JP2005132996A - Sulfonic acid group-containing aqueous dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sulfonic acid group-containing aqueous dispersion increasing a hydrophilic group content while retaining sufficient water resistance, having small volume resistance and improved in a film-forming property. <P>SOLUTION: The sulfonic acid group-containing aqueous dispersion comprises polymer particles containing a polyorganosiloxane as an essential component and an aqueous medium and further comprises a sulfonic acid group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to an aqueous dispersion containing a polymer having a hydrophilic group in the molecule. More specifically, the present invention relates to a binder, a coating material, a coating material for a battery separator, preferably a battery electrolyte, a fuel cell The present invention relates to a sulfonic acid group-containing aqueous dispersion that can be used for a molecular solid electrolyte, a solid capacitor, an ion exchange membrane, various sensors, and the like.

Conventionally, polymers having hydrophilic groups such as sulfonic acid groups, carboxyl groups (carboxylic acid groups), and phosphoric acid groups are known. Surfactants, emulsifiers, dispersants, polymer solid electrolytes, ion exchange membranes It is used for such as. On the other hand, in recent years, binders have been utilized by taking advantage of such characteristics as dispersibility of hydrophilic groups, hydrophilicity, ion trapping properties, small volume resistance (hereinafter sometimes referred to as small resistance), and adhesion to substrates. Applications to resins, coating materials, surface treatment agents, and battery electrolytes are being studied. In particular, a sulfonic acid group-containing polymer has the strong ionic property of a sulfonic acid group, and thus easily exhibits the above characteristics, and its applicability has been attracting attention. For example, Patent Document 1 or Patent Document 2 proposes application of a polymer copolymerized with acrylamide sulfonic acid to an ion exchange membrane or a polymer electrolyte for a fuel cell.

However, a hydrophilic group-containing polymer such as a sulfonic acid group is resistant to water when the content of the hydrophilic group is higher than a certain level due to the hydrophilic property of the hydrophilic group, in other words, water solubility. For example, when used as a film material, binder material, or coating material, the film significantly expands in the presence of water, resulting in a significant decrease in the mechanical strength of the film or peeling from the substrate. There is a problem that it tends to occur and the durability is lowered. For this reason, the content of the hydrophilic group is limited, and the characteristics such as small resistance and hydrophilicity have not been sufficiently exhibited.

Further, organic-inorganic composite materials are disclosed in Patent Document 3, Patent Document 4, and Patent Document 5 as sulfonic acid group-containing materials having relatively good water resistance. However, these materials have a drawback of poor film formability. In addition, although water-based materials that can reduce organic solvents have been demanded in consideration of recent environmental problems, sulfonic acid group-containing water-based materials composed of organic-inorganic composites have been put to practical use to a level that can be used industrially. Not.
Japanese Patent Laid-Open No. 11-302410 JP 2002-343381 A JP 2000-90946 A JP 2001-307752 A JP 2001-307752 A

An object of the present invention is to provide a sulfonic acid group-containing aqueous dispersion in which hydrophilic group content is increased while maintaining sufficient water resistance, volume resistance is small, and film formability is improved.

The present invention provides an aqueous dispersion containing polymer particles containing polyorganosiloxane as essential components and an aqueous medium, and further containing an aqueous dispersion containing a sulfonic acid group.
In the aqueous dispersion of the present invention, the average particle diameter of the polymer particles is preferably 0.002 to 1 μm, and the sulfonic acid group is preferably contained in an amount of 0.2 to 5 mmol / g. . Furthermore, in the aqueous dispersion of the present invention, the volume resistance of the solid obtained by evaporating the aqueous medium is preferably 10 ⁻² to 10 ³ Ω · cm.

In addition, according to the present invention, the following (A) to (D) components are mixed, and an aqueous dispersion is obtained by performing radical polymerization as required, including the step of reducing the average particle size of the emulsion to 1 μm or less. A method for producing an aqueous dispersion is provided.
(A) General formula (1)
_{^{(R 1) n -Si- (OR}} 2) 4-n ...... (1)
(Wherein the same or different when R ¹ is present twice, a monovalent organic group of the phenyl group or 1 to 8 carbon atoms, R ² are the same or different, an alkyl group or a carbon number of 1 to 5 carbon atoms An acyl group of 1-6, n is an integer of 0-2)
1 to 100 parts by weight (B) radical polymerizable monomer 99 to 0 parts by weight [provided that (A) + ( B) = 100 parts by weight]
(C) 0.1-50 parts by weight of emulsifier [provided that (A) + (B) = 100 parts by weight]
(D) 50 to 2,000 parts by weight of water [provided that (A) + (B) = 100 parts by weight]
In the above-described method for producing an aqueous dispersion, the components (A) to (D) are mixed and before and / or after the average particle size of the emulsion is reduced to 1 μm or less, The catalyst (E) that promotes the decomposition / condensation reaction is preferably used in combination, and when the component (B) is used, the radical polymerization initiator (F) is preferably used.

According to the aqueous dispersion of the present invention, there are excellent effects that the hydrophilic group content is increased while maintaining sufficient water resistance, the volume resistance is small, and the film formability is improved.

Hereinafter, the present invention will be sequentially described.
<Polyorganosiloxane>
The aqueous dispersion of the present invention contains polyorganosiloxane as an essential component. In the polyorganosiloxane, silanol groups of the hydrolyzate of organosilane are condensed to form Si—O—Si bonds, but in the present invention, it is not necessary that all of the silanol groups are condensed. It is also a concept that includes a mixture of those having a silanol group condensed or a mixture of those having different degrees of condensation.

The polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) of the polyorganosiloxane is preferably 800 to 1,000,000, and more preferably 1,000 to 500,000. When the Mw of the polyorganosiloxane is less than 800, the storage stability of the aqueous dispersion may be inferior, and when the Mw exceeds 1,000,000, the film formability may be inferior. Mw is measured using polystyrene as a standard substance by a gel permeation chromatography (abbreviated as GPC) method that has been widely adopted as a general measurement method.

The amount of the polyorganosiloxane is preferably 1 to 100% by weight, more preferably 10 to 90% by weight, based on the total solid content contained in the aqueous dispersion. When the amount of the polyorganosiloxane is less than 1% by weight, the water resistance is poor.

<Average particle size>
The aqueous dispersion of the present invention contains polymer particles containing polyorganosiloxane as an essential component, preferably having an average particle diameter of 0.002 to 0.5 μm, more preferably 0.01 to 0.2 μm. In the present invention, the average particle diameter of the polymer particles is a volume average particle diameter determined by measurement based on the light scattering method. When the average particle diameter of the polymer particles is less than 0.002 μm, the storage stability is inferior, and when it exceeds 0.5 μm, the water resistance may be inferior or the storage stability may be inferior.

<Sulfonic acid group>
The sulfonic acid group-containing aqueous dispersion of the present invention contains a sulfonic acid group.
Examples of the location of the sulfonic acid group in the aqueous dispersion include the inside of the polymer particles, the surface of the polymer particles, and in the aqueous medium. Examples of the existence form of the sulfonic acid group include a form covalently bonded to the polyorganosiloxane, a form covalently bonded to a polymer other than the polyorganosiloxane, and a form present in an emulsifier or an inorganic salt. A specific method for introducing a sulfonic acid group will be described in the description of the production method described later.
The amount of the sulfonic acid group is preferably 0.2 to 5 mmol / g, more preferably 0.5 to 4 mmol / g, and most preferably 1 to 3 mmol / g in the solid content. If it is less than 0.2 mmol / g, the volume resistance is large, and if it exceeds 5 mmol / g, the water resistance is poor.

<Aqueous medium>
The aqueous medium in the aqueous dispersion of the present invention consists essentially of water, but in some cases, an organic solvent such as alcohol may be contained up to about several weight percent. Specific amounts of water and organic solvents will be described later in the description of the production method.

<Volume resistance>
The aqueous dispersion of the present invention preferably has a solid volume resistance after drying of 10 ⁻² to 10 ³ Ω · cm, more preferably 10 ⁻² to 10 ² Ω · cm. The volume resistance of the solid after drying in the present invention means that the aqueous medium is evaporated from the aqueous dispersion while adding a crosslinking agent, an organic solvent, etc., which will be described later, to the aqueous dispersion, if necessary, and heating as necessary. This refers to the volume resistance when a film-like solid having a thickness of 1 mm or less is cured in water at 25 ° C. for 24 hours. The volume resistance in the present invention can be obtained by bringing an electrode into contact with a film wet at 25 ° C. and measuring the AC impedance. The measurement electrode is preferably one that does not involve a chemical reaction due to a voltage load, for example, platinum. The resistance measuring device is not particularly limited as long as it is a general impedance meter, and the measurement frequency is, for example, about 1 kHz.

<About each component in a manufacturing method and a manufacturing method>
The aqueous dispersion of the present invention includes the steps of mixing the following components (A) to (D), and further, if necessary, the component (E) to refine the average particle size of the emulsion to 1 μm or less. The component (F) is added according to the above and radical polymerization is performed.

Component (A) The organosilane (hereinafter also referred to as “organosilane (i)”) in the component (A) constituting the aqueous dispersion of the present invention is generally represented by the following general formula (1).
(R ¹ ) _n Si (OR ² ) _4-n (1)
(In the formula, R ^1, same or different when there are two pieces, a monovalent organic group having 1 to 8 carbon atoms, R ² are the same or different, 1 to 5 carbon atoms alkyl group or a C An acyl group of 1 to 6 is shown, and n is an integer of 0 to 2.)

The hydrolyzate of the organosilane (i) is not necessarily required to have all the OR ² groups in the general formula (1) contained in the organosilane contained in 2 to 4 hydrolyzed, for example, only one. May be hydrolyzed, two or more may be hydrolyzed, or a mixture thereof.

The organosilane (i) condensate is formed by condensation of silanol groups of organosilane hydrolyzate to form Si—O—Si bonds. In the present invention, all silanol groups are condensed. It is a concept that includes a mixture of a small part of silanol groups, a mixture of those having different degrees of condensation, and the like.

In the general formula (1), examples of the monovalent organic group having 1 to 8 carbon atoms of R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group. Group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and other alkyl groups; acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group Acyl groups such as trioyl group and caproyl group; vinyl group, allyl group, cyclohexyl group, phenyl group, epoxy group, glycidyl group, (meth) acryloxy group, ureido group, amide group, fluoroacetamide group, isocyanate group, etc. In addition to these, substituted derivatives of these groups can be mentioned.

Examples of the substituent in the substituted derivative of R ¹ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, and a (meth) acryloxy group. Ureido group, ammonium base and the like. However, the number of carbon atoms in R ¹ consisting of substituted derivatives thereof is 8 or less including the carbon atoms in the substituent.

An aqueous dispersion having a small volume resistance is obtained by selecting and sulfonating the component (A) having R ¹ containing a functional group capable of introducing a sulfonic acid group by sulfonation, such as an epoxy group, a mercapto group, or a vinyl group. Can do.
In the general formula (1), when two R ^{1 s} are present, they may be the same as or different from each other.

Examples of the alkyl group having 1 to 5 carbon atoms of R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, and n. -A pentyl group etc. can be mentioned, As a C1-C6 acyl group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, a caproyl group etc. can be mentioned, for example.
A plurality of R ² present in the general formula (1) may be the same as or different from each other.

Specific examples of such organosilane include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane; methyltrimethoxysilane , Methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane , N-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxy Silane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyl Trimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrime Xysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxy Trialkoxysilanes such as silane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldi Ethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyl Diethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n- Heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, etc. In addition to alkoxysilanes, methyltri Cetyl silane, dimethyl di acetyloxy silane can be exemplified.

Of these, trialkoxysilanes and dialkoxysilanes are preferably used, and examples of trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane. Further, dialkoxysilanes are preferably dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane.

The component (A) is at least one selected from organosilane (i), a hydrolyzate of the organosilane, and a condensate of the organosilane. That is, the component (A) may be only one of these three types, a mixture of any two types, or a mixture including all three types. In the present invention, the condensate of organosilane is also referred to as “polyorganosiloxane”. When polyorganosiloxane is used as the component (A) in the production of the aqueous dispersion of the present invention, the polymerization stability when the vinyl compound is polymerized is remarkably improved, and it can be polymerized at a high solid content, so that it can be industrialized easily. There are advantages.

Polyorganosiloxane is used as a condensate of organosilane by previously hydrolyzing and condensing organosilane. At this time, when preparing the polyorganosiloxane, it is preferable to hydrolyze and condense the organosilane by adding an appropriate amount of water to the organosilane and, if necessary, an organic solvent.
Here, the usage-amount of water is 1.2-3.0 mol normally with respect to 1 mol of organosilane, Preferably it is about 1.3-2.0 mol.

In this case, the organic solvent used as necessary is not particularly limited as long as it can uniformly mix the polyorganosiloxane and the later-described component (B). For example, alcohols, aromatic hydrocarbons, There may be mentioned ethers, ketones, esters and the like.

Among these organic solvents, specific examples of alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n -Octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, diacetone alcohol and the like.

Specific examples of aromatic hydrocarbons include benzene, toluene and xylene, specific examples of ethers include tetrahydrofuran and dioxane, and specific examples of ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Specific examples of esters such as diisobutylketone and the like include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate.
These organic solvents can be used alone or in admixture of two or more.
When the organic solvent is contained in the polyorganosiloxane, the organic solvent can be removed from the aqueous dispersion before the condensation / polymerization reaction described later.

Commercially available products of polyorganosiloxane include MKC silicate manufactured by Mitsubishi Chemical Corporation, ethyl silicate manufactured by Colcoat, modified silicone oils manufactured by Toray Dow Corning Silicone (trade names: SF series, SH series), GE Silicone varnish for modification made by Toshiba Silicone (trade name: TSR series), silicone resin (trade name: TSR series), hydroxy-terminated dimethylpolysiloxane (trade name: YF series), silicone alkoxy oligomer made by Shin-Etsu Chemical Co., Ltd. ( (Product name: X series, KR series), hydroxyl group-containing polydimethylsiloxane manufactured by Dow Corning Asia, NUC-reactive silicone oil (product name: FZ series) manufactured by Nihon Unicar, glass resin manufactured by Showa Denko There are , Or it may be used by further condensation.

(B) The radically polymerizable monomer (B) is not particularly limited as long as it is a monomer having an unsaturated double bond capable of radical polymerization.

Examples of the component (B) include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t -Butyl (meth) acrylylate, amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, cyclohexyl methacrylate, etc. (Meth) acrylic acid esters; hydroxyl-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate; ethylene glycol Di (meta) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, tetrapropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyfunctionality such as pentaerythritol tetra (meth) acrylate ( (Meth) acrylic acid esters; trifluoroethyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate, octafluoropentyl Fluorine atom-containing (meth) acrylic esters such as (meth) acrylate and pentadecafluorooctyl (meth) acrylate; 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) Examples include amino group-containing (meth) acrylic esters such as acrylate; and (meth) acrylic compounds such as epoxy group-containing (meth) acrylic esters such as glycidyl (meth) acrylate.

In addition, the component (B) includes styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxy. Styrene, 3,4-dimethylstyrene, 3,4-diethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chloro-3-methylstyrene, 4-t-butylstyrene, 2,4-dichlorostyrene, 2 Aromatic vinyl monomers such as 1,6-dichlorostyrene and 1-vinylnaphthalene;

Tetrafluoroethylene, hexafluoropropylene, 3,3,3-trifluoropropylene, chlorotrifluoroethylene, methyl trifluorovinyl ether, ethyl trifluorovinyl ether, methoxyethyl trifluorovinyl ether, ethoxyethyl trifluorovinyl ether, perfluoro (methyl vinyl ether) Fluoroolefins and fluoroolefin derivatives such as perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether), perfluoro (propoxypropyl vinyl ether);
Other polyfunctional monomers such as divinylbenzene;

(Meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-normalpropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hexyl ( (Meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-2-ethylhexyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N- Acid amide compounds such as butoxymethyl (meth) acrylamide, N, N′-methylenebisacrylamide, diacetone acrylamide, maleic acid amide, maleimide;

Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile;
4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1, Piperidine monomers such as 2,2,6,6-pentamethylpiperidine;
Other examples include dicaprolactone.

Furthermore, as the component (B) having a functional group, for example, unsaturated carboxylic acids other than the above, such as crotonic acid, maleic acid, fumaric acid, and itaconic acid; unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride ; (Meth) acrylamide sulfonic acids such as acrylamide t-butyl sulfonic acid; phosphoric acid group-containing (meth) acrylic esters such as 2- (meth) acryloyloxyethyl acid phosphate; other than the above such as 2-hydroxyethyl vinyl ether; Hydroxyl group-containing vinyl monomers; amino group-containing vinyl monomers such as 2-aminoethyl vinyl ether; 1,1,1-trimethylamine (meth) acrylimide, 1-methyl-1-ethylamine (meth) acrylimide 1,1-dimethyl-1- (2-hydroxypropyl) amine (me ) Acrylimide, 1,1-dimethyl-1- (2'-phenyl-2'-hydroxyethyl) amine (meth) acrylimide, 1,1-dimethyl-1- (2'-hydroxy-2'-phenoxypropyl) ) Amine imide group-containing vinyl monomers such as amine (meth) acrylimide; Epoxy group-containing vinyl monomers other than the above such as allyl glycidyl ether.

Among the above components (B), (meth) acrylic acid, (meth) acrylic compounds, acid amide compounds, and (meth) acrylamide sulfonic acids are preferable, and among them, acrylic acid, methacrylic acid, trifluoroethyl (meth) Acrylate, hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, pentadecafluorooctyl (meth) acrylate, N-isopropyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, acrylamide t-butylsulfonic acid Is particularly preferred.

By using a monomer having a sulfonic acid group such as acrylamide t-butylsulfonic acid, the sulfonic acid group can be directly introduced into the organic-inorganic composite, and the volume resistance can be reduced. In addition, the volume resistance can be reduced by selecting and sulfonating the component (B) containing a functional group capable of introducing a sulfonic acid group by sulfonation, such as a phenyl group, an alcoholic hydroxyl group, an epoxy group, or a mercapto group. .
In addition, when the radically polymerizable monomer containing an acidic functional group is used in (B) component, since the effect excellent as (E) component mentioned later is shown, it is preferable.

The mixing ratio of the component (A) and the component (B) in the aqueous dispersion of the present invention is such that the total amount of the component (A) is preferably 1 to 100 parts by weight, more preferably 1 to 95 parts by weight, particularly preferably. 10 to 90 parts by weight, component (B) is preferably 99 to 0 parts by weight, more preferably 99 to 5 parts by weight, particularly preferably 90 to 10 parts by weight [provided that (A) + (B) = 100 parts by weight Part]. Here, about the component which acts as both (A) component and (B) component, such as 3- (meth) acryloxypropyl triethoxysilane, the weight is divided by 2 and (A) component and (B) component Shall be treated as
When the proportion of the component (B) exceeds 99 parts by weight, the deterioration of water resistance becomes remarkable, which is not preferable.

(C) As surfactants used as emulsifiers, anionic surfactants such as alkyl sulfates (salts), alkylaryl sulfates (salts), alkyl phosphates (salts), and fatty acids (salts); Cationic surfactants such as alkylamine salts and alkyl quaternary amine salts; Nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers and block polyethers; Carboxylic acid types (for example, amino acid types) ), Amphoteric surfactants such as sulfonic acid type, etc., under the trade names, Latemul S-180A (manufactured by Kao Corporation), Eleminol JS-2 (manufactured by Sanyo Kasei Co., Ltd.), Aqualon HS-10, KH-10 [Daiichi Kogyo Seiyaku Co., Ltd.], Adekaria soap SE-10N, SR-10 [Asahi Denka Kogyo Ltd.], Antox MS-60 [manufactured by Nippon Emulsifier Co., Ltd.], it is possible to use any of such reactive emulsifier such as.

By using an emulsifier having a sulfonic acid group such as an alkyl sulfate ester or an alkylaryl sulfate ester in an acid form, the volume resistance can be reduced.
In particular, use of a reactive emulsifier is preferable because of excellent water resistance.

Among the polymers having a hydrophilic group, those having a dispersing function can also be used as an emulsifier. Examples of such polymers include styrene / maleic acid copolymer, styrene / acrylic acid copolymer, polyvinyl alcohol, polyalkylene glycol, sulfonated polyisoprene, sulfonated hydrogenated styrene / butadiene copolymer, styrene / Examples thereof include a sulfonated product of a maleic acid copolymer and a sulfonated product of a styrene / acrylic acid copolymer. In particular, the volume resistance can be reduced by using a polymer having a sulfonic acid group in an acid form. Examples of such a polymer include a sulfonated product of polyisoprene, a sulfonated product of hydrogenated styrene / butadiene copolymer, a sulfonated product of styrene / maleic acid copolymer, and a sulfonated product of styrene / acrylic acid copolymer. Can do.

These emulsifiers can be used alone or in combination of two or more.
Although the usage-amount of an emulsifier is not specifically limited, 0.1-50 weight part normally with respect to 100 weight part of total amounts of (A) component and (B) component, Preferably it is 0.2-20 weight Parts, more preferably 0.5 to 5 parts by weight. If it is less than 0.1 part by weight, emulsification is not sufficient, and stability during hydrolysis / condensation and radical polymerization is unfavorable. On the other hand, when the amount exceeds 50 parts by weight, foaming and water resistance become problems, which is not preferable.

(D) Water The water used as the main component of the aqueous medium used in the production of the aqueous dispersion of the present invention may be water existing in the aqueous mixture of the component (A) added in advance, or Further, water added together with the emulsifier (C) may be added to the mixture of the component (A).
The amount of water used is not particularly limited, but is usually 50 to 2,000 parts by weight, preferably 80 to 1,000 parts by weight, with respect to 100 parts by weight of the total amount of component (A) and component (B). Parts, more preferably 100 to 500 parts by weight. If it is less than 50 parts by weight, emulsification is difficult or the stability of the emulsion after emulsification is lowered, which is not preferable. On the other hand, when the amount exceeds 2,000 parts by weight, productivity is lowered, which is not preferable.

(E) Hydrolysis catalysts (A) to (D) are mixed, and before and / or after the average particle size of the emulsion is reduced to 1 μm or less, the hydrolysis / condensation reaction of component (A) is promoted. A catalyst (E) may be used in combination.
By using the component (E), the polymerization stability is improved, and the molecular weight of the polysiloxane resin produced by the polycondensation reaction of the component (A) used is increased to obtain a material having excellent water resistance. Can do.

As such component (E), acidic compounds, alkaline compounds, salt compounds, amine compounds, organometallic compounds and / or partial hydrolysates thereof (hereinafter referred to as organometallic compounds and / or partial hydrolysates thereof) (Referred to as “organometallic compound etc.”).
Examples of the acidic compound include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl titanic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, phthalic acid, etc., preferably hydrochloric acid, sulfuric acid, phosphoric acid , Dodecylbenzenesulfonic acid.

Examples of the alkaline compound include sodium hydroxide and potassium hydroxide. However, since the volume resistance may increase, it is preferable not to use an alkaline compound.
Examples of the salt compounds include alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid.

Examples of the amine compound include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, m-phenylenediamine, p-phenylenediamine, ethanolamine, triethylamine, and 3-aminopropyl. Trimethoxysilane, 3-aminopropyl triethoxysilane, 3- (2-aminoethyl) -aminopropyl trimethoxysilane, 3- (2-aminoethyl) -aminopropyl triethoxysilane, 3- (2 -Aminoethyl) -aminopropyl-methyl-dimethoxysilane, 3-anilinopropyl-trimethoxysilane, alkylamine salts, quaternary ammonium salts, as well as various curing agents for epoxy resins Aminopropyl trimethoxysilane - like can be mentioned sex amines, preferably, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3- (2-aminoethyl).

Examples of the organometallic compound include a compound represented by the following general formula (2) (hereinafter referred to as “organometallic compound (2)”), an alkyl having 1 to 10 carbon atoms bonded to the same tin atom. Examples thereof include tetravalent tin organometallic compounds having 1 to 2 groups (hereinafter referred to as “organotin compounds”), partial hydrolysates of these compounds, and the like.

M (OR ³ ) _r (R ⁴ COCHCOR ⁵ ) _s (2)
Wherein, M represents zirconium, titanium or aluminum, R ³ and R ⁴ are the same or different, an ethyl group, n- propyl group, i- propyl, n- butyl group, sec- butyl group, t -A monovalent hydrocarbon group having 1 to 6 carbon atoms such as a butyl group, an n-pentyl group, an n-hexyl group, a cyclohexyl group, and a phenyl group, and R ⁵ has the same carbon number as R ³ and R ⁴ 1-6 monovalent hydrocarbon groups, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, lauryloxy group, stearyloxy Represents an alkoxyl group having 1 to 16 carbon atoms such as a group, and r and s are integers of 0 to 4, and (r + s) = (valence of M). ]

Specific examples of the organometallic compound (2) include
(I) Tetra-n-butoxyzirconium, tri-n-butoxyethylacetoacetatezirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n Organic zirconium compounds such as propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium;

(B) Tetra-i-propoxy titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (acetylacetate) titanium, di-i-propoxy bis (acetylacetone) titanium, etc. Organic titanium compounds;
(C) Tri-i-propoxyaluminum, di-i-propoxyethyl acetoacetate aluminum, di-i-propoxy acetylacetonate aluminum, i-propoxy bis (ethylacetoacetate) aluminum, i-propoxy bis ( Organoaluminum compounds such as acetylacetonato) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonate bis (ethylacetoacetate) aluminum;
And so on.

Among these organometallic compounds (2) and partial hydrolysates thereof, tri-n-butoxy ethylacetoacetate zirconium, di-i-propoxy bis (acetylacetonato) titanium, di-i-propoxy ethylacetate Acetate aluminum, tris (ethyl acetoacetate) aluminum, or a partial hydrolyzate of these compounds is preferred.

Moreover, as a specific example of an organotin compound,
(C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ ,
_{(C 4 H 9) 2 Sn} (OCOCH = CHCOOCH 3) 2,
_{(C 4 H 9) 2 Sn} (OCOCH = CHCOOC 4 H 9) 2,
(C ₈ H ₁₇ ) ₂ Sn (OCOC ₈ H ₁₇ ) ₂ ,
(C ₈ H ₁₇ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ ,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOCH 3) 2,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOC 4 H 9) 2,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOC 8 H 17) 2,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOC 16 H 33) 2,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOC 17 H 35) 2,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOC 18 H 37) 2,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOC 20 H 41) 2,

(C ₄ H ₉ ) ₂ SnOCOCH ₃
｜
O
｜
(C ₄ H ₉ ) ₂ SnOCOCH ₃ ,
_{(C 4 H 9) Sn (} OCOC 11 H 23) 3,
(C ₄ H ₉ ) Sn (OCONa) ₃
Carboxylic acid type organotin compounds such as;

_{(C 4 H 9) 2 Sn} (SCH 2 COOC 8 H 17) 2,
_{(C 4 H 9) 2 Sn} (SCH 2 CH 2 COOC 8 H 17) 2,
_{(C 8 H 17) 2 Sn} (SCH 2 COOC 8 H 17) 2,
_{(C 8 H 17) 2 Sn} (SCH 2 CH 2 COOC 8 H 17) 2,
_{(C 8 H 17) 2 Sn} (SCH 2 COOC 12 H 25) 2,
_{(C 8 H 17) 2 Sn} (SCH 2 CH 2 COOC 12 H 25) 2,
_{(C 4 H 9) Sn (} SCOCH = CHCOOC 8 H 17) 3,
_{(C 8 H 17) Sn (} SCOCH = CHCOOC 8 H 17) 3,

_{(C 4 H 9) 2 Sn} (SCH 2 COOC 8 H 17)
｜
O
｜
(C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ )
Mercaptide-type organotin compounds such as

(C ₄ H ₉ ) ₂ Sn = S, (C ₈ H ₁₇ ) ₂ Sn = S,
(C ₄ H ₉ ) ₂ Sn = S
｜
S
｜
(C ₄ H ₉ ) ₂ Sn = S
Sulfide-type organotin compounds such as;

_{(C 4 H 9) SnCl 3} , (C 4 H 9) 2 SnCl 2,
(C ₈ H ₁₇ ) ₂ SnCl ₂ ,
_{(C 4 H 9) 2 Sn} -Cl
｜
S
｜
_{(C 4 H 9) 2 Sn} -Cl
Chloride-type organotin compounds such as;

Reaction of organotin oxides such as (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO, and ester compounds such as silicates, dimethyl maleate, diethyl maleate and dioctyl phthalate Product;
And so on.

In addition, when (E) component contains radically polymerizable acids, such as acrylic acid and methacrylic acid, since it copolymerizes as (B) component, the effect that water resistance is not deteriorated is acquired.
(E) Although the usage-amount of a component is not specifically limited, It is 0.01-5 weight part normally with respect to 100 weight part of the said (A) component, Preferably it is 0.1-5 weight part, More preferably, it is 0.1-3 weight part.

(F) When the radical polymerization initiator (B) component is used, the radical polymerization initiator (F) is used. As radical polymerization initiators, persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxymaleic acid, succinic peroxide, 2,2 Water-soluble initiators such as' -azobis [2-N-benzylamidino] propane hydrochloride; benzoyl peroxide, cumene hydroperoxide, diisopropyl peroxydicarbonate, cumylperoxyneodecanoate, cumylperoxyoctoate, An oil-soluble initiator such as azobisisobutyronitrile; a redox initiator combined with a reducing agent such as acidic sodium sulfite, Rongalite, and ascorbic acid can be used.

Among these (F) components, a water-soluble initiator is preferable from the viewpoint of polymerization stability.
Although the usage-amount of these radical polymerization initiators is not specifically limited, 0.01-5 weight part with respect to 100 weight part of (B) component, Preferably it is 0.05-4 weight part, More preferably, it is 0.8. 1 to 3 parts by weight. If it is less than 0.01 part by weight, the radical polymerization reaction may be deactivated in the middle, while if it exceeds 5 parts by weight, the water resistance may be inferior.

<Production of aqueous dispersion>
In the aqueous dispersion of the present invention, the components (A) to (D) are mixed, the average particle size of the emulsion is refined to 1 μm or less, and then the component (F) is added as necessary to perform radical polymerization. It is obtained by doing.
Further, in the miniaturization, the system is made into a mini-emulsion by using a mechanical means such as a high-pressure homogenizer, an ultrasonic wave, a homomixer or the like. At this time, the average particle size of the emulsion is preferably 1 μm or less, more preferably 0.01 to 0.5 μm, and particularly preferably 0.01 to 0.2 μm. When the average particle diameter of the emulsion exceeds 1 μm, the water resistance is inferior, which is not preferable.

Moreover, as for the reaction conditions of radical polymerization reaction, temperature is 25-120 degreeC normally, Preferably it is 40-90 degreeC, and reaction time is 0.5 to 15 hours normally, Preferably it is 1 to 8 hours.
In addition, when the aqueous dispersion of the present invention contains an organic solvent used as necessary when preparing the component (A), the organic solvent can be removed from the aqueous dispersion.
Furthermore, in the aqueous dispersion of the present invention, various organic solvents as described above used at the time of preparing the component (A) can be added as necessary. In order to avoid flammability, it is desirable to reduce the flammable organic solvent by means such as heating and distillation.

The sulfonic acid group-containing aqueous dispersion of the present invention contains a sulfonic acid group.
Illustrating the method of introducing sulfonic acid groups,
a. Epoxy group, a mercapto group, introducing the component (A) having R ¹ containing a functional group capable of introducing a sulfonic acid group by sulfonation such as a vinyl group, a method of sulfonation.
b. A method of introducing a sulfonic acid group by using a monomer having a sulfonic acid group such as acrylamide t-butylsulfonic acid for production.
c. A method in which a component (B) containing a functional group capable of introducing a sulfonic acid group by sulfonation, such as an epoxy group or a mercapto group, is introduced for sulfonation.
d. A method in which an emulsifier having a sulfonic acid group such as an alkyl sulfate ester or an alkylaryl sulfate ester is used in an acid form.
e. A method of adding a polymer having a sulfonic acid group.

For the sulfonation of a and c, a known method can be used. For example, when the functional group is an epoxy group, sulfuric acid is added. When the functional group is a mercapto group, an oxidizing agent such as hydrogen peroxide is added. When the functional group is an unsaturated double bond such as a vinyl group, it can be sulfonated by adding hydrogen sulfite.

b. In the method of introducing a sulfonic acid group by using a monomer having a sulfonic acid group such as acrylamide t-butylsulfonic acid for production, the monomer having a sulfonic acid group as the component (b-1) and (B) is combined with the component (A). Method of mixing, (b-2) Method of adding monomer having sulfonic acid group after fine emulsification, then adding (F) component and polymerizing, (b-3) After fine emulsification, (F ) Component may be added, and then a monomer having a sulfonic acid group may be added for polymerization.
The method b is preferable from the viewpoint of water resistance, and the method (b-2) or (b-3) is preferable from the viewpoint of polymerization stability.

e. The polymer having a sulfonic acid group is not particularly limited. For example, a sulfonated product of a conjugated diene (co) polymer such as a sulfonated product of polybutadiene or a sulfonated product of polyisoprene; a sulfonated product of polystyrene or a styrene-butadiene copolymer. Sulfonated products, sulfonated products of hydrogenated styrene / butadiene copolymers, sulfonated products of styrene / maleic acid copolymers, sulfonated products of styrene / acrylic acid copolymers, sulfonated products of acetophenone ketone resins, aromatic polyimide resins Sulfonated products, sulfonated products of aromatic (co) polymers such as sulfonated products of polyethersulfone resins; (co) polymers of sulfonic acid group-containing monomers such as isoprenesulfonic acid and acrylamide 2-methylpropanesulfonic acid; DuPont NAFION (Product name Fluorine-based polymer can be cited having a sulfonic acid group represented by. The amount of the polymer having a sulfonic acid group is preferably 99% by weight or less, more preferably 50% by weight or less, and most preferably 30% by weight or less based on 100% by weight of the solid content of the aqueous dispersion. If it exceeds 99% by weight, the water resistance is poor. The addition of the polymer having a sulfonic acid group may be carried out in any step from the initial stage of production to after the production. In the case of a polymer having a sulfonic acid group having, there are a method of adding the component (C) at the initial stage of production, a method of adding it after production and immediately before film formation, and the like.

The methods a to e can be used in combination, and these methods are preferably used in combination for the purpose of reducing the volume resistance.
The amount of the sulfonic acid group depends on the amount of the functional group to be introduced and the amount of the sulfonating agent in the methods a and c, the amount of the monomer having a sulfonic acid group in the method b, and the amount of the acid type emulsifier in the method d. Thus, in the method e, the amount of the sulfonic acid group in the polymer to be added can be adjusted.

<Additives>
In the sulfonic acid group-containing aqueous dispersion of the present invention, various additives such as a crosslinking agent, a solvent, and particles can be used as necessary.
(Crosslinking agent)
A compound capable of reacting with the functional group introduced by the component (A) and / or the component (B) to form a cured product can be used as a crosslinking agent.

Examples of such a cross-linking agent include all or part of an active methylol group such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, (poly) methylolated urea. Etherified nitrogen-containing compounds;
Phenolic resins such as novolak resins, polyhydroxystyrene and copolymers thereof, and low molecular weight phenol compounds;
Epoxy compounds such as phenol novolac epoxy resins, cresol novolac epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins;
Etc.

When a carbonyl group is introduced into the aqueous dispersion, such as when diacetone acrylamide is used as the component (B), a polyhydric hydrazide compound such as adipic acid dihydrazide can be used as a crosslinking agent.
The component (E) also functions as a curing catalyst for the component (A), and an organic metal compound is particularly preferably used as a post-added crosslinking agent.

(solvent)
The solvent used in the present invention is added to improve the handleability of the sulfonic acid group-containing aqueous dispersion and to adjust the viscosity and storage stability.

Such a solvent is not particularly limited as long as it is an organic solvent that does not impair the object of the present invention.
Alcohols such as methanol, ethanol, isopropanol, n-butanol;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;

Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether;
Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;

Cellosolves such as ethyl cellosolve and butyl cellosolve;
Carbitols such as butyl carbitol;
Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate;
Aliphatic carboxylic acid esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate;
Esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate;

Aromatic hydrocarbons such as toluene and xylene;
Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;
Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
Examples include lactones such as γ-butyrolacun. Moreover, you may mix and use aliphatic hydrocarbons etc. as needed.
These solvents can be used alone or in combination of two or more.

(Other additives)
The sulfonic acid group-containing aqueous dispersion according to the present invention may contain other additives such as inorganic or organic particles, adhesion aids, sensitizers, leveling agents, and coloring agents.

Examples of the inorganic particles include SrTiO ₃ , FeTiO ₃ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , In ₂ O ₃ , ZnO, Fe ₂ O ₃ , RuO ₂ , CdO, CdS, CdSe, GaP, GaAs, CdFeO. _{3, MoS 2, LaRhO 3,} GaN, CdP, ZnS, ZnSe, ZnTe, Nb 2 O 5, ZrO 2, InP, GaAsP, InGaAlP, AlGaAs, PbS, InAs, PbSe, InSb, SiO 2, Al 2 O 3, AlGaAs, Al (OH) ₃ , Sb ₂ O ₅ , Si ₃ N ₄ , Sn—In ₂ O ₃ , Sb—In ₂ O ₃ , MgF, CeF ₃ , CeO ₂ , 3Al ₂ O ₃ .2SiO ₂ , BeO, SiC, AlN, Fe, Co, Co-FeO x, CrO 2, Fe 4 N, BaTiO 3, BaO-Al 2 O 3 -SiO 2, Ba ferrite, Sm _{O 5, YCO 5, CeCO 5} , PrCO 5, Sm 2 CO 17, Nd 2 Fe 14 B, Al 4 O 3, α-Si, SiN 4, CoO, Sb-SnO 2, Sb 2 O 5, MnO 2, _{MnB, Co 3 O 4, Co} 3 B, LiTaO 3, MgO, MgAl 2 O 4, BeAl 2 O 4, ZrSiO 4, ZnSb, PbTe, GeSi, FeSi 2, CrSi 2, CoSi 2, MnSi 1.73, Mg 2 Si , Β-B, BaC, BP, TiB ₂ , ZrB ₂ , HfB ₂ , Ru ₂ Si ₃ , TiO ₂ (rutile type, anatase type), TiO ₃ , PbTiO ₃ , Al ₂ TiO ₅ , Zn ₂ SiO ₄ , Zr _{2 SiO 4, 2MgO 2 -Al 2} O 3 -5SiO 2, Nb 2 O 5, Li 2 O-Al 2 O 3 -4SiO 2, Mg ferrite, Ni ferrite, Ni-Zn ferrite, Li ferrite, S Examples include r-ferrite, Pt, Au, Ag, Fe, and Cu. By using such metal oxides or metal particles, control of optical properties such as refractive index of a cured film obtained by curing a sulfonic acid group-containing aqueous dispersion, electrical properties such as dielectric constant, insulation, and conductivity. Properties can be controlled. These particles can be used alone, but may be supported on particles such as carbon black and calcium carbonate.

The sulfonic acid group-containing aqueous dispersion of the present invention can be applied to various uses such as a coating material, particularly a coating material for a nonwoven fabric for battery separators, a binder resin, and a polymer solid electrolyte membrane. Moreover, when applying to various uses, in order to improve physical properties etc., another polymer can also be used together. Examples of other polymers include known resins such as urethane resins, acrylic resins, polyester resins, polyamide resins, polyethers, polystyrenes, polyester amides, polycarbonates, polyvinyl chloride, and diene polymers such as SBR and NBR.

Moreover, the sulfonic acid group-containing aqueous dispersion of the present invention can obtain a film with high accuracy by using a molding method such as cast film molding, and can be suitably used for, for example, an ion exchange membrane.

The sulfonic acid group-containing aqueous dispersion of the present invention is usually used as a single product or as a blend containing various additives. When used as a coating material, the coating method is not particularly limited, and brush coating, spraying, roll coater, flow coater, bar coater, dip coater and the like can be used. The coating film thickness varies depending on the use, but is usually a dry film thickness of 0.01 to 1,000 μm, preferably 0.05 to 500 μm.

Moreover, there is no restriction | limiting in particular in the base material used, For example, non-ferrous metals, such as polycarbonate resin, an acrylic resin, ABS resin, polyester resin, polyethylene, polypropylene, nylon, nonferrous metals, such as aluminum, copper, and duralumin, stainless steel Steel plates such as iron, glass, wood, paper, gypsum, alumina, and hardened inorganic materials. There is no restriction | limiting in particular in the shape of a base material, It can use for porous materials, such as a flat thing, a nonwoven fabric.

The sulfonic acid group-containing aqueous dispersion of the present invention can be used as a dry membrane for a solid polymer electrolyte such as a fuel cell or a modifier for a substrate surface. For example, by coating on a hydrophobic surface, it becomes possible to develop or maintain hydrophilicity and hygroscopicity. In addition, it is possible to prevent dirt and dust due to static electricity. Further, when coated on a porous material such as a non-woven fabric, it exhibits an action of capturing weak bases such as ammonia and amines present in air or water, or ionic substances. In addition, by coating the surface of the battery separator, it is possible to expect an effect that the affinity with the battery electrolyte is improved and the battery characteristics such as self-discharge characteristics are improved. In addition, it is one of the characteristics that the various particles are highly dispersed, and the function of the particles can be sufficiently exhibited.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. In addition, various evaluation and measurement in an Example and a comparative example were implemented with the following method.

<Evaluation method>
(Measurement of average particle size)
About the obtained dispersion, the volume average particle diameter was measured using the Nikkiso Co., Ltd. microtrac particle size distribution measuring apparatus (UPA150).

(Measurement of storage stability)
80 g of the obtained dispersion was put in a 100 cc glass screw tube, sealed, and allowed to stand at 25 ° C. for 3 days. The state of the dispersion was visually observed, and storage stability was determined according to the following criteria.
○: No precipitation or thickening was observed, and the initial state was maintained.
Δ: A small amount of precipitation or thickening was observed.
X: It isolate | separated into the transparent supernatant and white precipitation, or the whole system gelatinized.

(Measurement of the amount of sulfonic acid group)
About the obtained dispersion, the amount of sulfonic acid groups was measured by acid-base titration using phenolphthalein as an indicator and potassium hydroxide ethanol solution as a base.

(Evaluation of water resistance)
The obtained dispersion is poured into a frame made of a tetrafluoroethylene polymer (registered trademark: Teflon) so that the film thickness after drying becomes 0.2 mm, and left for 24 hours at 25 ° C. to volatilize the solvent. It was. Subsequently, after heat-treating at 150 ° C. for 1 hour, it was cured at a temperature of 25 ° C. and a relative humidity of 60% for 24 hours. The obtained film was immersed in water at 60 ° C. for 12 hours, dried, and the film remaining rate was measured from the weight change before and after immersion.

(Measurement of volume resistance)
The obtained dispersion is poured into a frame made of a tetrafluoroethylene polymer (registered trademark: Teflon) so that the film thickness after drying becomes 0.2 mm, and left for 24 hours at 25 ° C. to volatilize the solvent. It was. Subsequently, after heat-treating at 150 ° C. for 1 hour, it was cured at a temperature of 25 ° C. and a relative humidity of 60% for 24 hours. The obtained film was immersed in water at 25 ° C. for 24 hours, and then sandwiched between two Teflon blocks provided with platinum foil, and four corners were stopped to prepare a measurement cell. At this time, the distance between the platinum foils was adjusted to 0.5 cm when viewed from the direction perpendicular to the film. A 3532-80 chemical impedance meter manufactured by Hioki Electric Co., Ltd. was connected to the platinum electrode portion of this cell, and the alternating current impedance between both platinum electrodes was measured at a frequency of 1 kHz to calculate the volume resistance of the film.

Example 1
(Method of introducing and sulfonating component (A) having R ¹ containing a functional group capable of introducing a sulfonic acid group by sulfonation)
(Synthesis of mercapto group-containing emulsion)
(A) Polyorganosiloxane (X40-9246: manufactured by Shin-Etsu Silicone Co., Ltd., condensate having an average molecular weight of 870 consisting of 50 mol% of dimethyldimethoxysilane and 50 mol% of methyltrimethoxysilane), 45 parts by weight, γ-mercaptopropyltrimethoxysilane (KBM-803: manufactured by Shin-Etsu Silicone) 15 parts by weight, 1 part by weight of γ-methacryloxypropyltrimethoxysilane, (B) 15 parts by weight of methyl methacrylate, 10 parts by weight of 2-ethylhexyl acrylate, 8 parts by weight of cyclohexyl methacrylate, hydroxy 2 parts by weight of ethyl methacrylate, 4 parts by weight of diacetone acrylamide, (C) 0.8 part by weight of dodecylbenzenesulfonic acid, 3 parts by weight of polyoxyethylene alkyl ether (Emulgen 147: manufactured by Kao Corporation), (D) 300 parts by weight of water The beaker In charge, after stirred for 2 hours at room temperature, high-pressure homogenizer (Mizuho Industrial Co., Ltd., trade name: Microfluidizer M110Y) at a pressure of 70MPa was fine with. The average particle size at this time was 0.14 μm. This emulsion was put into a separable flask, and after substitution with nitrogen while stirring, 0.2 part by weight of (F) azobisisobutyronitrile was added and polymerized at 75 ° C. for 4 hours.

[Oxidation of mercapto group]
After completion of the polymerization reaction, the mixture was cooled to 60 ° C., 100 parts by weight of 10% aqueous hydrogen peroxide and 250 parts by weight of 1% ferrous sulfate aqueous solution were added, and the mixture was stirred at 60 ° C. for 1 hour to carry out an oxidation reaction. After cooling, the mixture was filtered through a 200 mesh stainless steel wire mesh to obtain a sulfonic acid group-containing aqueous dispersion. The obtained aqueous dispersion was subjected to various measurements and tests according to the above-mentioned methods. The results are shown in Table 1. In addition, 2 parts by weight of (E) adipic acid dihydrazide was added as a crosslinking agent before film formation.

Example 2
(Method of introducing a sulfonic acid group by using a monomer having a sulfonic acid group for production)
(A) 60 parts by weight of X40-9246, 1 part by weight of γ-methacryloxypropyltrimethoxysilane, (B-1) 8 parts by weight of isopropylacrylamide, 4 parts by weight of 2-ethylhexyl acrylate, 4 parts by weight of cyclohexyl methacrylate, hydroxyethyl methacrylate 1 part by weight, 2 parts by weight of diacetone acrylamide, 0.8 part by weight of (C) dodecylbenzenesulfonic acid, 3 parts by weight of Emulgen 147, and (D) 300 parts by weight of water were charged and stirred at room temperature for 2 hours. Then, it refined | miniaturized with the high pressure homogenizer (microfluidizer M110Y) with the pressure of 70 MPa. The average particle size at this time was 0.10 μm. This emulsion was put into a separable flask, temperature increase was started, 0.2 parts by weight of (F) azobisisobutyronitrile was added at a reactor internal temperature of 60 ° C., polymerization was performed at 75 ° C. for 30 minutes, and water was added. 70.5 parts by weight of an aqueous solution in which 20 parts by weight of (B-2) 2-acrylamido-2-methylpropanesulfonic acid and 0.5 parts by weight of octylthioglycol are dissolved in 100 parts by weight is added to the separable flask over 30 minutes. The solution was added dropwise, and the mixture was stirred for 3 hours while being kept at 75 ° C. and then cooled. This was filtered with a 200 mesh stainless steel wire mesh to obtain a sulfonic acid group-containing aqueous dispersion. The obtained aqueous dispersion was subjected to various measurements and tests according to the above-mentioned methods. The results are shown in Table 1. In addition, (E) 1 part by weight of adipic acid dihydrazide and 1 part of dibutyltin dilaurate were added as a crosslinking agent before film formation.

Example 3
(Method of introducing and sulfonating component (B) containing a functional group capable of introducing a sulfonic acid group)
(Synthesis of precursor emulsion)
(A) 60 parts by weight of X40-9246, 1 part by weight of γ-methacryloxypropyltrimethoxysilane, (B) 33 parts by weight of glycidyl methacrylate, 2 parts by weight of hydroxyethyl methacrylate, 4 parts by weight of diacetone acrylamide, (C) dodecylbenzene 1 part by weight of sodium sulfonate, 3 parts by weight of Emulgen 147, and 300 parts by weight of (D) water were added, stirred for 2 hours at room temperature, and then refined with a high-pressure homogenizer (microfluidizer M110Y) at a pressure of 70 MPa. . The average particle size at this time was 0.11 μm. This emulsion was put into a separable flask, and after substitution with nitrogen while stirring, 0.2 part by weight of (F) azobisisobutyronitrile was added and polymerized at 75 ° C. for 4 hours.

[Introduction and oxidation of mercapto group]
After completion of the polymerization reaction, the mixture was cooled to 60 ° C., 18 parts by weight of 2-mercaptoethylamine was added and stirred for 1 hour, and 100 parts by weight of 10% hydrogen peroxide and 250 parts by weight of 1% ferrous sulfate aqueous solution were added. The oxidation reaction was carried out by stirring at 60 ° C. for 1 hour. After cooling, the mixture was filtered through a 200 mesh stainless steel wire mesh to obtain a sulfonic acid group-containing aqueous dispersion. The obtained aqueous dispersion was subjected to various measurements and tests according to the above-mentioned methods. The results are shown in Table 1. In addition, 2 parts by weight of (E) adipic acid dihydrazide was added as a crosslinking agent before film formation.

Example 4
(Method of adding a polymer having a sulfonic acid group)
(A) 60 parts by weight of X40-9246, 1 part by weight of γ-methacryloxypropyltrimethoxysilane, (B-1) 8 parts by weight of isopropylacrylamide, 4 parts by weight of 2-ethylhexyl acrylate, 4 parts by weight of cyclohexyl methacrylate, hydroxyethyl methacrylate 1 part by weight, 2 parts by weight of diacetone acrylamide, (C) 1 part by weight of sodium dodecylbenzenesulfonate, 3 parts by weight of Emulgen 147 and (D) 300 parts by weight of water were added and stirred at room temperature for 2 hours. The material was refined with a high-pressure homogenizer (Microfluidizer M110Y) at a pressure of 70 MPa. The average particle size at this time was 0.10 μm. The emulsion was put into a separable flask, stirring and heating were started, 0.2 parts by weight of azobisisobutyronitrile was added at a reactor internal temperature of 60 ° C, and stirring was continued for 3 hours while maintaining the temperature at 75 ° C. After cooling, an aqueous dispersion containing no sulfonic acid group was obtained.

In a separate separable flask, 100 parts by weight of water, 20 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 2 parts by weight of diacetone acrylamide, and 0.5 parts of octylthioglycol were charged, and the temperature was raised. At an internal temperature of 60 ° C., 0.2 part by weight of (F) azobisisobutyronitrile was added, and stirring was continued for 3 hours while maintaining at 75 ° C., followed by cooling to obtain a polymer having sulfonic acid groups.

While stirring the aqueous dispersion containing no sulfonic acid group, the polymer having the sulfonic acid group was added thereto, and this was filtered through a 200-mesh stainless wire mesh to obtain a sulfonic acid group-containing aqueous dispersion. . The obtained aqueous dispersion was subjected to various measurements and tests according to the above-mentioned methods. The results are shown in Table 1. Before film formation, 2 parts by weight of (E) adipic acid dihydrazide and 1 part of dibutyltin dilaurate were added as a crosslinking agent.

Example 5
(Example of large average particle size)
The same operation was performed except that only 0.05 part by weight of dodecylbenzenesulfonic acid was used as the component (C) in Example 1.

Comparative Example 1
(Example not containing polyorganosiloxane)
In Example 2, component (A) was not added, and component (B) was (B-1) 38 parts by weight of isopropylacrylamide, 20 parts by weight of 2-ethylhexyl acrylate, 19 parts by weight of cyclohexyl methacrylate, and 1 part by weight of hydroxyethyl methacrylate. The same operation was performed except that 2 parts by weight of diacetone acrylamide and 20 parts by weight of (B-2) 2-acrylamido-2-methylpropanesulfonic acid were used.

Comparative Example 2
(Example without sulfonic acid group)
In Example 2, (B-1) 18 parts by weight of isopropylacrylamide, 9 parts by weight of 2-ethylhexyl acrylate, 9 parts by weight of cyclohexyl methacrylate, 1 part by weight of hydroxyethyl methacrylate, 2 parts by weight of diacetone acrylamide, (C) dodecylbenzenesulfone The same operation was carried out except that 0.8 part by weight of sodium acid was added and (B-2) 2-acrylamido-2-methylpropanesulfonic acid was not added.

As shown in Table 1, since Examples 1 to 5 had an average particle diameter within the range of the present invention and had a sulfonic acid group, both water resistance and volume resistance were satisfactory.
Since the comparative example 1 did not contain the polyorganosiloxane which expresses water resistance, it resulted in inferior water resistance.
Since Comparative Example 2 did not contain a sulfonic acid group, the volume resistance was large.

The sulfonic acid group-containing aqueous dispersion of the present invention can be applied to various uses such as a coating material, particularly a non-woven fabric coating material for a battery separator, a binder resin, and a polymer solid electrolyte membrane. Moreover, it is applicable also to a film and can be used suitably for an ion exchange membrane etc., for example.
The sulfonic acid group-containing aqueous dispersion of the present invention can be used as a dry membrane for a solid polymer electrolyte such as a fuel cell or a modifier for a substrate surface.

The sulfonic acid group-containing aqueous dispersion of the present invention can be applied to various uses. When applied to porous materials, etc., for example, for removing cation dyeing aids for fibers, water-absorbing nonwoven fabrics, antifouling materials, ion exchange fibers, battery separator hydrophilizing agents, ammonia, ionic substances, etc. Filter applications such as air purification filters, water purification filters, leukocyte removal filters, hay fever allergen removal materials, water vapor permeable materials, antibacterial materials, deodorant fibers, deodorant paints, deodorant paper, antifogging materials, anti-condensation materials Humidity control materials such as antistatic materials, anticorrosion materials, oxygen absorbents, sanitary products, and surface modification of activated carbon. Further, it can be applied to photographic materials such as floor polish, masking material, paper size material, paper strength enhancing material, adhesive, and silver halide photographic light-sensitive material.

Moreover, the sulfonic acid group-containing aqueous dispersion of the present invention can be applied to various applications by combining various functional particles. For example, battery materials such as general paint, circuit board paint, conductive material, solid electrolyte binder, or electrode material binder, electromagnetic shielding material, antistatic paint, sheet heating element, electrochemical reaction electrode plate, electric Contact materials, friction materials, antibacterial materials, sliding materials, polishing materials, magnetic recording media, thermal recording materials, electrochromic materials, light diffusion films, water shielding materials for communication cables, light shielding films, sound insulation sheets, plastic magnets, X-rays Examples include intensifying screens, printing inks, agricultural chemical granules, and electrophotographic toners. In addition, as a coating material for surface protection, for example, metals such as stainless steel, aluminum and copper, inorganic materials such as concrete and slate, polyolefin materials such as polyethylene and polypropylene, polymer materials such as polyester such as polyethylene terephthalate, wood and paper Application is also possible.

Claims (11)

An aqueous dispersion containing polymer particles containing polyorganosiloxane as an essential component and an aqueous medium,
Further, an aqueous dispersion containing sulfonic acid groups. The aqueous dispersion according to claim 1, wherein an average particle diameter of the polymer particles is 0.002 to 1 μm. The aqueous dispersion according to claim 1 or 2, wherein the sulfonic acid group is contained in an amount of 0.2 to 5 mmol / g. The aqueous dispersion according to any one of claims 1 to ³ , wherein the volume resistance of the solid obtained by evaporating the aqueous medium is 10 ^-2 to 10 ³ Ω · cm. The coating material which consists of an aqueous dispersion of any one of Claims 1-4. The film which consists of an aqueous dispersion of any one of Claims 1-4. A polymer solid electrolyte comprising the aqueous dispersion according to claim 1. A filter comprising the aqueous dispersion according to any one of claims 1 to 4. The following (A)-(D) component is mixed, and the process of refine | miniaturizing the average particle diameter of an emulsion to 1 micrometer or less is included, Manufacture of an aqueous dispersion which obtains an aqueous dispersion by performing radical polymerization as needed Method.
(A) General formula (1)
_{^{(R 1) n -Si- (OR}} 2) 4-n ...... (1)
(In the formula, when two R ¹ exist, they are the same or different, a phenyl group or a monovalent organic group having 1 to 8 carbon atoms, R ² is the same or different, and an alkyl group or carbon number having 1 to 5 carbon atoms. An acyl group of 1-6, n is an integer of 0-2)
1 to 100 parts by weight (B) radical polymerizable monomer 99 to 0 parts by weight [provided that (A) + ( B) = 100 parts by weight]
(C) 0.1-50 parts by weight of emulsifier [provided that (A) + (B) = 100 parts by weight]
(D) 50 to 2,000 parts by weight of water [provided that (A) + (B) = 100 parts by weight] Catalyst (E) that promotes hydrolysis / condensation reaction of component (A) before and / or after mixing the components (A) to (D) and reducing the average particle size of the emulsion to 1 μm or less. The method for producing an aqueous dispersion according to claim 9, wherein The method for producing an aqueous dispersion according to claim 9 or 10, wherein the radical polymerization initiator (F) is used when the component (B) is used.