. .

The polymerization method of the (meth)acrylic acid ester is not particularly limited, and examples of the polymerization method include known polymerization methods (emulsion polymerization method, suspension polymerization method, solution polymerization method, etc.).

As a method for producing the composite rubbery polymer (A) by an emulsion polymerization method, for example, a silicone-based rubbery polymer (S), a (meth)acrylic acid ester, a cross-linking agent, and if necessary are used in a reactor. Other vinyl compounds, an emulsifier, an initiator and a chain transfer agent are charged, heated and polymerized, and the composite rubbery polymer (A) is recovered from the latex containing the composite rubbery polymer (A) by a precipitation method. method.

(emulsifier)
Examples of emulsifiers used in producing the composite rubbery polymer (A) of the present invention include carboxylic acids such as oleic acid, palmitic acid, stearic acid, alkali metal salts of rosin acid, and alkali metal salts of alkenylsuccinic acid. Known emulsifiers such as acid-based emulsifiers, anionic emulsifiers selected from among alkyl sulfates, sodium alkylbenzenesulfonate, sodium alkylsulfosuccinate, sodium polyoxyethylene nonylphenyl ether sulfate, etc. alone or in combination of two or more. can be used in combination.
Part of the emulsifier can be added as appropriate during the polymerization reaction in order to stabilize the latex.

An excessive amount of emulsifier makes it easier for gas to adhere to the mold during production of molded articles, possibly reducing productivity. Therefore, the amount of emulsifier to be added is 0.01 parts per 100 parts by mass in total of the silicone rubber polymer (S), (meth)acrylic acid ester, cross-linking agent and other vinyl compounds used as necessary. It is preferably up to 3.0 parts by mass, more preferably 0.02 to 2.0 parts by mass, still more preferably 0.03 to 1.0 parts by mass. When the amount of the emulsifier added is within the above range, the composite rubbery polymer (A) can be stably produced.

(initiator)
Examples of initiators include azo polymerization initiators, photopolymerization initiators, inorganic peroxides, organic peroxides, and redox initiators obtained by combining organic peroxides, transition metals, and reducing agents. Among these, azo polymerization initiators, inorganic peroxides, organic peroxides, and redox initiators, which can initiate polymerization by heating, are preferred. These may be used alone or in combination of two or more.

Examples of azo polymerization initiators include 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′- Azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo]formamide, 4,4′-azobis(4-cyanovaleric acid), dimethyl 2,2′-azobis(2-methylpropionate), dimethyl 1,1′-azobis(1-cyclohexanecarboxylate) ), 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2′-azobis(N-butyl-2-methylpropionamide), 2,2′-azobis ( N-cyclohexyl-2-methylpropionamide), 2,2′-azobis[2-(2-imidazolin-2-yl)propane], 2,2′-azobis(2,4,4-trimethylpentane), etc. mentioned.

Examples of inorganic peroxides include potassium persulfate, sodium persulfate, ammonium persulfate, and hydrogen peroxide.

Examples of organic peroxides include peroxyester compounds. Specific examples include α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl- 1-methyl ethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1,3,3- tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy 2-hexylhexanoate, t-butylperoxy 2-hexylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis(m-toluoylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxy benzoate, bis(t-butylperoxy)isophthalate, 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 2,2-bis(t- Butylperoxy)butane, n-butyl 4,4-bis(t-butylperoxy)valerate, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, α,α'-bis(t- Butyl peroxide) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide Peroxide, dilauroyl peroxide, diisononanoyl peroxide, t-butyl hydroperoxide, benzoyl peroxide, lauroyl peroxide, dimethylbis(t-butylperoxy)-3-hexyne, bis(t-butylperoxyisopropyl)benzene, bis(t -butylperoxy)trimethylcyclohexane, butyl-bis(t-butylperoxy)valerate, t-butyl 2-ethylhexaneperoxyate, dibenzoyl peroxide, para-menthane hydroperoxide and t-butylperoxybenzoate.

As the redox initiator, a combination of an organic peroxide, ferrous sulfate, a chelating agent and a reducing agent is preferred. For example, one consisting of cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate, and dextrose, or a combination of t-butyl hydroperoxide, sodium formaldehyde sulfoxylate (Rongalite), ferrous sulfate, and disodium ethylenediaminetetraacetate. etc.

The amount of the initiator to be added is 0.001 to 5 parts per 100 parts by mass in total of the silicone rubber polymer (S), (meth)acrylic acid ester, cross-linking agent and other vinyl compounds used as necessary. Parts by weight are preferred.

Chain transfer agents include mercaptans, α-methylstyrene dimers, terpenes and the like.

The chain transfer agent can be used in an amount of 1.2 parts by mass or less with respect to a total of 100 parts by mass of the silicone rubber polymer (S), (meth)acrylic acid ester, and other vinyl compounds that are used as necessary. preferable.

As a method for producing the composite rubbery polymer (A) by a suspension polymerization method, for example, a reactor is charged with a silicone-based rubbery polymer (S), a (meth)acrylic acid ester, a cross-linking agent, and, if necessary, Other vinyl compounds to be used, a suspending agent, a suspending aid, an initiator and a chain transfer agent are charged, heated and polymerized, and the slurry is dehydrated and dried to recover the composite rubbery polymer (A). method.

Suspending agents include, for example, anionic water-soluble polymers, nonionic water-soluble polymers, and sparingly water-soluble inorganic salts.

Examples of anionic water-soluble polymers include polyacrylic acid, sodium polyacrylate, potassium polyacrylate, polymethacrylic acid, sodium polymethacrylate, potassium polymethacrylate, sodium methacrylate-alkyl methacrylate copolymer. etc. 1 type, or 2 or more types are mentioned. Among them, sodium polyacrylate and sodium polymethacrylate are preferred.

Examples of nonionic water-soluble polymers include polyvinyl alcohol, methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, hydroxypropylmethylcellulose, polyalkylene oxides such as polyethylene oxide, and polyoxyethylene-polyoxypropylene block copolymers. , polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol fatty acid ester, polyoxyethylene laurylamine, and the like. Polyvinyl alcohol and polyoxyethylene-polyoxypropylene copolymers are preferred, and polyoxyethylene-polyoxypropylene block copolymers are more preferred.

Examples of sparingly water-soluble inorganic salts include one or more of barium sulfate, tribasic calcium phosphate, magnesium carbonate, and the like. Tribasic calcium phosphate is preferred.

The suspending agent can be used in an amount of 0.1 to 3 parts by mass with respect to 100 parts by mass of the silicone rubber polymer (S), (meth)acrylic acid ester, and optionally other vinyl compounds. preferable.

Suspension aids include carboxylates (e.g., sodium sarcosinate, fatty acid potassium, fatty acid sodium, potassium alkenyl succinate, dipotassium alkenyl succinate, rosin acid soap, etc.), alkyl sulfate salts, sodium alkylbenzene sulfonate, alkyl One or more dibasic acids having an alkyl group and/or an alkenyl group such as sodium sulfosuccinate, sodium polyoxyethylene nonylphenyl ether sulfate, or salts thereof may be used.

As the suspension aid, it is preferable to use potassium alkenyl succinate from the viewpoint of stability during production.

The suspension aid should be used in an amount of 0.0001 to 1 part by mass per 100 parts by mass of the silicone rubbery polymer (S), (meth)acrylic acid ester, and other vinyl compounds that are optionally used. is preferred.

Initiators include organic peroxides.

It is preferable to use 0.001 to 5 parts by mass of the initiator with respect to 100 parts by mass of the silicone rubber polymer (S), (meth)acrylic acid ester, and optionally other vinyl compounds. .

Chain transfer agents include mercaptans, α-methylstyrene dimers, terpenes and the like.

The chain transfer agent can be used in an amount of 1.2 parts by mass or less with respect to a total of 100 parts by mass of the silicone rubber polymer (S), (meth)acrylic acid ester, and other vinyl compounds that are used as necessary. preferable.

<Volume average particle size of composite rubbery polymer (A)>
The volume average particle size of the composite rubbery polymer (A) of the present invention is preferably 5 to 200 nm, more preferably 10 to 170 nm, particularly preferably 30 to 150 nm.

If the volume average particle size of the composite rubbery polymer (A) is at least the above lower limit, stable production is possible. If the volume average particle size of the composite rubbery polymer (A) is equal to or less than the above upper limit value, the resulting thermoplastic resin molded article will have good appearance characteristics.

[Graft copolymer (B)]
The graft copolymer (B), which is the water repellency-imparting agent of the present invention, comprises the composite rubbery polymer (A) of the present invention, a vinyl compound (b) such as aromatic vinyl, (meth)acrylic acid ester, and vinyl cyanide and at least one vinyl compound (b) is graft-polymerized to form a graft layer.

The vinyl compound (b) may contain vinyl compounds other than (meth)acrylic acid ester, aromatic vinyl, and vinyl cyanide.

The graft ratio of the graft layer of the graft copolymer (B) was calculated by the following method, and the graft ratio was determined by this method also in the examples described later.

<Calculation of graft ratio>
80 mL of acetone is added to 2.5 g of the graft copolymer (B) and the mixture is refluxed in a hot water bath at 65° C. for 3 hours to extract acetone-soluble matter. The remaining acetone-insoluble matter is separated by centrifugation, dried and weighed. From the mass of the acetone-insoluble matter in the obtained graft copolymer (B) and the mass of the composite rubbery polymer (A) used in the production of the graft copolymer (B), using the following formula: , to calculate the graft ratio.

The graft ratio of the graft copolymer (B) of the present invention is preferably 10 to 90%, more preferably 30 to 85%. If the graft ratio of the graft copolymer (B) is within the above range, the graft copolymer (B) can be used to obtain a thermoplastic resin molded product with good impact resistance and molding appearance.

As the (meth)acrylic acid ester to be graft polymerized to the composite rubbery polymer (A) of the present invention, one of the (meth)acrylic acid esters exemplified as the (meth)acrylic acid ester used for producing the composite rubbery polymer (A) of the present invention is used. A species or two or more species can be used.
As the aromatic vinyl and vinyl cyanide, one of aromatic vinyl and vinyl cyanide respectively exemplified as other vinyl compounds used as necessary in the production of the composite rubbery polymer (A) of the present invention, or Two or more kinds can be used.

The vinyl compound (b) used in the production of the graft copolymer (B) of the present invention may contain vinyl compounds other than the aforementioned (meth)acrylic acid ester, aromatic vinyl and vinyl cyanide. . Other vinyl compounds include (meth)acrylic acid esters, aromatic vinyls, One or two or more vinyl compounds other than vinyl cyanide may be used.

The graft copolymer (B ) is preferable because it has excellent thermal stability. In this case, the ratio of the aromatic vinyl such as styrene and the vinyl cyanide such as acrylonitrile is preferably 80 to 60% by mass of the aromatic vinyl and 20 to 40% by mass of the vinyl cyanide (however, the aromatic vinyl The total amount of vinyl and vinyl cyanide is 100% by mass).

The graft layer of the graft copolymer (B) is obtained by emulsion graft polymerization of 70 to 10% by mass of the vinyl compound (b) with respect to 30 to 90% by mass of the composite rubbery polymer (A). and the thermoplastic resin molded article obtained using this graft copolymer (B) have an excellent appearance (however, the total amount of the composite rubbery polymer (A) and the vinyl compound (b) is 100% by mass. ). More preferably, the ratio is 40 to 70 mass % of the composite rubbery polymer (A) and 60 to 30 mass % of the vinyl compound (b).

As a method of graft polymerization of the vinyl compound (b) to the composite rubbery polymer (A), the vinyl compound (b) is added to the latex of the composite rubbery polymer (A) obtained by the above emulsion polymerization or the like. , single-stage or multi-stage polymerization. When the polymerization is carried out in multiple stages, it is preferable to add the vinyl compound (b) in the presence of the rubber latex of the composite rubbery polymer (A) in a divided manner or continuously. Good polymerization stability can be obtained by such a polymerization method, and a latex having a desired particle size and particle size distribution can be stably obtained.
Examples of the polymerization initiator used for graft polymerization include the same radical polymerization initiators as those used for producing the composite rubbery polymer (A) of the present invention.

When polymerizing the composite rubbery polymer (A) with the vinyl compound (b), the latex of the composite rubbery polymer (A) is stabilized, and the average particle diameter of the resulting graft copolymer (B) is adjusted to Emulsifiers can be added for control. The emulsifier used here is not particularly limited, but includes the same emulsifiers as those used in the production of the composite rubbery polymer (A) of the present invention. As emulsifiers, anionic emulsifiers and nonionic emulsifiers are preferred.

The amount of the emulsifier to be used when the vinyl compound (b) is graft-polymerized to the composite rubbery polymer (A) is not particularly limited, but is from 0.01 to 0.01 per 100 parts by mass of the resulting graft copolymer (B). 10 parts by mass is preferable, and 0.02 to 5 parts by mass is more preferable.

Although the method for recovering the graft copolymer (B) from the latex of the graft copolymer (B) obtained by emulsion polymerization is not particularly limited, the following methods may be mentioned.

The latex of the graft copolymer (B) is poured into hot water in which a coagulant is dissolved to solidify the graft copolymer (B).
Next, the solidified graft copolymer (B) is redispersed in water or hot water to form a slurry, and the emulsifier residue remaining in the graft copolymer (B) is eluted into water and washed.
Next, the slurry is dehydrated with a dehydrator or the like, and the resulting solid is dried with a flash dryer or the like to recover the graft copolymer (B) as powder or particles.

The coagulant includes inorganic acids (sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, etc.), metal salts (calcium chloride, calcium acetate, aluminum sulfate, etc.), and the like. A coagulant is appropriately selected according to the type of emulsifier. For example, when only a carboxylate (fatty acid salt, rosin acid soap, etc.) is used as an emulsifier, any coagulant may be used. When using an emulsifier such as sodium alkylbenzenesulfonate which exhibits stable emulsifying power even in an acidic range, an inorganic acid is insufficient and a metal salt must be used.

The volume average particle size of the graft copolymer (B) of the present invention is preferably 50-250 nm, more preferably 60-200 nm.

If the volume average particle size of the graft copolymer (B) is at least the above lower limit, stable production is possible. If the volume average particle size of the graft copolymer (B) is equal to or less than the above upper limit value, the resulting thermoplastic resin molded article will have good appearance characteristics.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present invention contains the water repellency-imparting agent of the present invention comprising the graft copolymer (B) described above. The thermoplastic resin composition of the present invention usually comprises a mixture of the water repellency-imparting agent of the present invention and another thermoplastic resin.

The content of the water repellency-imparting agent of the present invention in the thermoplastic resin composition of the present invention is such that the desired effect of imparting water repellency can be obtained by blending the water repellency-imparting agent of the present invention. Although there is no particular limitation, it is preferable that the amount satisfies the following composite rubbery polymer (A) content, silicone rubbery polymer (S) content, and surface Si content.

<Content of composite rubbery polymer (A)>
The content of the composite rubbery polymer (A) contained in the graft copolymer (B), which is the water repellency-imparting agent of the present invention, in the thermoplastic resin composition of the present invention is the resin in the thermoplastic resin composition. It is preferably 10 to 50% by mass with respect to 100% by mass of the component.

If the content of the composite rubbery polymer (A) in the thermoplastic resin composition is less than the above lower limit, a sufficient effect of imparting water repellency cannot be obtained, and antifouling properties may not be sufficient. Even if the content of the composite rubbery polymer (A) exceeds the above upper limit, there is no difference in the effect of improving the water repellency, and rather the water repellency and antifouling properties tend to decrease.

A more preferable content of the composite rubbery polymer (A) is 20 to 45% by mass, more preferably 25 to 45% by mass, based on 100% by mass of the resin component in the thermoplastic resin composition.

Here, the resin component in the thermoplastic resin composition is the sum of the graft copolymer (B), which is the water repellency imparting agent of the present invention, and other thermoplastic resins, which are usually contained in the thermoplastic resin composition. It corresponds to a component other than the below-described additive usually contained in a thermoplastic resin composition.

<Content of silicone-based rubbery polymer (S)>
Containment of the silicone-based rubbery polymer (S) in the composite rubbery polymer (A) contained in the graft copolymer (B), which is the water repellency-imparting agent of the present invention, in the thermoplastic resin composition of the present invention The amount is preferably 2 to 30% by mass with respect to 100% by mass of the resin component in the thermoplastic resin composition.

If the content of the silicone-based rubbery polymer (S) is less than the above lower limit, a sufficient water repellency-imparting effect cannot be obtained, and the antifouling property may not be sufficient. Even if the content of the silicone-based rubbery polymer (S) exceeds the above upper limit, there is no difference in the effect of improving the water repellency, and rather the water repellency and antifouling properties tend to decrease.

A more preferable content of the silicone-based rubbery polymer (S) is 4 to 20% by mass, more preferably 7 to 15% by mass, based on 100% by mass of the resin component in the thermoplastic resin composition.

The resin components in the thermoplastic resin composition are as described above.

<Surface Si amount>
The thermoplastic resin composition of the present invention preferably contains the water repellency-imparting agent of the present invention so that the surface Si amount measured by the following fluorescent X-ray analysis is 50 to 400 cps.
<Fluorescent X-ray analysis>
The surface of the test piece obtained by molding the thermoplastic resin composition was subjected to measurement time of 100 seconds, sample chamber atmosphere He purge, collimator 0.5 × 0.5 mm, excitation voltage 50 kv, tube current 100 μA. Fluorescent X-ray analysis is performed under the conditions, and the Si detection intensity of 1.60 to 1.88 keV is taken as the surface Si amount.

If the surface Si content as determined by fluorescent X-ray analysis is less than the above lower limit, a sufficient water repellency-imparting effect cannot be obtained, and the antifouling property may not be sufficient. Even if the surface Si amount exceeds the above upper limit, there is no difference in the effect of improving the water repellency, and rather the water repellency and antifouling properties tend to decrease.
A more preferable surface Si amount is 100 to 350 cps, more preferably 200 to 300 cps.

A specific method of X-ray fluorescence spectrometry for determining the surface Si content is as described in Examples below.

The thermoplastic resin composition of the present invention contains the water repellency imparting agent of the present invention so as to satisfy the above-mentioned content of the composite rubbery polymer (A), the content of the silicone rubbery polymer (S) and the amount of surface Si. preferably included in

The content of the water repellency imparting agent of the present invention and other thermoplastic resins in the thermoplastic resin composition of the present invention is the content of the composite rubbery polymer (A) contained in the water repellency imparting agent of the present invention, Depending on the content of the silicone-based rubbery polymer (S) contained in the composite rubbery polymer (A), it is usually in 100 parts by mass of the water repellency-imparting agent of the present invention and other thermoplastic resins in total. 10 to 80 parts by weight, particularly 20 to 70 parts by weight of the water repellency-imparting agent of the present invention. If the content of the water repellency imparting agent of the present invention is within the above range, fluidity (moldability) and sufficient water repellency imparting effect can be obtained, and the impact resistance, rigidity, and other physical properties of the molded product can be balanced. tend to be better.

Other thermoplastic resins used in the thermoplastic resin composition of the present invention include, for example, polyvinyl chloride, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-styrene-methyl methacrylate copolymer, styrene-acrylonitrile-N- Phenylmaleimide copolymer, α-methylstyrene-acrylonitrile copolymer, polymethyl methacrylate, methyl methacrylate-styrene copolymer, methyl methacrylate-N-phenylmaleimide copolymer, polycarbonate, polyamide, polyethylene terephthalate, poly Polyester such as butylene terephthalate, polyphenylene ether-polystyrene composite, polypropylene, olefin resin such as polyethylene, acrylonitrile-styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyphenylene ether resin, polyoxymethylene resin , polysulfone-based resins, polyacrylate-based resins, polyphenylene-based resins, thermoplastic polyurethanes, and the like. Among these, acrylonitrile-styrene copolymers are preferred from the viewpoint of impact resistance and fluidity.

The thermoplastic resin composition of the present invention may, if necessary, contain additives that are blended in ordinary thermoplastic resin compositions.

Examples of additives include coloring agents such as pigments and dyes, fillers (carbon black, silica, titanium oxide, etc.), flame retardants, stabilizers, reinforcing agents, processing aids, heat-resistant agents, antioxidants, weather-resistant agents, release agents, plasticizers, antistatic agents, lubricants, and the like.

As described above, these additives may be added in the step of preparing the pre-emulsion in the production of the composite rubbery polymer (A) of the present invention.

Among these additives, the inclusion of the lubricant (E) in particular is preferable because the water repellency stability and water repellency durability can be enhanced.

The lubricant (E) preferably contains at least one selected from higher fatty acids, acid esters, acid amides and higher alcohols.

Examples of higher fatty acids include arachidonic acid, isostearic acid, undecylenic acid, oleic acid, stearic acid, palmitic acid, behenic acid, myristic acid, lauric acid, lanolin fatty acid, linoleic acid, and linolenic acid.

Acid esters include, for example, ceyl myristate, stearyl stearate, behenyl behenate, pentaerythritol distearylate, pentaerythritol tetrastearylate, pentaerythritol tetrabehenate, polyoxyethylene, hydrogenated castor oil and the like.

Examples of acid amides include stearic acid monoamide, oleic acid monoamide, erucic acid monoamide, ethylenebisstearic acid amide, ethylenebisoleic acid amide, and ethylenebislauric acid amide.

Examples of higher alcohols include lauryl alcohol, mystyryl alcohol, cetyl alcohol, and stearyl alcohol.

Among these, acid amides are preferred as the lubricant (E) in order to efficiently develop water repellency. Examples of acid amides include monoamides and bisamides, and bisamides are particularly preferred from the viewpoint of exhibiting a sustained effect of water repellency.

When the thermoplastic resin composition of the present invention contains a lubricant (E), the content of the lubricant (E) in the thermoplastic resin composition is 0.2 to 0.2 parts per 100 parts by mass of the resin component in the composition. It is more preferably 10 parts by mass, preferably 0.5 to 8 parts by mass, still more preferably 0.8 to 6 parts by mass, and particularly preferably 1 to 5 parts by mass.
By containing the lubricant (E) within this range, stable water repellency can be exhibited and the durability of the water repellency can be improved.

The thermoplastic resin composition of the present invention is prepared by mixing and dispersing the water repellent agent of the present invention and, if necessary, additives such as other thermoplastic resins and lubricants (E) using a V-type blender, Henschel mixer, or the like. , the resulting mixture is melt-kneaded using a kneader such as an extruder, Banbury mixer, pressure kneader, rolls, or the like.
The mixing order of each component is not particularly limited as long as all the components are uniformly mixed.

〔Molding〕
The molded article of the present invention is obtained by molding the thermoplastic resin composition of the present invention, and is excellent in water repellency and antifouling properties and durability thereof. Further, by adjusting other thermoplastic resins to be used in combination and their blending amounts, etc., it is also possible to make the molding excellent in impact resistance, mechanical properties such as rigidity, and molding appearance.

Examples of methods for molding the thermoplastic resin composition of the present invention include injection molding, injection compression molding, extrusion, blow molding, vacuum molding, air pressure molding, calender molding and inflation molding. mentioned. Among these, the injection molding method and the injection compression molding method are preferable because they are excellent in mass productivity and can obtain molded articles with high dimensional accuracy.

A molded article according to another aspect of the present invention is a molded article obtained by molding a thermoplastic resin composition, and is characterized by having a surface Si content of 50 to 400 cps as measured by the following fluorescent X-ray analysis. .
<Fluorescent X-ray analysis>
Fluorescent X-ray analysis was performed on the surface of the molded product under the following conditions: measurement time 100 seconds, sample chamber atmosphere He purge, collimator 0.5×0.5 mm, excitation voltage 50 kv, tube current 100 μA. The Si detection intensity of ~1.88 keV is defined as the surface Si amount.

<Surface Si amount>
If the surface Si content is less than 50 cps as determined by fluorescent X-ray analysis, sufficient water repellency and durability cannot be obtained, and antifouling properties may not be sufficient. Even if the surface Si amount exceeds 400 cps, there is no difference in the effect of improving the water repellency, and rather the water repellency and antifouling properties tend to decrease.
A more preferable surface Si amount is 100 to 350 cps, more preferably 200 to 300 cps.

A specific method of X-ray fluorescence spectrometry for determining the surface Si content is as described in Examples below.

There are no particular restrictions on the shape of the molded product of the present invention that satisfies the above surface Si content. For this reason, in the fluorescent X-ray analysis of the surface Si amount, if the shape of the molded product is not suitable for fluorescent X-ray analysis, the same molding method using the thermoplastic resin composition used for molding the molded product may be used. By molding a molded article having a shape suitable for X-ray analysis and measuring the fluorescent X-ray analysis of this molded article, the surface Si content of the molded article can be obtained. The same applies to the measurement of the contact angle of water and the sliding angle of water, which will be described later.

<Water contact angle>
The molded product of the present invention preferably has a surface contact angle of water of 90° or more. The larger the contact angle of water, the better the water repellency.
The method for measuring the water contact angle of the molded article of the present invention is as follows, and more specifically, it is measured by the method described in the Examples section below.

<Method for measuring contact angle of water>
A water droplet of 20 μL is dropped on the horizontal surface of the molded product, and the contact angle of water immediately after dropping is measured.

<Sliding angle of water>
The molded product of the present invention preferably has a sliding angle of water on the surface of 20° or less, more preferably 10° or less. The smaller the sliding angle of water, the better the water repellency.
The method for measuring the sliding angle of water of the molded article of the present invention is as follows, and more specifically, it is measured by the method described in the section of Examples below.

<Measurement of sliding angle of water>
A water droplet of 0.2 mL is dropped on the horizontal surface of the molded product, and the angle at which the water droplet starts to slide when the molded product is tilted at a speed of about 2°/sec is measured.

<How to achieve the surface Si content, water contact angle, and water sliding angle>
As a method for obtaining the molded article of the present invention having a surface Si amount of 50 to 400 cps as determined by X-ray fluorescence analysis, preferably a water contact angle on the surface of 90° or more and a water sliding angle of 20° or less, There is no particular limitation as long as a molded product having such a surface Si content, and furthermore, a contact angle of water and a sliding angle of water can be obtained. For example, there is a method of using the above-described water repellency-imparting agent of the present invention, and using the thermoplastic resin composition of the present invention in which the water repellency-imparting agent is blended at a predetermined ratio as a molding material.

[Use]
INDUSTRIAL APPLICABILITY The molded article of the present invention is excellent in water repellency and antifouling properties and durability thereof, and therefore is suitable for members whose surfaces are easily soiled by the adhesion of water droplets or muddy water. For example, vehicle parts (mudguards, emblems, etc.), building materials (wall materials, window frames, etc.), exterior parts, home appliance housings, office equipment, air conditioner housings, toilet fixtures, bathroom fixtures, etc. have excellent repellency on their surfaces. Being water-based, it repels water, prevents the adhesion of water scale, hot water scale, and mud stains, and can easily remove the adhered stains.

Hereinafter, the present invention will be described more specifically with reference to Synthesis Examples, Examples and Comparative Examples. The present invention is by no means limited to the following examples as long as the gist thereof is not exceeded.
In the following, "parts" means "mass parts" and "%" means "mass%".

[Measurement of volume average particle size]
Silicone-based rubbery polymer (S-1), composite rubbery polymers (A-1) to (A-3), and graft copolymers (B-1) to The volume average particle size of (B-3) and ABS graft copolymer (X-1) was determined by dynamic light scattering using Nanotrac UPA-EX150 manufactured by Nikkiso Co., Ltd.

[Production of silicone-based rubbery polymer (S)]
<Synthesis Example I: Production of Silicone Rubber Polymer (S-1)>
98 parts of octamethylcyclotetrasiloxane and 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane mixture. To this, an aqueous solution consisting of 0.67 parts of sodium dodecylbenzenesulfonate and ³⁰⁰ parts of ion-exchanged water was added. A stable premixed organosiloxane latex was obtained.

Separately, 10 parts of dodecylbenzenesulfonic acid and 90 parts of ion-exchanged water were injected into a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater, and a stirring device to prepare a 10% dodecylbenzenesulfonic acid aqueous solution. . While this aqueous solution was heated to 85° C., the premixed organosiloxane latex was added dropwise over 4 hours, and after the completion of dropwise addition, the temperature was maintained for 1 hour and cooled. Then, the mixture was neutralized with a 10% aqueous sodium hydroxide solution to obtain a latex of silicone rubbery polymer (S-1) (solid content: 18.2%).
The volume average particle size of the silicone rubbery polymer (S-1) dispersed in the silicone rubbery polymer (S-1) latex was 50 nm.

[Production and Evaluation of Composite Rubber Polymer (A)]
<Synthesis Example II-1: Production of composite rubbery polymer (A-1)>
A composite rubbery polymer (A-1) was produced with the following formulation.

(Formulation)
Silicone rubbery polymer (S-1) latex (as solid content) 14 parts Sodium polyoxyethylene alkylphenyl ether sulfate 0.2 parts n-butyl acrylate (BA) 86 parts Allyl methacrylate (AMA) 0.52 1,3-butylene glycol dimethacrylate 0.17 parts t-butyl hydroperoxide 0.22 parts ferrous sulfate 0.0002 parts sodium formaldehyde sulfoxylate 0.33 parts disodium ethylenediaminetetraacetate 0.0004 parts ion exchange 430 parts of water

14 parts of silicone rubbery polymer (S-1) latex (as a solid content), 430 parts of ion-exchanged water, poly 0.2 parts of sodium oxyethylene alkylphenyl ether sulfate, 86 parts of n-butyl acrylate, 0.52 parts of allyl methacrylate, 0.17 parts of 1,3-butylene glycol dimethacrylate, 0.22 parts of t-butyl hydroperoxide was charged, and the inside of the reaction vessel was replaced with nitrogen while stirring. After heating to 60° C., ferrous sulfate, sodium formaldehyde sulfoxylate and disodium ethylenediaminetetraacetate were added to initiate the polymerization reaction. After the heat of polymerization was confirmed, the internal temperature was set to 75° C., and the polymerization was continued until the heat of polymerization was no longer confirmed. A latex of 1) was obtained.
The composite rubbery polymer (A-1) in the resulting latex had a solid content of 19.1% and a volume average particle size of 90 nm.

<Synthesis Examples II-2 to II-3: Production of composite rubbery polymers (A-2) to (A-3)>
Synthesis Example II-1, except that the amounts of the silicone-based rubbery polymer (S-1), n-butyl acrylate, allyl methacrylate, and 1,3-butylene glycol dimethacrylate were changed as shown in Table 1. Latexes of composite rubbery polymers (A-2) to (A-3) were obtained in the same manner.

The volume average particle diameters of the obtained composite rubbery polymers (A-1) to (A-3) were as shown in Table 1.

Table 1 shows the silicone rubbery polymer (S-1)/n-butyl acrylate mass ratio of each composite rubbery polymer (A-2) to (A-3) as the SLx/BA ratio.

[Production and Evaluation of Graft Copolymer (B)]
<Synthesis Example III-1: Production of graft copolymer (B-1)>
A reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirring device was charged with raw materials according to the following composition, and the internal temperature was raised to 75° C. while stirring.

(Formulation)
Water (including water in composite rubbery polymer (A-1) latex) 240 parts composite rubbery polymer (A-1) latex (as solid content) 50 parts sodium dodecylbenzenesulfonate (DBS-Na) 0 .5 parts Sodium formaldehyde sulfoxylate 0.42 parts Ferrous sulfate heptahydrate 0.001 parts Disodium ethylenediaminetetraacetate 0.003 parts

Next, the temperature was raised to 80° C. while dropping a mixture containing acrylonitrile (AN), styrene (ST) and t-butyl hydroperoxide in the following composition over 100 minutes.

(Formulation)
Acrylonitrile (AN) 12.5 parts Styrene (ST) 37.5 parts t-butyl hydroperoxide 0.2 parts

After completion of dropping, the temperature was maintained at 80° C. for 30 minutes and then cooled to obtain a latex of graft copolymer (B-1).
The graft copolymer (B-1) in the obtained latex had a solid content of 28.6%, a volume average particle diameter of 120 nm, and a graft ratio of 45%.

Next, 100 parts of a 1.5% calcium acetate aqueous solution was heated to 80° C., and while stirring the aqueous solution, 100 parts of the graft copolymer (B-1) latex was gradually added dropwise to the aqueous solution to obtain a graft copolymer. (B-1) was solidified, and the temperature was raised to 95° C. and held for 10 minutes.
The solidified product was then dehydrated, washed and dried to obtain a powdery graft copolymer (B-1).

<Synthesis Examples III-2 to III-3: Production of graft copolymers (B-2) to (B-3)>
Synthesis Example II-1 was repeated except that latexes of the composite rubbery polymers (A-2) to (A-3) were used instead of the latex of the composite rubbery polymer (A-1). to obtain graft copolymers (B-2) to (B-3), respectively.

Table 2 summarizes the raw material blends, volume average particle diameters, and graft ratios of the graft copolymers (B-1) to (B-3) produced.

20 g of each of the powders of the graft copolymers (B-1) to (B-3) was weighed into a cylindrical container (5.6 cm in diameter), and a weight of 20 kg was placed on the powder so that a uniform load was applied to the powder. The powders of the graft copolymers (B-1) to (B-3) were formed into blocks by leaving them for 2 hours in an environment at a temperature of 35°C. The block-shaped graft copolymers (B-1) to (B-3) are placed on a sieve with an opening of 3.35 mm, and the time required for the sieving rate to reach about 100% with a sieve shaker. The anti-blocking property was evaluated by measuring (the time required for almost the entire amount to drop from the sieve). The results are also shown in Table 2. The shorter this time, the better the anti-blocking property, and if it is 100 seconds or less, it is judged that the anti-blocking property is excellent.

[Manufacture of ABS resin]
<Synthesis Example IV: Production of ABS resin (X-1)>
175 parts of ion-exchanged water, 54 parts of emulsified latex of polybutadiene (in terms of solid content), 32.2 parts of styrene, 13.8 parts of acrylonitrile, and 1.3 parts of disproportionated potassium rosinate; 0.0046 parts of ferrous sulfate, 0.28 parts of fructose, 0.11 parts of t-dodecyl mercaptan and 0.20 parts of cumene hydroperoxide were charged, the reaction was started at 60°C, and the temperature was raised to 70°C on the way. After two and a half hours of warming, the emulsion graft polymerization was completed. The reactant latex was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain ABS resin (X-1) (hereinafter referred to as "graft copolymer (X-1)").
The graft copolymer (X-1) had a graft ratio of 55% and a volume average particle diameter of 320 nm.

[Lubricant (E)]
In Examples 11 to 18 and Comparative Example 6 below, the following lubricant (E-1) or lubricant (E-2) was used.
Acid monoamide-based lubricant (E-1): "Amamide AP-1" (stearic acid amide) manufactured by Mitsubishi Chemical Corporation
Acid bisamide-based lubricant (E-2): "Slipax L" (ethylenebislauric acid amide) manufactured by Mitsubishi Chemical Corporation

[Silicone oil masterbatch]
In Comparative Examples 1 to 6 below, the following silicone oil masterbatch was used.
Silicone oil masterbatch: Fuji Chemical Co., Ltd. “Crinbell CB-50AB” (silicone oil/ABS resin = 50/50 (mass ratio) silicone oil masterbatch)

[Examples 1 to 18, Comparative Examples 1 to 6: Production and evaluation of thermoplastic resin compositions]
<Production of AN-ST thermoplastic resin composition>
In Examples 1 to 18, graft copolymers (B-1) to (B-3) in proportions shown in Tables 3A and 3B and acrylonitrile (AN)-styrene (ST) copolymer produced by a suspension polymerization method were used. Combined (“UMG AXS Resin S202N” manufactured by Techno-UMG Co., Ltd.) was blended. In Examples 11 to 18, a lubricant (E-1) or (E-2) was added at the ratio shown in Tables 3A and 3B.

In Comparative Examples 1 to 6, the graft copolymer (X-1), the acrylonitrile (AN)-styrene (ST) copolymer, and the silicone oil masterbatch were blended in the proportions shown in Table 3B (however, in Comparative Example 1 , acrylonitrile-styrene copolymer and silicone oil masterbatch only). In Comparative Example 6, a lubricant (E-2) was added at the ratio shown in Table 3B.

Furthermore, 0.5 part of carbon black was added to the entire thermoplastic resin composition and mixed using a Henschel mixer.

This mixture was supplied to an extruder heated to 220° C. and kneaded to obtain pellets of the thermoplastic resin composition.

<Preparation of test compact>
Using the pellets of the thermoplastic resin composition, each J85AD-110H manufactured by Japan Steel Works, Ltd. was molded under the conditions of a cylinder temperature of 240 ° C., a mold temperature of 50 ° C., and an injection speed of 25 mm / sec. A plate-shaped compact having a height of 86 mm, a width of 50 mm and a thickness of 3 mm was obtained.
In Comparative Example 5, the screw slipped during molding and weighing was not possible, and molding was impossible. Therefore, the following evaluation could not be performed.

<Evaluation>
(Molding Appearance: Evaluation of Color Development)
The lightness L* of the test molded product was measured by the SCE method using a spectrophotometer ("CM-3500d" manufactured by Konica Minolta Optips, Inc.). Let the measured L* be “L* (ma)”. It was determined that the lower the L*, the blacker the color, and the better the color developability.
“Lightness L*” means a lightness value (L*) among color values in the L*a*b* color system adopted in JIS Z8729.
The “SCE method” means a method of measuring color by using a spectrophotometer conforming to JIS Z 8722 and removing specularly reflected light with a light trap.

(Molding Appearance: Measurement of Surface Gloss)
Using a "digital variable angle gloss meter UGV-5D" manufactured by Suga Test Instruments Co., Ltd., reflectance (%) of the surface of the test molded body at an incident angle of 60 ° and a reflection angle of 60 ° in accordance with JIS K 7105 was measured. A higher reflectance means a better surface appearance.

(Measurement of surface Si content (fluorescent X-ray analysis))
Using a fluorescence X-ray analyzer EA6000VX manufactured by Hitachi High-Tech Science Co., Ltd., the surface of the test molded body was measured for 100 seconds, the sample chamber atmosphere was He purged, the collimator was 0.5 × 0.5 mm, the excitation voltage was 50 kv, and the tube Fluorescent X-ray analysis was performed at a current of 100 μA, and the Si detection intensity of 1.60 to 1.88 keV was taken as the surface Si amount.

(Water repellency: measurement of water contact angle)
A contact angle meter CA-S Micro 2 manufactured by Kyowa Interface Science Co., Ltd. was used to measure the contact angle of water immediately after dropping 20 μL of ion-exchanged water on the surface of the test molded body placed horizontally.
The contact angle of water is 90° or more, and the larger the contact angle, the better the water repellency.

(Water repellency: measurement of sliding angle of water)
Using a HEIDON Static Friction TESTER HEIDON-10 manufactured by Shinto Kagaku Co., Ltd., 0.2 mL of ion-exchanged water is dropped on the horizontal upper surface of the test molded body, and the molded body is tilted at a speed of about 2°/second. rice field. At this time, the angle at which the water droplet started to slide was measured, and it was defined as the water slide angle.
The smaller the sliding angle, ie, 20° or less, or 10° or less, the better the water repellency.

(Anti-fouling property: Evaluation of degree of adhesion of muddy water)
The test molded body was placed at an inclination angle of 45°, and 50 mL of the following muddy water was sprayed on the inclined surface of the molded body from the lotus mouth of a watering can. Then, after air-drying, the surface on which the mud was sprayed was observed, and the ratio (percentage) of the adhered area of the dried and solidified mud to the area of the plate surface of the compact was visually estimated and evaluated according to the following criteria. The higher the score, the more excellent the water repellency and antifouling properties.
Muddy water: JIS class 8 powder (Kanto loam layer sand)/pure water/neutral surfactant = 20/79.75/0.25 (parts by mass)
<Evaluation criteria>
1 point: adhesion area ratio almost 100%
2 points: Adhesion area ratio about 80 to 100%
3 points: Adhesion area ratio about 50 to 80%
4 points: Adhesion area ratio about 20 to 50%
5 points: Almost no adhesion.

The above water repellency and antifouling properties were evaluated on molded articles degreased by the method described below. From this evaluation, it can be seen that the water repellency and antifouling properties are exhibited without being affected by the degreasing treatment, that is, the durability of the water repellency and antifouling properties is excellent.
(Degrease treatment method)
The compact was degreased by wiping it lightly with isopropyl alcohol soaked in absorbent cotton.

(sustainability evaluation)
In Examples 1 to 3, 11 to 18 and Comparative Example 6, the test molded article was aged for 100 hours in a high-humidity constant temperature bath at a temperature of 60 ° C. and a humidity of 50%. The angle was measured, and the degree of adhesion of muddy water was evaluated as an antifouling property.

The results of Examples 1-18 and Comparative Examples 1-6 are shown in Tables 3A and 3B.

From Tables 3A and 3B, the molded articles made of the thermoplastic resin compositions of Examples 1 to 18 blended with the graft copolymer (B), which is the water repellency imparting agent of the present invention, or the surface Si amount is 50 to 400 cps. It can be seen that the molded article of the present invention is excellent in water repellency and antifouling properties. In addition, it can be seen that the addition of the water repellent imparting agent scarcely impairs the moldability and molded appearance, and the molded appearance is superior to those of Comparative Examples 2 to 4 and 6, in which ordinary ABS resins are blended.

From the content of the composite rubbery polymer (A), the content of the silicone-based rubbery polymer (S), and the surface Si amount of the thermoplastic resin composition in Examples 1 to 18, the composite rubber of the thermoplastic resin composition The content of the rubbery polymer (A) is in the range of 25-45% by mass, the content of the silicone-based rubbery polymer (S) is in the range of 7-15% by mass, and the amount of surface Si is in the range of 200-300cps. It can be seen that the water repellency-imparting effect is particularly excellent when the content is in the range.

Further, from Examples 11 to 18 in which the lubricant (E) was blended, it can be seen that the blending of the lubricant (E) improved the water repellency effect. In particular, Examples 12, 14, 16, and 18 using a bisamide-based lubricant as the lubricant (E) are found to exhibit an excellent long-lasting effect of water repellency.
On the other hand, in Comparative Example 6, even if the lubricant (E) is blended, such an effect cannot be obtained.

Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application 2019-179865 and Japanese Patent Application 2019-179870 filed on September 30, 2019, the entirety of which is incorporated by reference.

Claims (9)

A graft copolymer (B) obtained by graft-polymerizing a vinyl compound (b) to a composite rubbery polymer (A) obtained by conjugated a silicone-based rubbery polymer (S) with a (meth)acrylic acid ester. and a lubricant (E) . The ratio of the silicone-based rubbery polymer (S) to the total 100% by mass of the silicone-based rubbery polymer (S) and the (meth)acrylic acid ester in the composite rubbery polymer (A) is 10 to The thermoplastic resin composition according to claim 1, which is 65% by mass. The vinyl compound (b) contains aromatic vinyl and vinyl cyanide, and the graft copolymer (B) is added to the composite rubbery polymer (A) in an amount of 30 to 90% by mass, the vinyl compound ( b) The heat according to claim 1 or 2, obtained by graft polymerization of 70 to 10% by mass (where the total of the composite rubbery polymer (A) and the vinyl compound (b) is 100% by mass) A plastic resin composition . The content of the composite rubbery polymer (A) is 10 to 50% by mass, and the content of the silicone-based rubbery polymer (S) is 2 to 30% by mass, based on 100% by mass of the resin component in the composition. The thermoplastic resin composition according to any one of claims 1 to 3 . 5. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the lubricant (E) is contained in an amount of 0.2 to 10 parts by mass with respect to 100 parts by mass of the resin component in the composition. 6. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the lubricant (E) is an acid amide lubricant. The thermoplastic resin composition according to any one of claims 1 to 6, which has a surface Si amount of 50 to 400 cps as measured by the following fluorescent X-ray analysis.
<Fluorescent X-ray analysis>
The surface of the test piece obtained by molding the thermoplastic resin composition was subjected to measurement time of 100 seconds, sample chamber atmosphere He purge, collimator 0.5 × 0.5 mm, excitation voltage 50 kv, tube current 100 μA. Fluorescent X-ray analysis is performed under the conditions, and the Si detection intensity of 1.60 to 1.88 keV is taken as the surface Si amount. A molded article obtained by molding the thermoplastic resin composition according to any one of claims 1 to 7 . 9. The molded article according to claim 8 , which is a vehicle member, building material, exterior member, household appliance housing, office equipment or air conditioner housing.