JP2001226486A - Polyorganosiloxane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyorganosiloxane containing carboxyl groups and/or their salts, easily synthesized and useful as a raw material and the like for water-based paints. SOLUTION: This polyorganosiloxane contains carboxyl groups and/or their salts and is expressed by formula (1): HpR1qQrAsSiO(4-p-q-r-s)/2 (1) [wherein 0<=p<4; 0<=q<4; 0<=r<4; 0<s<4; (p+q+r+s)<4; R1 expresses monovalent organic group; Q expresses a group selected from an alkoxy, hydroxy and a halogen; A is a group expressed by formula (2) and/or formula (3) (wherein the aforesaid formulas (2) and (3), R2 expresses a divalent organic group or a direct bond; R3 expresses a monovalent organic group or H; R4 expresses a trivalent organic group; B expresses H, an alkali metal, an alkaline earth metal, ammonium or a substituted ammonium)].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION Carboxyl group-containing polyorganosiloxanes are rich in hydrophilicity and can be uniformly dissolved or dispersed in aqueous solvents. It is useful in applications such as emulsifiers, surface coating agents for inorganic materials, modifiers such as polyester resins, epoxy resins, alkyd resins, and urethane resins, and cosmetics.

[0002]

However, it is difficult to synthesize such a hydrophilic carboxyl group-containing polyorganosiloxane. For example, when a hydrogen siloxane and a carboxylic acid compound are directly reacted in an organic solvent, the carboxyl group and the hydrogen siloxane , The desired carboxyl group-containing polyorganosiloxane cannot be obtained, for example, the reaction product gels during the reaction. For that purpose, various synthesis methods have been devised. For example, a method in which a dichlorosilane or dialkoxysilane having a cyano group, an organodisiloxane, and a cyclic organosiloxane are equilibrated in the presence of sulfuric acid or sulfonic acid, and then heated under acidic conditions to convert the cyano group into a carboxyl group. , An equilibration reaction between a carboxyl group-containing disiloxane at both ends and a cyclic organosiloxane, and an addition reaction of an alkenyl compound having a carboxyl group such as acrylic acid, methacrylic acid, undecylenic acid, or an ester or silyl ester thereof to a polyorganohydrogensiloxane. After that, if necessary, a processing method (Japanese Patent Application Laid-Open No. 61-148184,
No. 26135), a method of monoamidating an amino group-containing polyorganosiloxane with a dicarboxy compound (see JP-A-58-213025), and dissolving a phenyl group-containing polyorganosiloxane in an acylating agent such as acetyl chloride. Thereafter, this is reacted in the presence of a Friedel-Crafts type catalyst such as aluminum chloride for acylation, and then oxidized to a carboxyl group by oxidizing a carbonyl group using an oxidizing agent such as hypochlorous acid (Japanese Patent Application Laid-Open No. 61
Using an organometallic complex such as iron, cobalt and palladium, an inorganic base such as an alkali metal or an alkaline earth metal or an organic base such as an amine can be prepared by using a halomethylphenyl group-containing polyorganosiloxane. A method in which a halomethylphenyl group is converted into a carboxymethylphenyl group by reacting with water and carbon monoxide in the presence (see JP-A-5-132556), and an organocarboxyalkyl group obtained by hydrolysis of silalactone. Method for subjecting siloxane and organodichlorosilane to a hydrolysis-condensation polymerization reaction (Japanese Unexamined Patent Publication No.
No. 56017) and the reaction of an organosiloxane having a carboxyalkyl group and a hydrogensilyl group obtained by hydrolysis of silalactone with an organosiloxane having a vinyl group at both terminals in the presence of a catalyst such as chloroplatinic acid. Method (Japanese Patent Laid-Open No. 10-195
No. 201). However, these production methods have problems in that expensive cyanosilane, highly corrosive concentrated hydrochloric acid, toxic alkyl halides are used, or unnecessary residues of protecting groups are formed after the treatment. In addition, each method has a disadvantage that many steps must be obtained.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyorganosiloxane containing a carboxyl group and / or a salt thereof, which can be easily synthesized and is useful as a raw material for water-based paints.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors have found that a polyorganosiloxane containing a carboxyl group and / or a salt thereof can be easily prepared by using a compound having a special carboxyl group. Have been found, and the present invention has been achieved. That is,
A first aspect of the present invention is represented by the following average composition formula (1):
A polyorganosiloxane containing a carboxyl group and / or a salt thereof.

[0005]

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(Where 0 ≦ p <4, 0 ≦ q <4, 0 ≦ r <
4, 0 <s <4, (p + q + r + s) <4, R ¹ each independently represents a substituted or unsubstituted monovalent organic group, and Q is selected from an alkoxy group, a hydroxy group and a halogen atom And A is a group represented by the following formulas (2) and / or (3).

[0007]

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[0008]

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(In the above formulas (2) and (3), R
² represents a substituted or unsubstituted divalent organic group or a direct bond, R ³ each independently represents a substituted or unsubstituted monovalent organic group or a hydrogen atom, and R ⁴ represents a substituted or unsubstituted 3 B represents a valent organic group, and B is each independently
It represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, or a substituted ammonium represented by the formula (4). HNR ⁵ R ⁶ R ⁷ (4) (R ⁵ , R ⁶ and R ⁷ each independently represent a monovalent organic group or a hydrogen atom.)) A second aspect of the invention is represented by the formula (3). The polyorganosiloxane according to the first aspect of the invention, wherein the group is a group represented by the formula (5).

[0010]

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(Wherein R ³ each independently represents a substituted or unsubstituted monovalent organic group or a hydrogen atom, and B each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or The substituted ammonium represented by the above formula (4) is shown.) A third aspect of the present invention is the formula (3)
The polyorganosiloxane according to the first aspect of the invention, wherein the group represented by is a group represented by the formula (6).

[0012]

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A fourth aspect of the present invention is the second aspect of the present invention, wherein only one of R ^{3 in} the group represented by the formula (5) is a methyl group, and all others are hydrogen atoms. It is a polyorganosiloxane described.

A fifth aspect of the present invention is to react a polyorganosiloxane (a) represented by the following average composition formula (7) with an organic compound (b) having an acid anhydride group and a carbon-carbon unsaturated group, 2. The method for producing a polyorganosiloxane according to the first aspect of the present invention, which is obtained by hydrolyzing an acid anhydride group. H _p R ¹ _q Q _r SiO _{(4-pqr) / 2} (7) (where 0 <p <4, 0 ≦ q <4, 0 <r <4, (p + q
+ R) <4, R ¹ each independently represents a substituted or unsubstituted monovalent organic group, and Q represents one or more selected from an alkoxy group, a hydroxy group, and a halogen atom The following groups are shown. A sixth aspect of the present invention is the production of the polyorganosiloxane according to the third aspect, wherein the organic compound (b) having an acid anhydride group and a carbon-carbon unsaturated group is represented by the formula (8). Is the way.

[0015]

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(Wherein R ³ each independently represents a substituted or unsubstituted monovalent organic group or hydrogen atom, and B each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or A substituted ammonium represented by the above formula (4) is shown.) According to a seventh aspect of the present invention, the organic compound (b) having an acid anhydride group and a carbon-carbon unsaturated group is 5-norbornene-2,3-.
A sixth aspect of the present invention, which is a dicarboxylic anhydride.
A method for producing the polyorganosiloxane described above. In an eighth aspect of the present invention, the organic compound (b) having an acid anhydride group and a carbon-carbon unsaturated group is methyl-5-norbornene-2,
The method for producing a polyorganosiloxane according to the sixth aspect of the present invention, which is a 3-dicarboxylic anhydride.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The carboxyl group represented by the average composition formula (1) and / or
Examples of R ^{1 in} the polyorganosiloxane containing the salt or a salt thereof include a group having a substituted or unsubstituted hydrocarbon group or hydrophilic group, and derivatives thereof. As the hydrocarbon group, a group having 1 to 30 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, a phenyl group,
Acetyl groups are more preferred. As the group having a hydrophilic group, a group having a sulfonic acid group and / or a salt thereof, and / or a group having a polyoxyalkylene group are preferable. Derivatives are more preferred.

[0018]

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[0019]

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(In the formulas (9) and (10), n is 5 to 5)
50. A in the polyorganosiloxane represented by the average composition formula (1) is a group having a carboxyl group and / or a salt thereof represented by the following formulas (2) and / or (3).

[0021]

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[0022]

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(In the above formulas (2) and (3), R
² represents a substituted or unsubstituted divalent organic group or a direct bond; R ³ each independently represents a substituted or unsubstituted monovalent organic group or a hydrogen atom; R ⁴ represents a substituted or unsubstituted B represents a trivalent organic group, and B independently represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a substituted ammonium represented by the formula (4). HNR ⁵ R ⁶ R ⁷ (4) (R ⁵ , R ⁶ , and R ⁷ each independently represent a monovalent organic group or a hydrogen atom.))

The substituent A is 1, which is derived from an acid anhydride group.
2 A group containing a dicarboxyl group is preferable, and specific examples include any one of the groups represented by the formulas (5) and (6), and R ^{3 in} the group represented by the formula (5). Only a methyl group, the others being all hydrogen atoms, groups represented by the following formulas (11) to (14), derivatives thereof, and the like. Among them, only one of R ³ in the group represented by the formula (5) is a methyl group, and the others are all hydrogen atoms, represented by the formulas (5) and (6). The group is easily introduced and more preferred.
These may include two or more types.

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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By introducing these dicarboxy groups, the finally obtained polyorganosiloxane is rich in hydrophilicity and can be uniformly dissolved or dispersed in an aqueous solvent. Examples of the polyorganosiloxane (a) represented by the average composition formula (7) include hydrogen-terminated polydimethylsiloxane, methylhydrogensiloxane-dimethylsiloxane copolymer, polymethylhydrogensiloxane, polyethylhydrogensiloxane, polyphenyl ( Dimethylhydrogensiloxy) siloxane hydrogen-terminated, methylhydrogensiloxane-phenylmethylsiloxane copolymer, hydrogen ladder silicone, and trialkylsilane, dialkylsilane,
There are siloxanes derived from alkylsilanes, trihalosilanes, dihalosilanes, halosilanes, and derivatives thereof, and these can be used alone or in combination of two or more.

Examples of the organic compound (b) having an acid anhydride group and a carbon-carbon unsaturated group include maleic anhydride, 2-chloromaleic anhydride, dichloromaleic anhydride, 2,3-dimethyl Maleic anhydride, itaconic anhydride, citraconic anhydride, aconitic anhydride,
Dodecenyl succinic anhydride (DDSA), nonenyl succinic anhydride (NSA), octenyl succinic anhydride, 5
-Norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride (M
NA), 1,4,5,6,7,7-hexachloro-5-
Norbornene-2,3-dicarboxylic anhydride, 1,2,2
3,6-tetrahydrophthalic anhydride, 3,4,5,6
-Tetrahydrophthalic anhydride, bicyclo [2,2,
2] oct-7-ene-2,3,5,6-tetracarboxylic anhydride and derivatives thereof.
Among these, the compound represented by the formula (8) is particularly preferred because of its good reactivity with the polyorganosiloxane (a). Further, 5-norbornene-2,3-dicarboxylic anhydride and methyl-5 -Norbornene-2,
3-Dicarboxylic anhydride (MNA) is more preferred because it is easily available. These can be used alone or in combination of two or more.

[0033]

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(Wherein R ³ independently represents a substituted or unsubstituted monovalent organic group or hydrogen atom, and B each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or The substituted ammonium represented by the above formula (4) is shown.) (A) and (b)
Can be carried out preferably in the presence or absence of a catalyst, in the presence or absence of an organic solvent at -80 ° C to 300 ° C.

The catalyst used in this reaction is a transition metal catalyst, that is, nickel, palladium, platinum, iron, ruthenium, osmium, cobalt, rhodium, iridium,
Compounds such as chromium are suitable, especially compounds of platinum, palladium and rhodium. Examples of platinum compounds include chloroplatinic acid (IV), dichlorodicyclopentadienyl platinum (II), divinyltetramethyldisiloxane platinum (0), bis (acetylacetonato) platinum (I
I), dichloro (1,5-cyclooctadienyl) platinum (II), platinum-phosphine complex, platinum-amine complex,
Platinum-olefin complex, platinum black, platinum-activated carbon, tetramethyltetravinylcyclotetrasiloxane platinum (0), a simple substance of platinum, and the like. Examples of the palladium compound include dibenzylideneacetone palladium (0),
Bisacetylacetonatopalladium (II), bishexafluoroacetylacetonatopalladium (II), sodium chloride palladium, palladium-phosphine complex, palladium-amine complex, palladium-olefin complex, palladium chloride, palladium black, palladium-activated carbon , Palladium-alumina, simple substance of palladium, etc. Examples of the rhodium compound include chlorotristriphenylphosphine rhodium (I) (Wilkinson complex), trisacetylacetonatotrodium (III),
Rhodium-phosphine complexes, rhodium-amine complexes, rhodium-olefin complexes and the like. These can be used alone or in combination of two or more.

The hydrolysis of the acid anhydride group is carried out by reacting the acid anhydride group with water at a temperature between 0 ° C. and 100 ° C., preferably in the presence of an acid or base catalyst. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and organic acids such as acetic acid, propionic acid, benzenesulfonic acid, paratoluenesulfonic acid, dodecylbenzenesulfonic acid, acrylic acid, and methacrylic acid. Examples of the base catalyst include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia, and organic bases such as diethylamine, triethylamine, diisopropylamine, and diisopropylethylamine. These can be used alone or in combination of two or more. Among them, the base catalyst is particularly preferable because hydrolysis proceeds rapidly at room temperature.

As the organic solvent to be used, acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether, diisopropyl ether, dibutyl ether,
Ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, butyl acetate, N, N-
Dimethylformamide, N, N-dimethylacetamide, benzene, toluene, xylene, dichloromethane,
Chloroform, carbon tetrachloride and the like can be mentioned. These can be used alone or in combination of two or more.

Hereinafter, embodiments of the present invention will be described in more detail with reference to Examples. In the following description, "parts" all mean "parts by weight".

[0039]

Example 1 Methyl hydrogen siloxane-dimethyl siloxane copolymer (HMS-07 manufactured by AZMAX Co., Ltd.)
1) 100 parts, dioxane 100 parts, 5% of chloroplatinic acid
0.11 part of an isopropanol solution is placed in a reaction vessel having a reflux cooling group, a thermometer, and a stirrer, heated to 80 ° C., and 39.8 parts of a 30% solution of 5-norbornene-2,3-dicarboxylic anhydride in dioxane. Was added dropwise over 30 minutes, followed by stirring for 1 hour to obtain an acid anhydride group-containing polyorganosiloxane solution (A).

When the infrared absorption spectrum (IR) of this polyorganosiloxane was measured, absorption due to acid anhydride groups was observed at 1784 cm ^-1 and 1861 cm ^-1 . This IR chart is shown in FIG. To 10 parts of this polyorganosiloxane solution (a), 1 part of triethylamine and 0.5 part of water were added, followed by stirring at room temperature for 30 minutes to obtain a carboxyl group-containing polyorganosiloxane solution. Thereafter, when the mixture was dropped into water, the polyorganosiloxane was dispersed, and the particle size was 89 nm. The Measurement of the IR of the polyorganosiloxane, absorption by acid anhydride group is not observed, instead absorbed by the carboxylic acid was observed at 1714 cm ^-1, a slightly absorption by Si-H bonds to 2156cm ^-1 Observed. Fig. 2 shows the IR chart.

[0041]

Example 2 Methyl hydrogen siloxane-dimethyl siloxane copolymer (HMS-07 manufactured by AZMAX Co., Ltd.)
1) 100 parts, dioxane 100 parts, 5% of chloroplatinic acid
0.11 part of an isopropanol solution is placed in a reaction vessel having a reflux cooling group, a thermometer, and a stirrer, and heated to 80 ° C., and polyoxyethylene allyl methyl ether (MUS
A solution prepared by dissolving 50 parts of -8 / Nippon Yushi Co., Ltd., weight average molecular weight 800) in 33 parts of dioxane was added dropwise over about 1 hour. Thereafter, 39.8 parts of a 30% solution of 5-norbornene-2,3-dicarboxylic anhydride in dioxane was added dropwise over 30 minutes, and the mixture was stirred for 1 hour, and an acid anhydride group-containing polyorganosiloxane solution (a) was added. Obtained.

This polyorganosiloxane solution (a) 1
20 parts of a 25% aqueous ammonia solution was added to 0 parts and stirred at room temperature for 30 minutes to obtain a carboxyl group-containing polyorganosiloxane solution. This solution was uniform and transparent, and could be uniformly mixed with the water-based coating composition.

[0043]

Example 3 1,3,5,7-tetramethylcyclotetrasiloxane (LS-8600 manufactured by Shin-Etsu Chemical Co., Ltd.) 12
0.2 part, 287.2 parts of octamethylcyclotetrasiloxane (LS-8620 manufactured by Shin-Etsu Chemical Co., Ltd.), 1,3,5
-Trimethyl-1,3,5-triphenylcyclotrisiloxane (LS-8490 manufactured by Shin-Etsu Chemical Co., Ltd.) 88.9
Part, hexamethyldisiloxane (LS- manufactured by Shin-Etsu Chemical Co., Ltd.)
7130) 16.2 parts and 10 parts of sulfated zirconia (manufactured by Wako Pure Chemical Industries, Ltd.) are placed in a reaction vessel having a reflux cooling system, a thermometer, and a stirrer, heated to 50 ° C., stirred for 3 hours, and further heated to 80 ° C. Heated and stirred for 5 hours. After filtering the sulfated zirconia, low boiling components were removed at 130 ° C under vacuum to obtain 400 parts of transparent silicone oil (c).

100 parts of this silicone oil (c), 100 parts of dioxane, and 0.11 part of a 5% solution of chloroplatinic acid in isopropanol are placed in a reaction vessel having a reflux cooling system, a thermometer and a stirrer, and heated to 90 ° C. A solution prepared by dissolving 30 parts of methyl-5-norbornene-2,3-dicarboxylic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) in 100 parts of dioxane.
Dropped over minutes. Thereafter, the mixture was stirred for 5 hours to obtain an acid anhydride group-containing polyorganosiloxane solution (d). Infrared absorption spectrum (IR) of this polyorganosiloxane
As a result, absorption by an acid anhydride group was observed at 1782 cm ^-1 and 1859 cm ^-1 . This IR chart is shown in FIG. This polyorganosiloxane solution (d) 1
To 0 part, 1 part of triethylamine and 0.5 part of water were added, and the mixture was stirred at room temperature for 30 minutes to obtain a carboxyl group-containing polyorganosiloxane solution.

Thereafter, 5 parts of the obtained carboxyl group-containing polyorganosiloxane solution was added to 10 parts of pure water to obtain an aqueous solution of the organosiloxane. This solution was uniform and transparent, and was uniformly mixed with the aqueous coating composition. It was possible to do. The IR of this polyorganosiloxane
Was measured, absorption due to the acid anhydride group is not observed, instead absorption by carboxylic acid 1718 cm ^-1 was observed, the absorption by Si-H bond was observed at 2156cm ^-1. Fig. 4 shows the IR chart.

[0046]

Example 4 Silicone oil used in Example 3 (c)
100 parts, dioxane 100 parts, dichlorodicyclopentadienylplatinum (Strem Chemicals, I
nc. 5.0 parts of a 0.25% solution of dioxane in a reaction vessel having a reflux cooling system, a thermometer, and a stirrer.
The mixture was heated to 0 ° C, and a solution prepared by dissolving 30 parts of 2-octenylsuccinic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 parts of dioxane was added dropwise over 30 minutes. Thereafter, the mixture was stirred for 7 hours to obtain an acid anhydride group-containing polyorganosiloxane solution (E).

This polyorganosiloxane solution (e) 1
To 0 part, 1 part of triethylamine and 0.5 part of water were added, and the mixture was stirred at room temperature for 30 minutes to obtain a carboxyl group-containing polyorganosiloxane solution. Thereafter, a uniform transparent polyorganosiloxane aqueous solution was obtained in the same manner as in Example 3.

[0048]

Comparative Example 1 Methyl hydrogen siloxane-dimethyl siloxane copolymer (HMS-07 manufactured by AZMAX Co., Ltd.)
1) 100 parts, dioxane 100 parts, 5% of chloroplatinic acid
0.11 part of an isopropanol solution is placed in a reaction vessel having a reflux cooling group, a thermometer, and a stirrer, heated to 80 ° C., and 39.8 parts of a 30% allylacetic acid dioxane solution is added to 3 parts.
After dropwise addition over 0 minutes and stirring for 1 hour, the mixture gelled in the reaction vessel and no carboxyl group-containing polyorganosiloxane was obtained.

[0049]

The polyorganosiloxane of the present invention can be easily synthesized and is a raw material for water-based paint or an additive thereof, a fiber treating agent, an emulsifier, a surface coating agent for inorganic materials, a polyester resin, an epoxy resin, an alkyd resin. ,
It is useful in applications such as modifying agents such as urethane resins and cosmetics.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum (IR) of the acid anhydride group-containing polyorganosiloxane of Example 1.

FIG. 2 is an infrared absorption spectrum (IR) of the carboxyl group-containing polyorganosiloxane of Example 1.

FIG. 3 is an infrared absorption spectrum (IR) of the acid anhydride group-containing polyorganosiloxane of Example 3.

FIG. 4 is an infrared absorption spectrum (IR) of the carboxyl group-containing polyorganosiloxane of Example 3.

Claims (8)

[Claims] 1. A polyorganosiloxane containing a carboxyl group and / or a salt thereof represented by the following average composition formula (1). ^{_{H p R 1 q Q r A}} s SiO (4-pqrs) / 2 (1) ( wherein, 0 ≦ p <4,0 ≦ q <4,0 ≦ r <4,0 <s <
4, (p + q + r + s) <4, R ¹ each independently represents a substituted or unsubstituted monovalent organic group, and Q represents one or two selected from an alkoxy group, a hydroxy group and a halogen atom A group consisting of the above is shown, and A is a group represented by the following formula (2) and / or (3). Embedded image Embedded image (In the above formula (2) and (3), R ² is a divalent organic group or a direct bond substituted or unsubstituted, R ³
Each independently represents a substituted or unsubstituted monovalent organic group or a hydrogen atom, R ⁴ represents a substituted or unsubstituted trivalent organic group, and B each independently represents a hydrogen atom, an alkali metal, Alkaline earth metal, ammonium or
The substituted ammonium represented by the formula (4) is shown. HNR ⁵ R ⁶ R ⁷ (4) (R ⁵ , R ⁶ , and R ⁷ each independently represent a monovalent organic group or a hydrogen atom.)) 2. The polyorganosiloxane according to claim 1, wherein the group represented by the formula (3) is a group represented by the formula (5). Embedded image (Wherein R ³ is independently substituted or unsubstituted 1
B represents a valent organic group or a hydrogen atom, and B independently represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a substituted ammonium represented by the above formula (4). ) 3. The polyorganosiloxane according to claim 1, wherein the group represented by the formula (3) is a group represented by the formula (6). Embedded image (In the formula, B independently represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, or a substituted ammonium represented by the above formula (4).) 4. The polyorgano according to claim 2, wherein only one of R ^{3 in} the group represented by the formula (5) is a methyl group, and all others are hydrogen atoms. Siloxane. 5. After reacting a polyorganosiloxane (a) represented by the following average composition formula (7) with an organic compound (b) having an acid anhydride group and a carbon-carbon unsaturated group,
The method for producing a polyorganosiloxane according to claim 1, wherein the acid anhydride group is hydrolyzed. H _p R ¹ _q Q _r SiO _{(4-pqr) / 2} (7) (where 0 <p <4, 0 ≦ q <4, 0 <r <4, (p + q
+ R) <4, R ¹ each independently represents a substituted or unsubstituted monovalent organic group, and Q represents one or more selected from an alkoxy group, a hydroxy group, and a halogen atom The following groups are shown. ) 6. The production of a polyorganosiloxane according to claim 5, wherein the organic compound (b) having an acid anhydride group and a carbon-carbon unsaturated group is a compound represented by the formula (8). Method. Embedded image (Wherein R ³ represents an independently substituted or unsubstituted monovalent organic group or a hydrogen atom, and B each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a compound represented by the above formula ( The substituted ammonium represented by 4) is shown.) 7. An organic compound (b) having an acid anhydride group and a carbon-carbon unsaturated group is 5-norbornene-2,3-
7. The method for producing a polyorganosiloxane according to claim 6, wherein the method is a dicarboxylic anhydride. 8. The organic compound (b) having an acid anhydride group and a carbon-carbon unsaturated group is methyl-5-norbornene-
7. The method for producing a polyorganosiloxane according to claim 6, wherein the method is 2,3-dicarboxylic anhydride.