TWI454531B - A film-forming organopolysiloxane latex composition and a fiber texture modifier - Google Patents

Description

Film-forming organic polyoxyalkylene emulsion composition and fiber texture modifier

The present invention relates to a latex composition and a fiber texture modifier which can obtain an organopolyoxane film without removing water using an organometallic catalyst such as a tin catalyst.

The organic polysiloxane which is formed by crosslinking and hardening to form a rubber film or a resin film is used as a binder for various substrate surface coating agents such as fibers, wood, rubber, and the like, and a coating additive such as a functional inorganic filler such as a photocatalyst. The sclerosing polyoxymethylene resin is generally a composition containing a metal-based compound such as a tin catalyst. (Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei No. Hei. Patent Documents 1 to 3). However, metal compounds such as tin catalysts have problems in terms of safety.

Further, a latex which is a metal-based compound such as a tin catalyst and a polyoxy-elastic system containing an MQ resin is known (Japanese Patent Publication No. 2007-508413: Patent Document 4). In the production of a polyoxymethylene elastomer containing a MQ resin, an alkali compound is reacted as a catalyst, but an ammonium compound or an amine compound is not exemplified. Further, the organic functional oxirane is not used in combination with the emulsification stability of the latex, and there is a problem that the properties of the film are inhibited because there is no component to be crosslinked.

[Patent Document 1] Japanese Patent Publication No. Hei 5-98579

[Patent Document 2] JP-A-2005-325253

[Patent Document 3] JP-A-2007-51236

[Patent Document 4] Japanese Patent Publication No. 2007-508413

The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a latex composition which is excellent in stability of an organic polyoxane film obtained by drying only a metal compound which does not contain a tin catalyst, and which is improved in fiber quality. Agent.

As a result of repeating the positive review for the above purpose, the present inventors have found that the film-forming organopolysiloxane latex composition containing the following components has good stability, does not contain a metal compound such as a tin catalyst, and can be dried only by drying. The organic polyoxane film is obtained, and is particularly effective as a fiber texture modifier, and thus the present invention has been completed: (A) an organopolysiloxane having a hydroxyl group terminated at both terminals represented by the following formula (I) and having the following The reaction product of the organopolyoxane having a trialkyl decyloxy unit and a decanoate unit and having a decyl alcohol group represented by the formula (II); (B) a water-miscible organic compound having an SP value of 8.0 to 11.0. Solvent; (C) emulsifier; and (D) water.

Further, although the present inventors have proposed a latex composition comprising a polyoxyxylene resin and a water-miscible organic solvent, the present invention relates to a total of a trialkyl decyloxy unit and a phthalate unit in the polyoxynoxy resin. A resin having a rate of less than 20% by mole of a semi-oxane unit, which is used in the case where the fiber is hardened when the fiber is treated.

Accordingly, the present invention provides a film-forming organic polyoxyalkylene emulsion composition and a fiber texture improving agent.

[1] A film-forming organic polyoxyalkylene emulsion composition comprising the following components:

(A) an organopolysiloxane having a hydroxyl group terminated at both terminals represented by the following formula (I) and a trialkyldecyloxy unit and a decanoate unit represented by the following composition formula (II) and having a decane The reaction product of an alcohol-based organic polyoxyalkylene:

100 parts by mass

HO-[R ¹ ₂ SiO] _n -H (I)

(wherein R ¹ is a group selected from a monovalent organic group having 1 to 20 carbon atoms, a hydroxyl group and a hydrogen atom, and n is a positive number of 2 to 5,000);

[R ² ₃ SiO _1/2 ] _a [R ² ₂ SiO _2/2 ] _b [SiO _4/2 ] _c (II)

(wherein R ² is a group selected from a monovalent organic group having 1 to 20 carbon atoms, a hydroxyl group and a hydrogen atom, and a, b, and c satisfy the following positive numbers: 0.1≦a≦0.7, 0≦b≦0.5, 0.3 ≦c≦0.7, a+b+c=1);

(B) Water-miscible organic solvent having an SP value of 8.0 to 11.0: 1 to 50 parts by mass

(C) emulsifier: 1 to 50 parts by mass

(D) Water: 25 to 20,000 parts by mass.

[2] The film-forming organic polyoxyalkylene emulsion composition according to the above [1], wherein the (A) component has a hydroxyl group-terminated organopolyoxane at both ends thereof and a trialkyldecyloxy unit and a hydrazine The reactant of the acid group unit and the organopolyoxane having a stanol group is obtained by reacting an ammonium compound and/or an amine compound as a catalyst in a latex state.

[3] The film-forming organic polyoxyalkylene emulsion composition according to the above [1] or [2], wherein, in the organopolyoxane terminated by a hydroxyl group at both terminals represented by the formula (I), R ¹ 0.01 to 20 mol% is a monovalent organic group having a carbon number of 1 to 20 containing a reactive group.

[4] The film-forming organic polyoxyalkylene latex composition according to [3] above, wherein the reactive group is any one of an amine group, an epoxy group, and a fluorenyl group.

[5] A texture improving agent for fibers, which is characterized by comprising the film-forming organic polyoxyalkylene emulsion composition according to any one of the above [1] to [4].

According to the present invention, the organopolyoxygen oxide film can be obtained only by drying without using an organometallic catalyst or the like, and the latex stability is also excellent. Further, when the fiber is treated, flexibility and water absorption prevention properties can be simultaneously imparted.

The invention is described in detail below.

First, a reactant of a hydroxyl group-terminated organopolyoxane at both ends of the component (A) and an organopolyoxane having a trialkyl decyloxy unit and a decanoate unit and having a decyl alcohol group is used. It is obtained by reacting a terminal hydroxyl group polyoxyalkylene oxide with an organopolyoxane having a trialkyl decyloxy unit and a phthalate unit and having a stanol group.

The two terminal hydroxyl group polyoxyalkylene oxides which are one of the raw materials are represented by the following general formula (I):

HO-[R ¹ ₂ SiO] _n -H (I)

(wherein R ¹ is a group selected from a monovalent organic group having 1 to 20 carbon atoms, a hydroxyl group and a hydrogen atom, and n is a positive number of 2 to 5,000).

Wherein R ¹ is selected from the group consisting of a carbon number of 1 to 20, particularly a monovalent organic group of 1 to 12, a hydroxyl group and a hydrogen atom group, and a specific example of a monovalent organic group having 1 to 20 carbon atoms, and examples thereof include a methyl group. Ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, a linear, branched or cyclic alkyl group such as a cyclohexyl group or a cycloheptyl group; an aryl group such as a phenyl group, a tolyl group or a naphthyl group; an alkenyl group such as a vinyl group or an allyl group; a methoxy group; Alkoxy groups of oxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, etc., 3-glycidoxypropyl, 2-(3,4-epoxy) a monovalent hydrocarbon group containing an epoxy group such as a cyclohexyl)ethyl group, a 3-aminopropyl group, an N-(2-aminoethyl)-3-aminopropyl group, and an N-(1,3-di) group A monovalent hydrocarbon group containing an amine group such as methylbutylene-3-aminopropyl group, N-phenyl-3-aminopropyl group or the like, a monovalent hydrocarbon group containing a mercapto group such as 3-mercaptopropyl group or the like.

In this case, 0.01 to 20 mol% of R ¹ , especially 0.01 to 10 mol %, is a monovalent organic group having a carbon number of 1 to 20 containing a reactive group, and the adhesion to the substrate and the texture of the treated fiber In terms of aspect, it is preferred. In addition, examples of the reactive group include an amine group, an epoxy group, and a fluorenyl group. Examples of the organic group containing the reactive group include a monovalent hydrocarbon group containing the above-mentioned amine group, epoxy group, and fluorenyl group.

Further, 80 mol% or more of R ¹ , particularly 90 mol% or more, is preferably a methyl group.

n is a positive number of 2 to 5,000. When it is more than 5,000, the reactivity with an organopolyoxane having a trialkylnonyloxy unit and a phthalate unit is lowered. It is preferably from 10 to 3,000, more preferably from 30 to 1,000.

Next, an organopolysiloxane having a trialkyl decyloxy unit and a decanoate unit and having a stanol group as a raw material is represented by the following formula (II).

[R ² ₃ SiO _1/2 ] _a [R ² ₂ SiO _2/2 ] _b [SiO _4/2 ] _c (II)

(wherein R ² is a group selected from a monovalent organic group having 1 to 20 carbon atoms, a hydroxyl group and a hydrogen atom, and a, b, and c satisfy the following positive numbers: 0.1≦a≦0.7, 0≦b≦0.5, 0.3 ≦c≦0.7, a+b+c=1);

Wherein R ² is selected from the group consisting of a monovalent organic group having 1 to 20 carbon atoms, a hydroxyl group and a hydrogen atom group, and a monovalent organic group having 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. Butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, cycloheptyl An alkyl group, an aryl group such as a phenyl group, a tolyl group or a naphthyl group, an alkenyl group such as a vinyl group or an allyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group or the like. An alkoxy group such as an oxy group, a heptyloxy group or an octyloxy group; an epoxy group such as a 3-glycidoxypropyl group or a 2-(3,4-epoxycyclohexyl)ethyl group; Propyl, N-(2-aminoethyl)-3-aminopropyl, N-(1,3-dimethylbutylidene)-3-aminopropyl, N-phenyl-3-amine An amine group such as a propyl group, a fluorenyl group such as a 3-mercaptopropyl group or the like. In the present invention, 80 mol% or more of R ² is preferably a methyl group.

The a, b, and c systems respectively satisfy the following positive numbers: 0.1≦a≦0.7, 0≦b≦0.5, 0.3≦c≦0.7, a+b+c=1, preferably satisfying the following positive numbers: 0.2≦a≦ 0.6,0≦b≦0.4, 0.4≦c≦0.6, a+b+c=1. Such organopolysiloxanes having a trialkylstannoxy unit and a phthalate unit, especially those wherein R ² is a methyl group, and b=0 is a resin which is well known to those skilled in the art. . When the organopolysiloxane having a trialkylnonanyloxy unit and a phthalate unit has a small amount of a stanol group remaining, the stanol group can be condensed with the hydroxyl group of the organic polyoxyalkylene having two terminal hydroxyl groups. The desired reaction product is obtained.

Further, in order to increase the stanol group in the organopolyoxane having a trialkyldecyloxy unit and a phthalate unit, the [R ² ₂ SiO _2/2 ] unit can be efficiently introduced. As for the introduction method, it is preferred to synthesize a trialkyl chlorodecane as a raw material in the production of a trialkyl decyloxy phthalate and a known method using a dialkyldichloromethane in water glass. In this case, b is 0 ≦ b ≦ 0.5, and if it is more than 0.5, the film property of the reactant is lowered, so it is necessary to be 0.5 or less.

The content of the stanol group is preferably from 0.01 to 2 mol per 100 g of the polyorganooxyl alkoxide of the formula (II) from the viewpoint of reactivity.

The addition ratio of the organic polyoxyalkylene having a hydroxyl group at both terminals to the organopolyoxane having a trialkyldecyloxy unit and a phthalate unit is 20/80 to 80/20 (mass ratio). When the ratio of the organic polyoxyalkylene having a hydroxyl group at both terminals is less than 20, the reactant cannot be formed into a film form and becomes a resin powder. Further, if the ratio of the organopolyoxane at both terminal hydroxyl groups is more than 80, the reactants are in the form of a paste or an oil, so that the organic polyoxyalkylene having both terminal hydroxyl groups and the trialkyldecyloxy unit and the tannic acid The ratio of the organopolysiloxane of the ester unit is preferably 20/80 to 80/20 (mass ratio). More preferably 30/70~75/25 (mass ratio).

The reaction of the two terminal hydroxyl group organopolyoxane with an organopolyoxane having a trialkyl decyloxy unit and a phthalate unit, using an ammonium compound or an amine compound as a catalyst, even at room temperature Can accelerate the reaction. Specific examples of the catalyst include ammonia, ammonium compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methylamine, ethylamine, propylamine, Monoalkylamines such as butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, decylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine, and a dialkylamine such as heptylamine, dioctylamine, diamine or diamine, trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, triheptylamine, trioctylamine, A trialkylamine such as tridecylamine or tridecylamine. In terms of reaction rate and latex stability, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, butylamine, hexylamine, octylamine, tripropylamine and tributylamine are preferred.

The amount of the catalyst used is 100 parts by mass based on the total amount of the organopolyoxane of the hydroxyl group at both terminals and the organopolyoxane having a trialkyl decyloxy unit and a decanoate unit and having a decyl alcohol group. 0.1 to 10 parts by mass.

If the amount of the catalyst used is too small, the condensation reaction does not proceed, and the film may not be formed. If the amount is too large, the latex stability may be lowered.

The reaction temperature is preferably from 0 to 50 ° C, more preferably from 5 to 30 ° C, and the reaction time is preferably from 3 to 100 hours, more preferably from 6 to 50 hours. After the reaction is completed, the latex stability can be improved by neutralizing with an acidic compound. The acidic compound at this time may, for example, be acetic acid, formic acid, phosphoric acid, hydrochloric acid, sulfuric acid or dodecylbenzenesulfonic acid.

Further, since the reactant of the organic polyoxyalkylene having both terminal hydroxyl groups and the organopolyoxane having a trialkyldecyloxy unit and a phthalate unit is in the form of a film, the emulsification of the reactant becomes difficult. Therefore, it is preferred to preliminarily emulsate the organopolyoxyalkylene having both terminal hydroxyl groups and the organopolyoxane having a trialkyldecyloxy unit and a phthalate unit to carry out the reaction in the latex.

Next, the water-miscible organic solvent having the SP value of the component (B) of 8.0 to 11.0 is used to improve the stability of the latex. Here, the SP value is a solubility parameter, which is a solubility coefficient, and is a property value promoted by Hildebrand as a standard for intermixing of liquids. When the SP value is less than 8.0 or greater than 11.0, since the latex stability at the time of emulsification is lowered, it is necessary to be 8.0 to 11.0. It is preferably 8.5 to 10.5. Further, it is necessary that the organic solvent be water-miscible. Latex stability will be reduced when it is not water miscible. The water miscibility is one in which the solubility in 100 g of water at 20 ° C is 1 g or more, more preferably 2 g or more.

Examples of the water-miscible organic solvent include an alcohol compound, a ketone compound, an ester compound, and an ether compound. Specifically, it is exemplified by cellosolve, propyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, methyl carbitol, carbitol, propyl carbene Alcohol, butyl carbitol, cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, butyl carbitol acetate, 2,2,4-trimethyl-1, 3-pentanediol monoisobutyrate or the like. Among them, preferred are butyl cellosolve, butyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate.

The amount of the component (B) to be added is 1 to 50 parts by mass based on 100 parts by mass of the component (A), and if it is less than 1 part by mass, the latex stability is deteriorated. Even if it is more than 50 parts by mass, there is no problem in characteristics, but if it is considered to be volatility to the environment when used, it is too poor. It is preferably 2 to 40 parts by mass, more preferably 3 to 30 parts by mass.

The emulsifier of the component (C) is emulsified in water as long as it is a reaction product of an organic polyoxane having a terminal hydroxyl group and an organopolysiloxane having a trialkyl decyloxy unit and a phthalate unit. There is no particular limitation, and examples thereof include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene propylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene fatty acid ester, and an alkyl group. An anionic surfactant such as a sulfate, an alkylbenzenesulfonate, an alkylsulfosuccinate, an alkyl phosphate, a polyoxyethylene alkyl ether sulfate, or a polyoxyethylene alkylphenyl ether sulfate; A cationic surfactant such as a quaternary ammonium salt or an alkylamine acetate; an amphoteric surfactant such as an alkylbetaine or an alkylimidazoline; or a water-soluble polymer compound such as polyvinyl alcohol.

Among them, in terms of stability, a nonionic surfactant such as polyoxyethylene alkyl ether, polyoxyethylene propylene alkyl ether or polyoxyethylene alkyl phenyl ether is preferred. Specific examples of such examples include polyoxyethylene octyl ether, polyoxyethylene decyl ether, polyoxyethylene decyl ether, polyoxyethylene propylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene propylene ten. Dialkyl ether, polyoxyethylene tridecyl ether, polyoxyethylene propylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxygen Ethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene styrene phenyl ether, and the like. These emulsifiers may be used singly or in combination of two or more.

Further, when a small amount of an anionic surfactant is used in combination with the nonionic surfactant, the latex stability can be further improved, so that an anionic surfactant is preferably used in combination.

The amount of the component (C) to be added is 1 to 50 parts by mass based on 100 parts by mass of the component (A). When the amount is less than 1 part by mass, the latex is difficult to be obtained, and when it is more than 50 parts by mass, the film properties are lowered. It is preferably 2 to 30 parts by mass, more preferably 3 to 20 parts by mass.

In the organic polyoxyalkylene emulsion composition of the present invention, water may be added as the component (D), but the water content of the component (D) is 25 to 20,000 parts by mass, more preferably 100 parts by mass of the component (A). It is 50 to 10,000 parts by mass. If the amount of water is too small, the viscosity of the latex becomes high, and the workability is lowered. If the amount is too large, the stability of the latex is lowered.

In this case, the reaction of the organopolyoxane of the above formula (I) with the organopolyoxyalkylene of the formula (II) is carried out by the mixture of the two organopolyoxanes in the above (B), Emulsifying in the components (C) and (D), in which the two organopolyoxanes are reacted under the above reaction conditions, whereby the latex composition of the present invention can be obtained.

The method for applying the organic polyoxyalkylene emulsion composition of the present invention to a substrate may be various conventionally known coating methods such as a dipping method, a spray method, a roll coating method, and a brush coating method. Further, the coating amount of the organopolyoxyalkylene emulsion composition is not particularly limited, but the coating amount is usually from 0.1 to 200 g/m ² , particularly from 1 to 100 g/m ² .

After coating, the organic polyoxyalkylene film can be obtained only by drying, and the drying can be carried out under conditions of volatilization of water and water-miscible organic solvent, and can be dried for 1 to 3 days at room temperature for heating. It can be dried at 100~180 °C for about 1~30 minutes.

The organic polyfluorene latex composition of the present invention can be used as a surface coating agent for various substrates, a binder for a functional inorganic filler such as a photocatalyst, a texture improving agent for fibers, and the like. Among them, at the time of fiber treatment, it is possible to impart flexibility and water absorption prevention at the same time.

Further, as the fiber, for example, natural fibers such as cotton, hemp, ray, and wool, polyester, polyamide, polyacrylonitrile, polyethylene, polypropylene, vinylon, polyvinyl chloride, and spandex are used. Such as synthetic fibers, semi-synthetic fibers such as acetate, etc., but are not limited thereto.

[Examples]

The present invention will be specifically described below by showing examples and comparative examples, but the present invention is not limited to the following examples. Further, in the following examples, % represents mass%, and the viscosity is a value of 25 ° C as determined by a BM type rotational viscometer.

[Manufacturing Example 1]

700 g of organopolyoxyalkylene having a terminal hydroxyl group of 3,000 mPa·s, represented by the general formula HO-[(CH ₃ ) ₂ Si-O] ₄₀₀ -H, in the composition formula [(CH ₃ ) ₃ SiO _{1/ 2} ] _0.36 [(CH ₃ ) ₂ SiO _2/2 ] _0.14 [SiO _4/2 ] _0.50 represents an organopolyoxane having a trialkyl decyloxy unit and a phthalate unit (the stanol group content is 0.2 mol) 500 g of 47% toluene solution of the ear/100 g) was charged into a vacuum stripping apparatus, and toluene was distilled off under reduced pressure at 50 ° C and 10 mmHg to obtain 1,000 g of the terminal hydroxyl group of the organopolysiloxane and having three Mixture A of alkyl alkoxy units and organopolyoxane units of phthalate units. It is an oil having a concentration of 9,700 mPa‧s.

[Example 1]

300 g of a mixture of an organic polyoxoxane having a terminal hydroxyl group obtained in Example 1 and an organopolyoxyalkylene having a trialkyldecyloxy unit and a phthalate unit, and a butyl acetate as a water-miscible organic solvent. 30 grams of fiber (SP value 8.9), NOIGEN XL40 (first industrial pharmaceutical: polyoxyalkylene ether, HLB10.5) 20g as emulsifier, NOIGEN XL400D (first industrial pharmaceutical: polyoxyalkylene ether ether) , 65% aqueous solution of HLB18.4), 16 grams of NEWCOL 291M (Japanese emulsifier: sodium sulfosuccinate 75% solution) 5 grams and 629 grams of ion-exchanged water were emulsified by a mixer, and then treated with a homogenizer for 30 MPa 1 Once, 1,000 grams of milky white latex was obtained. 40 g of a 25% aqueous solution of tetramethylammonium hydroxide was added thereto, and after reacting at 15 ° C for 20 hours, 7 g of acetic acid was added thereto for neutralization to obtain a milky white latex B. The nonvolatile content at 150 ° C / 3 hours was 32.4%, and the non-volatile residual portion was film-like. Moreover, the latex was not separated after 3 months at room temperature and was stabilized.

[Embodiment 2]

Latex C was obtained in the same manner as in Example 1 except that the water-miscible organic solvent was changed to 30 g of propylene glycol monomethyl ether acetate (SP value: 9.2). The nonvolatile content at 150 ° C / 3 hours was 32.0%, and the nonvolatile residue was in the form of a film. Moreover, the latex was not separated after 3 months at room temperature and was stabilized.

[Manufacturing Example 2]

700 g of organopolyoxyalkylene having a terminal hydroxyl group of 3,000 mPa·s, represented by the general formula HO-[(CH ₃ ) ₂ Si-O] ₄₀₀ -H, in the composition formula [(CH ₃ ) ₃ SiO _{1/ 2} ] _0.43 [SiO _4/2 ] _0.57 represents a 60% toluene solution of a polyalkyloxyalkylene unit and a decanoate unit of a polyorganosiloxane (the stanol group content of 0.1 mol/100 g) 500 g The mixture was placed in a vacuum stripping apparatus, and toluene was distilled off under reduced pressure at 50 ° C and 10 mmHg to obtain a mixture D of 1,000 g of the terminal hydroxyl group of the organopolyoxane and the trimethyldecyloxydecanoate. It is an oil with a viscosity of 6,100 mPa‧s.

[Example 3]

In the same manner as in Example 1, except that the mixture A of the organic polyoxyalkylene having a hydroxyl group at both terminal groups and the organopolyoxyalkylene having a trialkyldecyloxy unit and a phthalate unit was changed to the mixture D obtained in Production Example 2. Get latex E. Its nonvolatile content at 32 ° C / 3 hours was 32.3%, and the non-volatile residual fraction was film-like. Moreover, the latex was not separated after 3 months at room temperature and was stabilized.

[Comparative Example 1]

300 g of a mixture of an organic polyoxoxane having a terminal hydroxyl group obtained in Example 1 and an organopolyoxyalkylene having a trialkyldecyloxy unit and a phthalate unit, and NOIGEN XL40 as an emulsifier (first Industrial pharmaceutical: polyoxyalkylene decyl ether, HLB10.5) 20g, NOIGEN XL400D (first industrial pharmaceutical: polyoxyalkylene ether, 65% aqueous solution of HLB18.4) 16g, NEWCOL 291M (Japanese emulsifier: 5 g of sodium alkoxysulfosuccinate solution and 659 g of ion-exchanged water were emulsified by a mixer, and further treated with a homogenizer at 30 MPa to obtain 1,000 g of a milky white latex. 40 g of a 25% aqueous solution of tetramethylammonium hydroxide was added thereto, and reacted at 15 ° C for 20 hours, but the latex was separated during the reaction.

[Comparative Example 2]

300 g of a mixture of an organic polyoxoxane having a terminal hydroxyl group obtained in Example 1 and an organopolyoxyalkylene having a trialkyldecyloxy unit and a phthalate unit, and a butyl acetate as a water-miscible organic solvent. 30 grams of fiber (SP value 8.9), NOIGEN XL40 (first industrial pharmaceutical: polyoxyalkylene ether, HLB10.5) 20g as emulsifier, NOIGEN XL400D (first industrial pharmaceutical: polyoxyalkylene ether ether) , 65% aqueous solution of HLB18.4), 16 grams of NEWCOL 291M (Japanese emulsifier: sodium sulfosuccinate 75% solution) 5 grams and 629 grams of ion-exchanged water were emulsified by a mixer, and then treated with a homogenizer for 30 MPa 1 Once, the milky white latex F was obtained. Its non-volatile content at 32 ° C / 3 hours was 32.3%, and the non-volatile residue was oily. Moreover, the latex was not separated after 3 months at room temperature and was stabilized.

[Comparative Example 3]

A milky white latex G was obtained in the same manner as in Example 1 except that the 25% aqueous solution of tetramethylammonium hydroxide was changed to an 11% aqueous solution of sodium hydroxide. The non-volatile content at 150 ° C / 3 hours was 32.4%, and the non-volatile residual portion was in the form of a paste, and agglomerates occurred on the wall.

[Comparative Example 4]

Add [(CH ₃ )SiO _3/2 ] _0.65 [(C ₆ H ₅ )SiO _3/2 ] _{0.35 to} the organic polysiloxane resin 50% xylene solution 1 kg with butyl cellosolve acetate (SP value 8.9 125 g, xylene was distilled off under the conditions of 60 ° C / 20 mmHg. The butyl acetate cellosolve solution of the organic polyoxyl resin had a nonvolatile content of 80.1% at 150 ° C / 3 hours and a viscosity of 6,100 mPa ‧ . 375 g of butyl acetate cellosolve solution (polyoxyxylene resin / butyl acetate cellosolve = 80.1 / 19.8 mass ratio) of this organic polyoxyl resin, NOIGEN XL40 as an emulsifier (first industrial pharmaceutical: polyoxyalkylene fluorenyl) Ether, HLB10.5) 20g, NOIGEN XL400D (first industrial pharmaceutical: polyoxyalkylene ether, 65% aqueous solution of HLB18.4) 16g, NEWCOL 291M (Japanese emulsifier: sodium alkylsulfosuccinate 75% Solution 5 g and 584 g of ion-exchanged water were emulsified using a mixer to obtain a blue-white latex H. The nonvolatile content at 32 ° C / 3 hours was 32.5%, and the nonvolatile residue was in the form of a resin.

[Example 4, Comparative Example 5]

The latex B obtained in Example 1 and the latex H obtained in Comparative Example 4 were diluted 10 times with ion-exchanged water. The velvet cloth was immersed in the diluted solution, twisted by hand, and dried in a dryer at 150 ° C / 3 minutes. The texture of the treated cloth was evaluated by hand touch, and the water absorption prevention property was evaluated by the time before the water drop entered. The results are shown in Table 1.

[Manufacturing Example 3]

An organopolyoxane having a trialkyldecyloxy unit and a phthalate unit represented by the composition formula [(CH ₃ ) ₃ SiO _1/2 ] _0.39 [SiO _4/2 ] _0.61 (the stanol group content is 0.1 mol) Ear/100 g) 50% toluene solution 1,400 g, 300 g of butyl cellosolve (SP value 8.9) as a water-miscible organic solvent was charged into a vacuum stripping apparatus, and only decompressed at 50 ° C and 20 mmHg. The toluene was distilled off to obtain 1,000 g of a mixture I of an organopolyoxane having a trialkyldecyloxy unit and a phthalate unit and a water-miscible organic solvent. It is a solution having a nonvolatile content of 69.9% and a viscosity of 230 mPa·s at 150 ° C / 3 hours.

[Example 5]

The terminal hydroxyl group having a viscosity of 30,000 mPa ‧ is represented by the formula HO-[(CH ₃ ) ₂ Si-O] ₁₀₀₀ -[(CH ₃ )Si(C ₃ H ₆ NH ₂ )-O] ₄ -H 210 g of modified organopolyoxyalkylene, a mixture of an organopolysiloxane having a trialkyldecyloxy unit and a decanoate unit and a water-miscible organic solvent obtained in Production Example 3, 129 g, as an emulsifier NOIGEN XL40 (first industrial pharmaceutical: polyoxyalkylene ether, HLB10.5) 20 grams, NOIGEN XL400D (first industrial pharmaceutical: polyoxyalkylene ether, 65% aqueous solution of HLB18.4) 23 grams, NEWCOL 291 M (Japanese emulsifier: sodium sulfosuccinate 75% solution) 5 g and ion-exchanged water 613 g were emulsified by a mixer to obtain 1,000 g of milky white latex. 20 g of a 25% aqueous solution of tetramethylammonium hydroxide was added thereto, and after reacting at 15 ° C for 24 hours, 3.4 g of acetic acid was added thereto for neutralization to obtain a milky white latex J. Its non-volatile content at 31 ° C / 3 hours was 31.7%, and the non-volatile residual fraction was film-like. Moreover, the latex was not separated after 3 months at room temperature and was stabilized.

[Embodiment 6]

The latex J obtained in Example 5 was diluted 10 times with ion-exchanged water. The velvet cloth was immersed in the diluted solution, twisted by hand, and dried in a dryer at 150 ° C / 3 minutes. The texture of the treated cloth was evaluated by hand touch, and the water absorption prevention property was evaluated by the time before the water drop entered. The results are shown in Table 2.

Claims (5)

A film-forming organic polyoxyalkylene emulsion composition comprising the following components: (A) an organopolysiloxane having a hydroxyl group terminated at both ends represented by the following formula (I) and having the following composition The reaction product of the organopolyoxane having a trialkyl decyloxy unit and a decanoate unit and having a decyl alcohol group represented by the formula (II): 100 parts by mass of HO-[R ¹ ₂ SiO] _n -H (I (wherein R ¹ is a group selected from a monovalent organic group having 1 to 20 carbon atoms, a hydroxyl group and a hydrogen atom, and n is a positive number of 2 to 5,000); [R ² ₃ SiO _1/2 ] _a [R ² ₂ SiO _2/2 ] _b [SiO _4/2 ] _c (II) (wherein R ² is a group selected from a monovalent organic group having 1 to 20 carbon atoms, a hydroxyl group and a hydrogen atom, and a, b, and c systems satisfy the following Positive number: 0.1≦a≦0.7,0≦b≦0.5,0.3≦c≦0.7,a+b+c=1); (B) Water miscible organic solvent with SP value of 8.0~11.0: 1~50 mass Parts (C) Nonionic surfactant and anionic surfactant: 1 to 50 parts by mass (D) of water: 25 to 20,000 parts by mass. The film-forming organopolyoxyalkylene emulsion composition according to claim 1, wherein the (A) component has a hydroxyl group-terminated organopolyoxane at both ends and a trialkyldecyloxy unit and a decanoic acid. The reaction product of an ester unit and an organopolyoxane having a stanol group is obtained by reacting an ammonium compound and/or an amine compound as a catalyst in a latex state. The film-forming organic polyoxyalkylene emulsion composition according to claim 1 or 2, wherein, in the organopolyoxane terminated by a hydroxyl group at both terminals represented by the formula (I), 0.01 of R ¹ 20 mol% is a monovalent organic group having a carbon number of 1 to 20 containing a reactive group. The film-forming organic polyoxyalkylene emulsion composition according to claim 3, wherein the reactive group is any one of an amine group, an epoxy group, and a fluorenyl group. A fiber texture modifier comprising the film-forming organic polyoxyalkylene emulsion composition of any one of claims 1 to 4.