JP7375431B2 - Molding - Google Patents

Description

The present invention relates to a thermoplastic resin molded article having excellent water repellency and durability.

In order to prevent the adhesion of dirt on resin molded products due to water scale, hot water scale, and muddy water, and to make it easier to remove the adhered dirt, water repellency is imparted to the surface of resin molded products.

Conventionally, methods for imparting water repellency to resin molded products include coating the surface of the resin molded product with a water repellent coating agent to form a water repellent coating layer, or pasting a water repellent film on the surface of the resin molded product. However, with this method, the number of steps after molding the resin molded product increases, which increases manufacturing costs, and there is also the problem that the desired antifouling effect cannot be achieved due to wear of the water-repellent coating layer or peeling of the water-repellent film over time. be.

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

Japanese Patent Application Publication No. 2010-77270

However, the technique disclosed in Patent Document 1 has a problem in that silicone oil or the like blended into 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, but the measured value of the sliding angle of water in Examples of Patent Document 1 is about 30 to 40°. However, in order to obtain a sufficient antifouling effect, higher water repellency with a sliding angle of 20° or less, preferably 10° or less is desired.

An object of the present invention is to provide a thermoplastic resin molded article that has excellent water repellency and excellent sustainability of water repellency.

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that a molded product whose surface Si content is within a predetermined range as measured by a specific fluorescent X-ray analysis on the surface of the molded product can achieve the above object. I found out.
That is, the gist of the present invention is as follows.

[1] A molded article formed by molding a thermoplastic resin composition, which has 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 x 0.5 mm, excitation voltage 50 kV, tube current 100 μA. The Si detection intensity of ~1.88 keV is taken as the surface Si amount.

[2] The molded article according to [1], wherein the surface has a water contact angle of 90° or more and a water sliding angle of 20° or less.

[3] The thermoplastic resin composition is a composite rubbery polymer (A) formed 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 [1] or [2], which contains a water repellency imparting agent made of the polymerized graft copolymer (B).

According to the present invention, it has excellent water repellency and its sustainability, prevents the adhesion of stains due to limescale and muddy water over a long period of time, and can easily remove adhering stains. Thermoplastic resin molded products can be provided.

Embodiments of the present invention will be described in detail below.
In addition, in this specification, "unit" refers to a structural part derived from a monomer compound (monomer) before polymerization, and for example, "(meth)acrylic acid ester unit" means "(meth)acrylic acid ester unit". A structural part derived from esters. The content ratio of each monomer unit in the polymer corresponds to the content ratio of the monomer in the monomer mixture used for producing the polymer.
Moreover, "(meth)acrylic acid" means one or both of "acrylic acid" and "methacrylic acid." The same applies to "(meth)acrylate".
Furthermore, the term "molded product" means a product formed by molding a thermoplastic resin composition.

In addition, the volume average particle diameters of the silicone rubber polymer (S), composite rubber polymer (A), and graft copolymer (B) described below are measured by the method described in the Examples section below. is the value given.

The molded article of the present invention is a molded article formed by molding a thermoplastic resin composition, and has a surface Si content (hereinafter sometimes simply referred to as "surface Si content") measured by the following fluorescent X-ray analysis. .) is 50 to 400 cps.
<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 x 0.5 mm, excitation voltage 50 kV, tube current 100 μA. The Si detection intensity of ~1.88 keV is taken as the surface Si amount.

[Surface Si amount]
If the amount of surface Si determined by fluorescent X-ray analysis is less than 50 cps, sufficient water repellency and its sustainability cannot be obtained, and the antifouling property may also be insufficient. Even if the amount of surface Si exceeds 400 cps, there is no difference in the effect of improving water repellency, but rather there is a tendency for water repellency and antifouling properties to decrease.
A more preferable surface Si amount is 100 to 350 cps, and even more preferably 200 to 300 cps.

The specific method of fluorescent X-ray analysis for determining the amount of surface Si is as described in the Examples section below.

Note that there are no particular limitations on the shape of the molded product of the present invention. Therefore, in fluorescent X-ray analysis of the amount of Si on the surface, if the shape of the molded product is not suitable for fluorescent X-ray analysis, the thermoplastic resin composition used for molding the molded product can be By molding a molded article with a shape suitable for X-ray analysis and measuring the fluorescent X-ray analysis on this molded article, the amount of Si on the surface of the molded article can be determined. The same applies to the measurements of the contact angle of water and the sliding angle of water, which will be described later.

[Water contact angle]
The molded article of the present invention preferably has a surface water contact angle of 90° or more, and the larger the water contact angle, 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 of measuring water contact angle>
A 20 μL water droplet is dropped on the horizontal surface of the molded body, and the contact angle of the water immediately after dropping is measured.

[Water sliding angle]
In the molded article of the present invention, the sliding angle of water on the surface is preferably 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 water sliding angle of the molded product of the present invention is as follows, and more specifically, it is measured by the method described in the Examples section below.

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

[Method for achieving surface Si content, water contact angle, and water sliding angle]
The method for obtaining the molded article of the present invention, which has a surface Si content of 50 to 400 cps as determined by the aforementioned fluorescent X-ray analysis, preferably has a surface water contact angle of 90° or more and a water sliding angle of 20° or less, includes: There is no particular restriction as long as a molded product having such a surface Si content, water contact angle, and water sliding angle can be obtained, but for example, the following water repellency imparting agent may be used, and this water repellency imparting agent may be An example of this method is to use a thermoplastic resin composition blended with a predetermined ratio of the following as a molding material.

Hereinafter, the water repellency imparting agent suitably used in the present invention will be referred to as the "water repellency imparting agent of the present invention", and the thermoplastic resin composition blended with the water repellency imparting agent of the present invention will be referred to as the "thermoplastic resin composition of the present invention". "Plastic resin composition".

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

According to the thermoplastic resin composition containing the water repellent agent of the present invention, it has excellent water repellency and its sustainability, and can prevent the adhesion of stains such as water scale and muddy water over a long period of time, and can also prevent adhering stains. It is possible to provide a thermoplastic resin molded product with excellent stain resistance that can be easily removed.
Moreover, according to the water repellency imparting agent of the present invention, good water repellency can be imparted to the obtained thermoplastic resin molded product without significantly impairing the molded appearance.
In addition, the graft copolymer (B) constituting the water repellency imparting agent of the present invention is a composite rubbery polymer formed by combining (meth)acrylic acid ester with a silicone rubbery polymer (S) as a rubber component. The use of (A) also has the effect of excellent blocking properties, and is suitable for the present invention from the viewpoint of excellent handling properties.

[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 "the 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 ester, a crosslinking agent, and other vinyl compounds as necessary.

<Silicone rubber 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, it is composed of 0.3 to 3 mol% of siloxane units containing a vinyl polymerizable functional group (siloxane containing a vinyl polymerizable functional group) and 97 to 99.7 mol% of dimethylsiloxane units, and contains three or more siloxane units. A polyorganosiloxane in which the number of bonded silicon atoms is 1 mol % or less based on the total silicon atoms in the polydimethylsiloxane is preferred.

Examples of the dimethylsiloxane constituting the polyorganosiloxane include dimethylsiloxane-based cyclic bodies having three or more members. Among these, those having a 3- to 7-membered ring are preferred. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. 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 be bonded to dimethylsiloxane via a siloxane bond, but considering the reactivity with dimethylsiloxane, Various alkoxysilane compounds containing a vinyl polymerizable functional group are preferred. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, Methacryloyloxysiloxanes such as γ-methacryloyloxypropyldiethoxymethylsilane and ∂-methacryloyloxybutyldiethoxymethylsilane; Vinylsiloxanes such as tetramethyltetravinylcyclotetrasiloxane; p-vinylphenyldimethoxymethylsilane, γ-mercaptopropyl Examples include mercaptosiloxanes such as dimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane. These vinyl polymerizable functional group-containing siloxanes can be used alone or in combination of two or more.

The silicone rubbery polymer (S) may contain a siloxane crosslinking agent unit as a constituent component, if necessary.
Examples of the siloxane crosslinking agent include trifunctional or tetrafunctional silane crosslinking agents, such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane. These can be used alone or in combination of two or more.

The method for producing the silicone rubbery polymer (S) is not limited. For example, it can be manufactured by the following method.
First, a siloxane crosslinking agent is added as necessary to a siloxane mixture consisting of dimethylsiloxane and a siloxane containing a vinyl polymerizable functional group, and then the mixture is emulsified with an emulsifier and water to obtain an aqueous siloxane mixture dispersion. Next, the aqueous siloxane mixture dispersion is pulverized using a homomixer that pulverizes the mixture using shearing force generated by high-speed rotation, a homogenizer that pulverizes the mixture using the ejection force of a high-pressure generator, or the like. Here, it is preferable to use a high-pressure emulsification device such as a homogenizer because the particle size distribution of the silicone rubbery polymer (S) becomes smaller. Next, the aqueous dispersion of the finely divided siloxane mixture is added to an aqueous acid solution containing an acid catalyst and polymerized at high temperature. Then, the reaction solution is cooled and further neutralized with an alkaline substance such as caustic soda, caustic potash, or sodium carbonate to stop the polymerization, thereby obtaining a silicone-based rubbery polymer (S) dispersed in an aqueous dispersion.

The emulsifier used in the production of the silicone rubbery polymer (S) is preferably an anionic emulsifier. Examples of the anionic emulsifier include sodium alkylbenzene sulfonate, sodium polyoxyethylene nonylphenyl ether sulfate, and the like. Among these, sulfonic acid emulsifiers such as sodium alkylbenzenesulfonate and sodium laurylsulfonate are preferred. These emulsifiers may be used alone or in combination of two or more. These emulsifiers are used in an amount of about 0.05 to 5 parts by weight per 100 parts by weight (solid content) of the siloxane mixture.

Further, examples of the acid catalyst used in polymerization include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. These acid catalysts can be used alone or in combination of two or more. Among these, aliphatic substituted benzenesulfonic acid is preferred, and n-dodecylbenzenesulfonic acid is particularly preferred, since it has an excellent stabilizing effect on the aqueous dispersion of the silicone rubbery polymer (S). Furthermore, when n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used together, the emulsifier used in the aqueous dispersion of the silicone rubbery polymer (S) will affect the color development of the thermoplastic resin composition. You can minimize this as much as possible.

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

In the present invention, the volume average particle diameter 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 diameter of less than 1 nm is difficult to manufacture, and if it exceeds 100 nm, the molded appearance of a thermoplastic resin molded product obtained using the same becomes poor.
The particle size distribution of the silicone rubbery polymer (S) of the present invention is not particularly limited, but 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 diameter of the silicone rubbery polymer (S), for example, the method described in JP-A-5-279434 can be employed.

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

<(meth)acrylic acid ester>
Examples of the (meth)acrylic ester 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. , acrylic acid alkyl esters with an alkyl group having 1 to 22 carbon atoms such as benzyl acrylate; alkyl methacrylates with an alkyl group having 1 to 22 carbon atoms such as hexyl methacrylate, 2-ethylhexyl methacrylate, n-dodecyl methacrylate, etc. Examples include esters. This is because the water repellency, impact resistance, and gloss of thermoplastic resin molded products that are blended with a water repellent agent made of a graft copolymer (B) using the resulting composite rubbery polymer (A) are improved. Among the (meth)acrylic esters, n-butyl acrylate is preferred. These (meth)acrylic esters may be used alone or in combination of two or more.

<Silicone rubber polymer (S)/(meth)acrylic acid ester ratio>
The proportion of the silicone rubber polymer (S) in the total 100% by mass of the silicone rubber polymer (S) and (meth)acrylic acid ester used in the production of the composite rubber polymer (A) of the present invention is 10 ~65% by mass, the proportion of (meth)acrylic acid ester is preferably 90 to 35% by mass, and this proportion is 12 to 55% by mass of silicone rubber polymer (S), and (meth) Acrylic ester: more preferably 88 to 45% by mass, silicone rubber polymer (S): 15 to 55% by mass, and (meth)acrylic ester: 85 to 45% by mass. preferable. If the silicone rubber polymer (S) is less than the above range, the water repellent effect of the silicone rubber polymer (S) cannot be sufficiently obtained. Even if the amount of the silicone rubbery polymer (S) is too much than the above range, the details of the reason are not clear, but water repellency is achieved by the water repellency imparting agent using the composite rubbery polymer (A) of the present invention. In fact, the effect of this effect tends to decrease.

<Crosslinking agent>
When producing the composite rubbery polymer (A) of the present invention, in order to introduce a crosslinked structure into the (meth)acrylic acid ester unit obtained from the (meth)acrylic acid ester described above, preferably A crosslinking agent is used with the acid ester. If it is a crosslinked rubbery polymer (A) obtained using a crosslinking agent, the crosslinked portion thereof may be grafted to the vinyl compound (b) described below used in the production of the graft copolymer (B). It also functions as a crossing point.

Examples of the crosslinking agent 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, etc. It will be done. These may be used alone or in combination of two or more.

There is no particular limit to the amount of the crosslinking agent used, but the ratio of the crosslinking agent to 100 parts by mass of the silicone rubbery polymer (S) and (meth)acrylic acid ester is 0.1 to 5. The amount is preferably 0 parts by weight, particularly 0.2 to 4.0 parts by weight. If the proportion of the crosslinking agent is within the above range, a thermoplastic resin composition containing a water repellent agent made of a graft copolymer (B) using the resulting composite rubbery polymer (A) can be used. The resulting molded product 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 ester may be used as necessary. Other vinyl compounds are not particularly limited as long as they can be copolymerized with (meth)acrylic esters and crosslinking agents. For example, aromatic vinyls such as styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, pt-butylstyrene, ethylstyrene; cyanide vinyls such as acrylonitrile, methacrylonitrile; N -Maleimides such as cyclohexylmaleimide and N-phenylmaleimide, maleic anhydride, and the like. These may be used alone or in combination of two or more.

When other vinyl compounds are used in the production of the composite rubbery polymer (A) of the present invention, the amount of other vinyl compounds used is 100% in total of the silicone rubbery polymer (S) and (meth)acrylic acid ester. It is preferred that the proportion of other vinyl compounds to parts by weight be 30 parts by weight or less, particularly 20 parts by weight or less, especially 10 parts by weight 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 ester in the presence of a silicone rubbery polymer (S). In addition, in the production of the composite rubbery polymer (A) of the present invention, other rubber components and various additives other than the silicone rubbery polymer (S) mentioned in the explanation below may be added to the polymerization system. Can be done.
The polymerization method of the (meth)acrylic 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 a composite rubbery polymer (A) by an emulsion polymerization method, for example, silicone rubbery polymer (S), (meth)acrylic acid ester, a crosslinking agent, and optionally used Other vinyl compounds to be used, an emulsifier, an initiator, and a chain transfer agent are charged, polymerized by heating, and the composite rubbery polymer (A) is recovered from the latex containing the composite rubbery polymer (A) by a precipitation method. One method is to do so.

(emulsifier)
Examples of the emulsifier 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, alkali metal salts of alkenylsuccinic acid, etc. Known emulsifiers, such as anionic emulsifiers selected from acid emulsifiers, alkyl sulfate esters, sodium alkylbenzene sulfonates, sodium alkyl sulfosuccinates, sodium polyoxyethylene nonylphenyl ether sulfate, etc., alone or in combination. Can be used in combination. Further, a part of the emulsifier can be appropriately added during the polymerization reaction in order to stabilize the latex.

Excessive emulsifier can easily cause gas to adhere to the mold during the production of molded products and reduce productivity. Therefore, the amount of emulsifier added should be ) 0.01 to 3.0 parts by mass, more preferably 0.02 to 2.0 parts by mass, based on a total of 100 parts by mass of the acrylic ester, the crosslinking agent, and other vinyl compounds used as necessary. , more preferably 0.03 to 1.0 parts by mass. Within the above range, the composite rubbery polymer (A) can be stably produced.

(initiator)
Examples of the initiator include an azo polymerization initiator, a photopolymerization initiator, an inorganic peroxide, an organic peroxide, and a redox initiator that is a combination of an organic peroxide, a transition metal, and a reducing agent. Among these, preferred are azo polymerization initiators, inorganic peroxides, organic peroxides, and redox initiators that can initiate polymerization by heating. These may be used alone or in combination of two or more.

Examples of the azo polymerization initiator 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-cykhexanecarboxylate) ), 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. Can be mentioned.

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

Examples of organic peroxides include peroxy ester compounds, specific examples of which include α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3, 3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-Butylperoxypivalate, 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-butylperoxy2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyacetate, t-Butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoate, 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)cyclohexane -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-butylperoxide)diisopropylbenzene, dicumylperoxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylcumylperoxide , di-t-butyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 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-ethylhexane peroxyate, dibenzoylperoxide, paramenthane hydro Examples include peroxide and t-butyl peroxybenzoate.

The redox initiator is preferably a combination of an organic peroxide, ferrous sulfate, a chelating agent, and a reducing agent. For example, those consisting of cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate, and dextrose, or combinations of t-butyl hydroperoxide, sodium formaldehyde sulfoxylate (Rongalit), ferrous sulfate, and disodium ethylenediaminetetraacetate. Examples include things such as

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

Examples of chain transfer agents include mercaptans, α-methylstyrene dimer, and terpenes.
The chain transfer agent may be used in an amount of 1.2 parts by mass or less based on a total of 100 parts by mass of the silicone rubber polymer (S), (meth)acrylic acid ester, and other vinyl compounds used as necessary. preferable.

As a method for producing a composite rubbery polymer (A) by a suspension polymerization method, for example, a silicone rubbery polymer (S), a (meth)acrylic acid ester, a crosslinking agent, and optionally Other vinyl compounds to be used, a suspending agent, a suspension aid, an initiator, and a chain transfer agent are charged, polymerized by heating, and the slurry is dehydrated and dried to recover the composite rubbery polymer (A). There are several methods.

Examples of the suspending agent include anionic water-soluble polymers, nonionic water-soluble polymers, poorly water-soluble inorganic salts, and the like.

Examples of anionic water-soluble polymers include polyacrylic acid, sodium polyacrylate, potassium polyacrylate, polymethacrylic acid, sodium polymethacrylate, potassium polymethacrylate, and sodium methacrylate-alkyl methacrylate copolymer. One or more of the following may be mentioned. Among these, 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, and polyoxyethylene lauryl amine. Preferred are polyvinyl alcohol, polyoxyethylene-polyoxypropylene copolymers, and more preferred are polyoxyethylene-polyoxypropylene block copolymers.

Examples of poorly water-soluble inorganic salts include one or more of barium sulfate, tribasic calcium phosphate, magnesium carbonate, and the like. Preferably it is tricalcium phosphate.

The suspending agent may be used in an amount of 0.1 to 3 parts by mass based on a total of 100 parts by mass of the silicone rubber polymer (S), (meth)acrylic acid ester, and other vinyl compounds used as necessary. preferable.

Suspension aids include carboxylates (e.g., sodium sarcosinate, potassium fatty acids, sodium fatty acids, potassium alkenylsuccinate, dipotassium alkenylsuccinate, rosin acid soap, etc.), alkyl sulfate salts, sodium alkylbenzenesulfonates, alkyl Examples include one or more dibasic acids or salts thereof having an alkyl group and/or alkenyl group, such as sodium sulfosuccinate and sodium polyoxyethylene nonylphenyl ether sulfate.

As the suspension aid, potassium alkenyl succinate is preferably used from the viewpoint of stability during production.

The suspension aid should be used in a range 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 used as necessary. is preferred.

Examples of the initiator include organic peroxides.
The initiator is preferably used in an amount of 0.001 to 5 parts by mass based on a total of 100 parts by mass of the silicone rubbery polymer (S), (meth)acrylic acid ester, and other vinyl compounds used as necessary. .

Examples of chain transfer agents include mercaptans, α-methylstyrene dimer, and terpenes.
The chain transfer agent may be used in an amount of 1.2 parts by mass or less based on a total of 100 parts by mass of the silicone rubber polymer (S), (meth)acrylic acid ester, and other vinyl compounds used as necessary. preferable.

<Volume average particle diameter of composite rubbery polymer (A)>
The volume average particle diameter 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 diameter of the composite rubbery polymer (A) is equal to or greater than the above lower limit, stable production is possible, and if it is equal to or less than the above upper limit, the resulting thermoplastic resin molded product has good appearance characteristics. .

[Graft copolymer (B)]
The graft copolymer (B), which is a water repellency imparting agent of the present invention, is a composite rubbery polymer (A) of the present invention, and a vinyl compound (b), such as an aromatic vinyl, a (meth)acrylic ester, A graft layer is formed by graft polymerizing at least one vinyl compound (b) selected from vinyl cyanide and vinyl cyanide.
In addition, the vinyl compound (b) may contain other vinyl compounds other than (meth)acrylic acid ester, aromatic vinyl, and vinyl cyanide.

The grafting rate of the graft layer of the graft copolymer (B) was calculated by the following method, and the grafting rate was also determined by this method in the Examples described below.

<Calculation of graft rate>
80 mL of acetone was added to 2.5 g of graft copolymer (B), and the mixture was refluxed in a 65° C. water bath for 3 hours to extract the acetone-soluble components. The remaining acetone insoluble matter is separated by centrifugation, dried, and then the mass is measured. 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: , calculate the grafting rate.

The grafting ratio of the graft copolymer (B) of the present invention is preferably 10 to 90%, particularly 30 to 85%. If the grafting rate of the graft copolymer (B) is within the above range, a thermoplastic resin molded article with good impact resistance and molded appearance can be obtained using this graft copolymer (B).

As the (meth)acrylic ester to be graft-polymerized to the composite rubbery polymer (A) of the present invention, one of the exemplified (meth)acrylic esters used in the production of the composite rubbery polymer (A) of the present invention is used. A species or two or more species can be used. In addition, as the aromatic vinyl and vinyl cyanide, one of the 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. A species or two or more species can be used.

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

When a mixture of aromatic vinyl, preferably styrene, and vinyl cyanide, preferably acrylonitrile is used as the vinyl compound (b) forming the graft layer of the graft copolymer (B), the resulting graft copolymer (B) ) is preferable because it has excellent thermal stability. In this case, the ratio of aromatic vinyl such as styrene to vinyl cyanide such as acrylonitrile is preferably 20 to 40% by mass of vinyl cyanide to 80 to 60% by mass of aromatic vinyl (however, 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) to 30 to 90% by mass of the composite rubbery polymer (A). This is preferable because the thermoplastic resin molded product obtained using this graft copolymer (B) has an excellent appearance (however, the total amount of the composite rubbery polymer (A) and vinyl compound (b) is 100% by mass). ). This proportion is more preferably 40 to 70% by weight of the composite rubbery polymer (A) and 60 to 30% by weight of the vinyl compound (b).

As a method for graft polymerizing 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-mentioned emulsion polymerization etc. , a single-stage or multi-stage polymerization method. When polymerizing in multiple stages, it is preferable to polymerize by adding the vinyl compound (b) in portions or continuously in the presence of the rubber latex of the composite rubbery polymer (A). By such a polymerization method, good polymerization stability can be obtained, and a latex having a desired particle size and particle size distribution can be stably obtained. Examples of the polymerization initiator used in this graft polymerization include those similar to the above-mentioned radical polymerization initiators used in the production of the composite rubbery polymer (A) of the present invention.

When polymerizing the vinyl compound (b) into the composite rubbery polymer (A), the latex of the composite rubbery polymer (A) is stabilized, and the average particle diameter of the resulting graft copolymer (B) is Emulsifiers can be added for control. The emulsifier used here is not particularly limited, but includes those similar to the above-mentioned emulsifier used in the production of the composite rubbery polymer (A) of the present invention, and anionic emulsifiers and nonionic emulsifiers are preferred. The amount of emulsifier used when graft polymerizing the vinyl compound (b) to the composite rubbery polymer (A) is not particularly limited, but is 0.01 parts by mass per 100 parts by mass of the resulting graft copolymer (B). The amount is preferably 10 parts by weight, more preferably 0.02 to 5 parts by weight.

Methods for recovering the graft copolymer (B) from the latex of the graft copolymer (B) obtained by emulsion polymerization are not particularly limited, but include the following methods.
The latex of the graft copolymer (B) is poured into hot water in which a coagulant is dissolved, and the graft copolymer (B) is solidified. Next, the solidified graft copolymer (B) is redispersed in water or warm 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 using a dehydrator or the like, and the resulting solid is dried using a flash dryer or the like to recover the graft copolymer (B) as powder or particles.

Examples of the coagulant include inorganic acids (sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, etc.), metal salts (calcium chloride, calcium acetate, aluminum sulfate, etc.), and the like. The coagulant is appropriately selected depending on the type of emulsifier. For example, if only a carboxylate salt (fatty acid salt, rosin acid soap, etc.) is used as an emulsifier, any coagulant may be used. When an emulsifier that exhibits stable emulsifying power even in an acidic region, such as sodium alkylbenzenesulfonate, is used as an emulsifier, an inorganic acid is insufficient and a metal salt must be used.

The volume average particle diameter of the graft copolymer (B) of the present invention is preferably 50 to 250 nm, more preferably 60 to 200 nm.
When the volume average particle diameter of the graft copolymer (B) is at least the above lower limit, stable production is possible, and when it is at most the above upper limit, the resulting thermoplastic resin molded product has good appearance characteristics.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present invention contains the water repellency imparting agent of the present invention consisting of the above-mentioned graft copolymer (B), and usually contains the water repellency imparting agent of the present invention and other thermoplastic resins. It is made by mixing. By blending the water repellency imparting agent of the present invention in the thermoplastic resin composition of the present invention, the content of the water repellency imparting agent of the present invention satisfies the above-mentioned surface Si amount and imparts the desired water repellency. Although there is no particular limitation as long as the effect can be obtained, the following composite rubbery polymer (A) content and silicone rubbery polymer (S) content are preferred.

<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 amount is preferably 10 to 50% by weight based on 100% by weight of the components.
If the content of the composite rubbery polymer (A) in the thermoplastic resin composition is less than the above-mentioned lower limit, the above-mentioned surface Si amount may not be satisfied, and a sufficient water repellency imparting effect cannot be obtained. The stain resistance may also be insufficient. Even if the content of the composite rubbery polymer (A) exceeds the above upper limit, it may not satisfy the above-mentioned surface Si content, and there is no difference in the water repellency improvement effect, but rather the water repellency and stain resistance decrease. There is a tendency to
The content of the composite rubbery polymer (A) is more preferably 20 to 45% by mass, and even 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 refers to the combination 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. This is the total and corresponds to components other than the below-mentioned additives that are normally included in the thermoplastic resin composition.

<Content of silicone rubber polymer (S)>
Containment of the silicone 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 weight based on 100% by weight of the resin component in the thermoplastic resin composition.
If the content of this silicone-based rubbery polymer (S) is less than the above lower limit, the above-mentioned surface Si amount may not be satisfied, a sufficient water repellent effect cannot be obtained, and the stain resistance is also insufficient. There are cases. Even if the content of the silicone-based rubbery polymer (S) exceeds the above upper limit, it may not satisfy the above-mentioned surface Si content, and there is no difference in the water repellency improvement effect, but rather the water repellency and stain resistance There is a tendency to decrease.
The content of the silicone rubbery polymer (S) is more preferably 4 to 20% by mass, and even more preferably 7 to 15% by mass, based on 100% by mass of the resin component in the thermoplastic resin composition.
Note that the resin components in the thermoplastic resin composition are as described above.

The thermoplastic resin composition of the present invention contains the water repellency imparting agent of the present invention, satisfies the above-mentioned surface Si content, and further contains the above-mentioned composite rubbery polymer (A) content and silicone-based rubbery polymer (S). It is preferable to include it so as to satisfy the content. 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, Although it varies depending on the content of the silicone-based rubbery polymer (S) contained in the composite rubbery polymer (A), it is usually in a total of 100 parts by mass of the water repellent agent of the present invention and other thermoplastic resin. It is preferred that the water repellency imparting agent of the present invention be contained in an amount of 10 to 80 parts by mass, particularly 20 to 70 parts by mass. If the content of the water repellent agent of the present invention is within the above range, the 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. tends to be good.

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 Polyesters such as butylene terephthalate, polyphenylene ether-polystyrene composites, polypropylene, olefin resins such as polyethylene, acrylonitrile-styrene-butadiene copolymers, styrene-maleic anhydride copolymers, polyphenylene ether resins, polyoxymethylene resins , polysulfone resin, polyacrylate resin, polyphelene resin, thermoplastic polyurethane, and the like. Among these, acrylonitrile-styrene copolymer is preferred from the viewpoint of impact resistance and fluidity.

The thermoplastic resin composition of the present invention may contain additives that are blended into ordinary thermoplastic resin compositions, if necessary.
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, weathering agents, Examples include mold release agents, plasticizers, antistatic agents, and the like.
As described above, these additives may be added in the step of preparing a pre-emulsion during the production of the composite rubbery polymer (A) of the present invention.

<Method for manufacturing thermoplastic resin composition>
The thermoplastic resin composition of the present invention is obtained by mixing and dispersing the water repellency imparting agent of the present invention and, if necessary, other thermoplastic resins and additives using a V-type blender, Henschel mixer, etc. It is produced by melt-kneading the mixture using a kneading machine such as an extruder, Banbury mixer, pressure kneader, or roll.
There is no particular restriction on the mixing order of each component, as long as all components are mixed uniformly.

<Method for molding thermoplastic resin composition>
The molded article of the present invention obtained by molding the thermoplastic resin composition of the present invention is excellent in water repellency, stain resistance, and durability thereof. In addition, by adjusting other thermoplastic resins used in combination and their blending amounts, it is possible to obtain excellent impact resistance, mechanical properties such as rigidity, and molded 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, pressure molding, calendar molding, and inflation molding. Can be mentioned. Among these, the injection molding method and the injection compression molding method are preferable because they are excellent in mass production and can obtain molded products with high dimensional accuracy.

[Application]
The molded article of the present invention is excellent in water repellency and stain resistance, and its durability, and is therefore suitable for use as a member whose surface is likely to become dirty due to adhesion of water droplets or muddy water. For example, the surfaces of vehicle components (mudguards, emblems, etc.), building materials (wall materials, window frames, etc.), exterior components, home appliance housings, office equipment, air conditioner housings, toilet fixtures, bathroom fixtures, etc. have excellent repellency. Because it is water-based, it repels water, prevents the adhesion of water scale, scale, and mud stains, and can easily remove adhering stains.

The present invention will be described in more detail below with reference to Synthesis Examples, Examples, and Comparative Examples; however, the present invention is not limited to the following Examples unless it exceeds the gist thereof.
In the following, "part" means "part by mass" and "%" means "% by mass."

[Measurement of volume average particle diameter]
Silicone rubber polymers (S-1), composite rubber polymers (A-1) to (A-3), and graft copolymers (B-1) produced in Synthesis Examples, Examples, and Comparative Examples The volume average particle diameters of (B-3) and ABS graft copolymer (X-1) were determined by dynamic light scattering using Nanotrac UPA-EX150 manufactured by Nikkiso Co., Ltd.

[Production of silicone rubber 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, and the mixture was stirred for 2 minutes at 10,000 rpm in a homomixer, and then transferred to a homogenizer at a pressure of 300 kg/ ^cm2 . A stable premixed organosiloxane latex was obtained by circulation.

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 tube, a jacket heater, and a stirring device to prepare a 10% aqueous solution of dodecylbenzenesulfonic acid. . While this aqueous solution was heated to 85° C., the premixed organosiloxane latex was added dropwise over a period of 4 hours, and after the completion of the dropwise addition, the temperature was maintained for 1 hour and cooled. Next, the mixture was neutralized with a 10% aqueous sodium hydroxide solution to obtain a latex (solid content: 18.2%) of silicone rubbery polymer (S-1). Silicone Rubber Polymer (S-1) The volume average particle diameter of the silicone rubber polymer (S-1) dispersed in the latex was 50 nm.

[Manufacture and evaluation of composite rubbery polymer (A)]
<Synthesis Example II-1: Production of composite rubbery polymer (A-1)>
A composite rubbery polymer (A-1) was produced using the following formulation.

(Composition)
Silicone rubbery polymer (S-1) latex (as solid content) 14 parts Sodium polyoxyethylene alkyl phenyl ether sulfate 0.2 parts n-Butyl acrylate (BA) 86 parts Allyl methacrylate (AMA) 0.52 Parts 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 Water 430 parts

14 parts of silicone rubbery polymer (S-1) latex (as solid content), 430 parts of ion-exchanged water, and 430 parts of ion-exchanged water were placed in a nitrogen-purged reactor equipped with a reagent injection container, a cooling tube, a jacket heater, and a stirring device. Sodium oxyethylene alkyl phenyl ether sulfate 0.2 parts, n-butyl acrylate 86 parts, allyl methacrylate 0.52 parts, 1,3-butylene glycol dimethacrylate 0.17 parts, t-butyl hydroperoxide 0.22 parts was charged, and the inside of the reaction vessel was purged 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 polymerization heat generation was confirmed, the internal temperature was set to 75°C, and the polymerization was continued until the polymerization heat generation was no longer confirmed, and the polymerization was maintained for 60 minutes to complete the polymerization of the acrylic ester component and form a composite rubbery polymer (A- The latex of 1) was obtained. The solid content of the composite rubbery polymer (A-1) in the obtained latex was 19.1%, and the volume average particle diameter was 90 nm.

<Synthesis Examples II-2 to II-3: Production of composite rubber polymers (A-2) to (A-3)>
Synthesis Example II-1 except that the amounts of silicone rubbery polymer (S-1), n-butyl acrylate, allyl methacrylate, and 1,3-butylene glycol dimethacrylate were changed as shown in Table 1. In the same manner, latexes of composite rubbery polymers (A-2) to (A-3) were obtained.
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 rubber polymer (S-1)/n-butyl acrylate mass ratio of each composite rubber 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)>
Raw materials were charged in the following formulation into a reactor equipped with a reagent injection container, a cooling tube, a jacket heater, and a stirring device, and the internal temperature was raised to 75° C. while stirring.

(Composition)
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, a mixed solution containing acrylonitrile (AN), styrene (ST), and t-butyl hydroperoxide in the following formulation was added dropwise over 100 minutes while the temperature was raised to 80°C.

(Composition)
Acrylonitrile (AN) 12.5 parts Styrene (ST) 37.5 parts t-Butyl hydroperoxide 0.2 parts

After completion of the dropwise addition, the temperature was maintained at 80° C. for 30 minutes and then cooled to obtain a latex of graft copolymer (B-1). The solid content of the graft copolymer (B-1) in the obtained latex was 28.6%, the volume average particle diameter was 120 nm, and the grafting rate was 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 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 further raised to 95°C and held for 10 minutes.
Next, the solidified product was 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)>
The procedure was the same as in Synthesis Example II-1, except that the latex of composite rubber polymers (A-2) to (A-3) was used instead of the latex of composite rubber polymer (A-1). Graft copolymers (B-2) to (B-3) were obtained, respectively.

The raw material composition, volume average particle diameter, and grafting ratio of the produced graft copolymers (B-1) to (B-3) are summarized in Table 2.

In addition, 20 g of graft copolymer (B-1) and (B-2) powders were each weighed into a cylindrical container (diameter 5.6 cm), and a 20 kg weight was placed so that the powder was evenly loaded. It was placed on the tube and left for 2 hours in an environment at a temperature of 35° C., and the powders of the graft copolymers (B-1) and (B-2) were formed into blocks. The block-shaped graft copolymers (B-1) and (B-2) are placed on a sieve with an opening of 3.35 mm, and the time required for the sieving rate to reach approximately 100% using a sieve shaker. The blocking resistance was evaluated by measuring the time required for almost the entire amount to fall from the sieve, and the results are also listed in Table 2. The shorter this time is, the better the blocking resistance is, and if it is 100 seconds or less, it is judged that the blocking resistance 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), a monomer mixture consisting of 32.2 parts of styrene, 13.8 parts of acrylonitrile, 1.3 parts of disproportionated potassium rosin acid, 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, and the reaction was started at 60°C, and the temperature was raised to 70°C in the middle. After heating for 2 and a half hours, emulsion graft polymerization was completed. The latex of the reactive organism was coagulated with an aqueous sulfuric acid solution, washed with water, and then dried to obtain an ABS resin (X-1) (hereinafter referred to as "graft copolymer (X-1)"). The grafting rate of the graft copolymer (X-1) was 55%, and the volume average particle diameter was 320 nm.

[Manufacture and evaluation of AN-ST thermoplastic resin composition]
<Examples 1 to 10, Comparative Examples 1 to 5: Production of thermoplastic resin composition>
Graft copolymers (B-1) to (B-3), (X-1) in the proportions shown in Table 3 and acrylonitrile (AN)-styrene (ST) copolymer (TECHNO "UMG AXS Resin S202N" manufactured by UMG Co., Ltd.) and the silicone oil masterbatch described below for Comparative Examples 1 to 5 were blended in the proportions shown in Table 3 (However, in Comparative Example 1, acrylonitrile-styrene co- Polymer only) and 0.5 part of carbon black were added and mixed using a Henschel mixer.
Silicone oil masterbatch: "Crimbell CB-50AB" manufactured by Fuji Chemical Co., Ltd. (silicone oil masterbatch with silicone oil/ABS resin = 50/50 (mass ratio))
This mixture was supplied to an extruder heated to 220°C and kneaded to obtain pellets of a thermoplastic resin composition.

<Preparation of sample molded body>
The pellets of the above thermoplastic resin composition were molded using a J85AD-110H manufactured by Japan Steel Works, Ltd. 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 molded body having a length of 86 mm, a width of 50 mm, and a thickness of 3 mm was obtained.
However, in Comparative Example 5, the screw slipped during molding, making it impossible to measure and molding was impossible. For this reason, it was not possible to perform the following evaluation.

<Evaluation>
(Molded appearance: evaluation of color development)
The lightness L* of the sample molded article was measured using a spectrophotometer ("CM-3500d" manufactured by Konica Minolta Optics, Inc.) using the SCE method. Let the measured L* be "L*(ma)". The lower the L*, the blacker the color, and the better the color development was judged to be.
"Lightness L*" means the lightness value (L*) of the color values in the L*a*b* color system adopted in JIS Z 8729.
The "SCE method" refers to a method of measuring color by using a spectrophotometer compliant with JIS Z 8722 and removing specularly reflected light using an optical trap.

(Molded appearance: Measurement of surface gloss)
Using "Digital Variable Gloss Meter UGV-5D" manufactured by Suga Test Instruments Co., Ltd., in accordance with JIS K 7105, reflectance (%) of the surface of the test molded object at an incident angle of 60° and a reflection angle of 60° was measured. The higher the reflectance, the better the surface appearance.

(Measurement of surface Si amount (fluorescent X-ray analysis))
The surface of the sample molded body was measured using a fluorescence Fluorescent X-ray analysis was performed under the condition of a current of 100 μA, and the Si detection intensity of 1.60 to 1.88 keV was taken as the amount of surface Si.

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

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

(Antifouling property: evaluation of degree of adhesion of muddy water)
The test molded body was set at an inclination angle of 45°, and 50 mL of the following muddy water was sprayed onto the inclined surface of the molded body from the lotus mouth of a watering can. After air drying, the surface on which the mud was sprayed was observed, and the ratio (percentage) of the adhering area of the dried solidified mud to the area of the plate surface of the molded body was visually estimated and evaluated according to the following criteria. The higher the score, the better the water repellency and stain resistance.
Mud 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: Adhesive area ratio almost 100%
2 points: Adhesive area ratio approximately 80-100%
3 points: Adhesive area ratio approximately 50-80%
4 points: Adhesive area ratio approximately 20-50%
5 points: Almost no adhesion.

The evaluation of water repellency and stain resistance was performed on molded products that had been degreased using the method described below. Through this evaluation, water repellency and stain resistance were demonstrated without being affected by the degreasing treatment. In other words, it can be seen that the water repellency and stain resistance are excellent in durability.
(Degreasing method)
The molded article was degreased by lightly wiping it with absorbent cotton impregnated with isopropyl alcohol.

The results of Examples 1 to 10 and Comparative Examples 1 to 4 are shown in Table 3.

Table 3 shows that the molded products of Examples 1 to 10, which correspond to the present invention, have excellent water repellency and stain resistance. Further, from the surface Si amount in Examples 1 to 10, the content of the composite rubbery polymer (A) of the thermoplastic resin composition, and the content of the silicone rubbery polymer (S), the surface Si amount was 200 to 200. In the range of 300 cps, the content of the composite rubbery polymer (A) of the thermoplastic resin composition is in the range of 25 to 45% by mass, and the content of the silicone rubbery polymer (S) is 7 to 15% by mass. It can be seen that the range is particularly excellent in terms of the effect of imparting water repellency.
By adding the water repellency imparting agent of the present invention, the moldability and molded appearance are hardly impaired, and the molded appearance is superior to Comparative Examples 2 to 4 in which ordinary ABS resin is mixed.

Claims (2)

A molded product formed by molding a thermoplastic resin composition,
The thermoplastic resin composition is obtained by graft polymerizing a vinyl compound (b) to a composite rubbery polymer (A) formed by combining a silicone rubbery polymer (S) with a (meth)acrylic acid ester. Contains a water repellency imparting agent consisting of a graft copolymer (B) consisting of
The proportion of the silicone rubber polymer (S) in the total 100% by mass of the silicone rubber polymer (S) and (meth)acrylic acid ester used in the production of the composite rubber polymer (A) is 10 to 10%. 65% by mass, the proportion of (meth)acrylic ester is 90 to 35% by mass,
The grafting ratio of the graft copolymer (B) is 30 to 85%,
The content of the composite rubbery polymer (A) is 10 to 50% by mass based on 100% by mass of the resin component in the thermoplastic resin composition,
A molded product with a surface Si content of 50 to 400 cps as measured by the following fluorescent X-ray analysis.
<Fluorescence 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 x 0.5 mm, excitation voltage 50 kV, tube current 100 μA. The Si detection intensity of ~1.88 keV is taken as the surface Si amount. The molded article according to claim 1, wherein the surface has a water contact angle of 90° or more and a water sliding angle of 20° or less.