JPH1192665A - Production of diorganopolysiloxane containing epoxy group and textile-treating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polysiloxane having arbitrary viscosity, containing arbitrary amount of epoxy group and useful as a textile-treating agent in high productivity by the polycondensation of respectively specific polysiloxane and alkoxysilane. SOLUTION: The objective polysiloxane having a viscosity of preferably 100-100,000 cps at 25 deg.C and molecular terminals blocked with at least one alkoxy group is produced by the polycondensation of (A) a diorganopolysiloxane expressed by the formula; HO(R2 SiO)x H [R is a 1-20C (substituted) univalent hydrocarbon group; x>=5] and (B) an epoxy-containing alkoxysilane expressed by the formula; Q-R<1> -SiR<2> n (OR<3> )3n [R<1> is a 1-5C bivalent hydrocarbon group; Q is an epoxy group expressed by formula I or the formula II; R<2> is a 1-20C (substituted)univalent hydrocarbon group; R<3> is an alkyl; (n) is 0 or 1] or its partial hydrolyzate in the presence of a basic catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an epoxy group-containing diorganopolysiloxane and a fiber treating agent, and more particularly to an epoxy group-containing diorganopolysiloxane having an arbitrary viscosity and an arbitrary amount of epoxy groups. The present invention relates to a method for producing a polysiloxane with high productivity, and a fiber treating agent mainly comprising an epoxy group-containing diorganopolysiloxane obtained by the method.

[0002]

2. Description of the Related Art Conventionally, epoxy group-containing diorganopolysiloxanes have been used for natural fibers such as cotton, hemp, silk, wool, angora and mohair, regenerated fibers such as rayon and Bemberg, and semi-synthetic fibers such as acetate. Excellent flexibility in various fibers such as polyester, polyamide, polyacrylonitrile, polyvinyl chloride, vinylon, polyethylene, polypropylene, and synthetic fibers such as spandex.
Since it imparts smoothness, wrinkle resistance, rebound resilience, and the like, it is widely used as a fiber treatment agent. The present inventors have previously described a processing agent for fibers mainly containing such an epoxy group-containing diorganopolysiloxane as disclosed in
Japanese Patent No. 95768 proposes a diorganopolysiloxane having both an epoxy group and an alkoxy group at both ends of a molecular chain. This polysiloxane is produced by subjecting a diorganopolysiloxane capped with a silanol group at both ends to a condensation reaction of an epoxy group-containing alkoxysilane in the presence of a small amount of acetic acid. A diorganopolysiloxane can be obtained. However, in this method, the epoxy group in the obtained epoxy group-containing diorganopolysiloxane is limited to two and is bonded to the terminal of the molecular chain. When the degree of polymerization is high, the epoxy group content increases.On the other hand, when the degree of polymerization is high, only those having a low epoxy group content can be produced. However, there is a disadvantage that the diorganopolysiloxane cannot be produced. As a result, even if an attempt is made to produce a high-viscosity epoxy group-containing diorganopolysiloxane in order to impart more excellent flexibility and smoothness, the above-mentioned method has a small epoxy group content, so that the desired performance is not achieved. There was a problem that it could not be provided. JP-A-54-131661 discloses an emulsion polymerization of a cyclic organopolysiloxane and an epoxy group-containing trialkoxysilane in water in the presence of a sulfonic acid surfactant or a quaternary ammonium salt surfactant. An organopolysiloxane latex composition is proposed. However, in this method, since the emulsion polymerization is carried out in water, ring opening of the epoxy group easily occurs during the polymerization reaction, and almost all of the epoxy group is finally lost. As a result, there is a disadvantage that the flexibility, smoothness, wrinkle resistance and the like provided by the epoxy group are not sufficiently provided. Furthermore, because the cyclic siloxane is emulsion-polymerized, 10% or more of the siloxane oligomer is always present in the latex composition, and this oligomer adheres to an exhaust fan or the like during drying after the fiber treatment, causing oily stains. In addition, there is a problem that the oily substance falls and adheres to the fiber material to generate an oil spot. On the other hand, a known method for producing an epoxy group-containing diorganopolysiloxane includes an organohydrogenpolysiloxane having a methylhydrogensiloxane unit,
A method is known in which an epoxy compound having a vinyl group is subjected to an addition reaction in the presence of a platinum-based catalyst. According to this method, it is possible to produce a diorganopolysiloxane having an arbitrary viscosity and an arbitrary amount of an epoxy group. However, in this method, before the addition reaction, cyclic dimethyl polysiloxane, cyclic methyl hydrogen siloxane and hexamethyldisiloxane are equilibrium polymerized with an acid catalyst to produce an organohydrogen polysiloxane, or after the addition reaction, a dimethyl siloxane oligomer and Since a complicated procedure of stripping and removing the excess epoxy compound is required, productivity is low, and improvement has been desired. Further, in this method, when an epoxy group-containing diorganopolysiloxane having a higher viscosity is to be produced, the epoxy group may be ring-opened during the addition reaction, whereby gelation is liable to occur.

[0003]

The inventors of the present invention have made intensive studies to solve the above problems, and as a result, have reached the present invention.
That is, an object of the present invention is to provide a method for producing an epoxy group-containing diorganopolysiloxane having an arbitrary viscosity and an arbitrary amount of an epoxy group with high productivity, and an epoxy group-containing diorganopolysiloxane obtained by the method. An object of the present invention is to provide a fiber treating agent containing polysiloxane as a main component.

[0004]

[Means for Solving the Problems]

The present invention provides a compound represented by the general formula (A): HO (R ₂ SiO) _x H (where R is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, of which at least 5
0% is a methyl group, and x is an integer of 5 or more. A diorganopolysiloxane represented by), the general formula ^{(B): Q-R 1} -SiR 2 n (OR 3) 3-n ( wherein, R ¹ is a divalent hydrocarbon of 1 to 5 carbon atoms And Q is of the formula:

Embedded image Wherein R ² is a group having 1 to ² carbon atoms.
0 is an unsubstituted or halogen-substituted monovalent hydrocarbon group, R ³ is an alkyl group, and n is 0 or 1. ), And a method for producing an epoxy group-containing diorganopolysiloxane, which comprises condensation-polymerizing an epoxy group-containing alkoxysilane represented by the formula (1) or a partial hydrolyzate thereof with a basic catalyst. The present invention relates to a fiber treating agent mainly comprising the obtained epoxy group-containing diorganopolysiloxane.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below.
The diorganopolysiloxane represented by the general formula (A): HO (R ₂ SiO) _x H used as a raw material in the production method of the present invention is a diorganopolysiloxane in which both molecular chain terminals are blocked with hydroxyl groups. It is. In the above formula, R is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and specifically, methyl, ethyl, propyl, butyl, t-butyl, octyl An alkyl group such as a cycloalkyl group or a dodecyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; an aralkyl group such as a 2-phenylethyl group; an unsubstituted aryl group such as a phenyl group, a tolyl group, a naphthyl group, or a xylyl group. Or a monovalent hydrocarbon group in which a hydrogen atom of these groups is partially substituted with a halogen atom such as a chlorine atom or a fluorine atom. In addition, at least 50% of the R is a methyl group. x is an integer of 5 or more, preferably in the range of 10 to 1,000, and more preferably in the range of 20 to 500.

[0006] is used as another raw material in the production method of the present invention, the general formula ^{(B): Q-R 1} -SiR 2 n
(OR ³ ) In the epoxy group-containing alkoxysilane represented by _3-n , R ¹ is a divalent hydrocarbon group having 1 to 5 carbon atoms, specifically, a methylene group, an ethylene group, a propylene group, A butylene group is exemplified. Q is the formula:

Embedded image Is an epoxy group represented by R ² has 1 to ² carbon atoms
0 unsubstituted or halogen-substituted monovalent hydrocarbon group, specifically, alkyl group such as methyl group, ethyl group, propyl group, butyl group, t-butyl group, octyl group, dodecyl group; cyclopentyl group An unsubstituted monovalent hydrocarbon group such as an aryl group such as a phenyl group, a tolyl group, a naphthyl group, or a xylyl group, or a cycloalkyl group such as a cyclohexyl group; an aralkyl group such as a 2-phenylethyl group; Is a monovalent hydrocarbon group in which a hydrogen atom is partially substituted with a halogen atom such as a chlorine atom or a fluorine atom. R ³ is an alkyl group, and specific examples include a methyl group, an ethyl group, a propyl group, and a butyl group. n is 0 or 1. In addition, a partial hydrolyzate of this epoxy group-containing alkoxysilane can also be used as a raw material.

The basic catalyst used in the production method of the present invention is a basic catalyst which enables dehydration condensation of silanol groups and dealcoholation reaction between silanol groups and alkoxy groups. Hydroxides of alkali metals such as sodium, potassium hydroxide and cesium hydroxide; or siliconate compounds thereof; hydroxides of alkaline earth metals such as barium hydroxide. The amount of the catalyst added is 10 to 10 with respect to the total amount of the diorganopolysiloxane and the epoxy group-containing alkoxysilane.
It is preferably in the range of 2,000 ppm, and more preferably in the range of 100 to 1,000 ppm.

[0008] The reaction conditions in the production method of the present invention are not particularly limited as long as dehydration condensation of silanol groups or dealcoholation reaction between silanol groups and alkoxy groups occurs. Specifically, the above-mentioned diorganopolysiloxane having hydroxyl groups blocked at both ends and the epoxy group-containing alkoxysilane are uniformly mixed and dispersed, the temperature is raised to about 80 ° C., and potassium hydroxide or the like as a catalyst is added. The water and alcohol generated by the polycondensation reaction are removed under reduced pressure while maintaining the temperature even after the catalyst is charged, and when the desired viscosity is reached, neutralization is performed with an acid such as acetic acid to obtain an epoxy group-containing diamine. Organopolysiloxanes can be produced. The reaction temperature is preferably in the range of 70 to 100 ° C. When barium hydroxide is used as the catalyst, it is desirable to remove barium hydroxide by filtering when the desired viscosity is reached.
In addition, removal of water and alcohol is also possible by blowing nitrogen under normal pressure.

According to the manufacturing method of the present invention as described above,
In the polycondensation reaction using a basic catalyst, most of the epoxy groups introduced from the silane were not opened,
The desired epoxy group-containing diorganopolysiloxane,
That is, there is an advantage that an epoxy group-containing diorganopolysiloxane having an arbitrary viscosity and an arbitrary amount of an epoxy group can be efficiently obtained. According to the production method of the present invention, an epoxy-containing diorganopolysiloxane having a high degree of polymerization can be produced from a diorganopolysiloxane having both ends hydroxyl-blocked with a low degree of polymerization. The epoxy group-containing diorganopolysiloxane produced by the production method of the present invention includes compounds represented by the following formula. In the following formula, R, R ¹ , R ³ and Q are the same as described above, R ⁴ is R or OR ³ , a is an integer of 5 or more, b and d are integers of 0 or more, c is an integer of 4 or more, e is an integer of 3 or more, and f is an integer of 1 or more.

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The epoxy group-containing diorganopolysiloxane obtained by the production method of the present invention imparts excellent flexibility, smoothness, rebound resilience and wrinkle resistance to various fibers. It is suitably used as a treatment agent. In this case, the epoxy group-containing diorganopolysiloxane preferably has a molecular chain terminal blocked with at least one alkoxy group and contains two or more epoxy groups in the molecule. This is because the alkoxy group enhances the affinity for the fiber, and as a result, the smoothness and the flexibility are improved, and further, the entanglement with the fiber is increased by the polymerization of the alkoxy group by the polymerization reaction, whereby the durability is improved. It is to improve. 25 ℃
Is preferably 100 to 100,000 centipoise. If it is less than 100 centipoise, various properties such as flexibility, smoothness, wrinkle resistance and rebound resilience to the fiber are not sufficiently exhibited, and if it exceeds 100,000 centipoise, handling during production becomes poor and emulsification occurs. This is because difficulties are accompanied and the stability after emulsification is reduced. Preferably, 500 to 50,000
0 centipoise, more preferably 1,000 centipoise.
It ranges from 0 to 20,000 centipoise. Since the viscosity gradually increases as the water and alcohol are removed, the viscosity may be adjusted by stopping the reaction at the time when the desired viscosity is reached, while measuring at regular time intervals, when the desired viscosity is reached. In order to adjust the viscosity, an alcohol may be separately used as a terminal blocking agent. In this case, an alcohol may be added to the reaction system together with the above-mentioned diorganopolysiloxane having hydroxyl groups blocked at both ends and an alkoxysilane having an epoxy group, and polycondensation may be performed. The number of carbon atoms of the alcohol as the terminal blocking agent is not particularly limited, but is preferably in the range of 1 to 20, more preferably 1 to 10. The fiber treating agent of the present invention may include, if necessary, zinc, tin, zirconium such as zinc stearate, zinc oleate, dibutyltin diacetate, dibutyltin dioleate, dibutyltin dilaurate, and zirconium stearate. A silanol condensation catalyst such as an organic metal salt of the above; an amine dicarboxylic acid and an anhydride thereof such as a primary amine, a secondary amine and a tertiary amine, and an epoxy curing agent such as zinc borofluoride in combination Is also good.

[0011] When treating a fiber product using the fiber treating agent of the present invention, a usual method of dipping, padding and coating is used. As the treatment form, the epoxy group-containing diorganopolysiloxane oil alone, or after diluting the oil in a solvent, or emulsifying and dispersing the oil in water using a commonly used emulsifier to form an emulsion, Emulsion treatment liquids appropriately diluted with water can be used. These can be treated by adhering them to textiles by the above-described method and drying by heating.

As the fiber material to which the fiber treating agent of the present invention is applied, natural fibers such as wool, hemp, silk, cotton, Angola, mohair, and asbestos;
Regenerated fiber such as Bemberg; semi-synthetic fiber such as acetate; polyester, polyacrylonitrile, polyvinyl chloride, vinylon, polyethylene, polypropylene,
Synthetic fibers such as spandex; inorganic fibers such as glass fiber, carbon fiber, and silicone carbide fiber are exemplified; staples, filaments, tows, tops, and yarns are exemplified in shape; ,fabric,
Nonwoven fabric and paper are exemplified.

[0013]

Next, the present invention will be described in detail with reference to examples.
In the examples, “parts” means “parts by weight”, “%” means “weight percent”, and the viscosity is a value at 25 ° C.

[0014]

Example 1 760 g of dimethylpolysiloxane having hydroxyl groups blocked at both ends and having a viscosity of 85 centipoise (degree of polymerization: 50) and 40 g of γ-glycidoxydimethoxymethylsilane were charged into a 1-liter reaction vessel, and stirred while stirring.
After the temperature was raised to 50 ° C, 50% aqueous potassium hydroxide solution was added to 0.1%.
32 g were added. Thereafter, while maintaining the temperature at 80 ° C., nitrogen was continuously flowed at a flow rate of 200 ml / min from the capillary immersed in the liquid. After maintaining this state for 5 hours, 0.24 g of acetic acid was added.
In addition, it was neutralized. After holding the reaction solution for 30 minutes, it was stripped under the condition of 120 ° C./20 mmHg to obtain an oil having a viscosity of 7,500 centipoise.
When this was analyzed by ²⁹ Si-NMR and ¹³ C-NMR, the following formula was obtained.

Embedded image Was confirmed to be an epoxy group-containing diorganopolysiloxane represented by the formula:

1 part of the epoxy group-containing diorganopolysiloxane obtained above was dissolved in 99 parts of toluene to prepare a treatment liquid a. After dipping a 100% cotton knitted fabric having a size of 20 cm × 40 cm in the treatment liquid a for 10 seconds, squeezing it with a mangle roll so that the squeezing ratio becomes 100%, and allowing it to stand at room temperature for 3 hours. Under a temperature condition of 5 minutes. The cloth thus treated was divided into two equal parts, and one of the treated cloths was washed once using an automatic reversing washing machine under the following conditions, and then rinsed with water twice for 5 minutes. This was defined as one wash, and a total of two washes were performed. The feeling of the treated cloth before and after washing was measured by touch. The residual ratio (%) of the epoxy group-containing diorganopolysiloxane in the treated cloth before and after washing was calculated by measuring the silicon atom intensity using a fluorescent X-ray analyzer (manufactured by Rigaku Denki Kogyo Co., Ltd.). The results are shown in Table 1. <Cleaning conditions> Bath ratio 1:50 Temperature 40 ° C Detergent Lab (manufactured by Nissan Soap Co., Ltd.) 0.5% aqueous solution Time 50 minutes

[0016]

Example 2 A liter reaction vessel was charged with 684 g of a hydroxyl-terminated dimethylpolysiloxane having a viscosity of 85 centipoise (degree of polymerization 50) and 76 g of a hydroxyl-terminated dimethylpolysiloxane having a viscosity of 2,100 centipoise (degree of polymerization 290). Dehydration was performed under reduced pressure at 80 ° C./30 mmHg. Next, 40 g of γ-glycidoxypropyldimethoxymethylsilane and 2.4 g of distilled water were blended at normal pressure, and then 0.32 g of a 50% aqueous potassium hydroxide solution was added. While maintaining the temperature at 80 ° C., the pressure was gradually reduced by a pressure reduction gradient of 60 mmHg / 10 minutes, and finally reduced to 30 mmHg. The reaction solution was kept at 80 ° C./30 mmHg for 2 hours, and then neutralized by adding 0.24 g of acetic acid. After further holding for 30 minutes, stripping was performed under the conditions of 120 ° C./20 mmHg to obtain an oil having a viscosity of 3,500 centipoise. When this was analyzed by ²⁹ Si-NMR and ¹³ C-NMR, the following formula was obtained.

Embedded image Was confirmed to be an epoxy group-containing diorganopolysiloxane represented by the formula:

Using the epoxy group-containing diorganopolysiloxane obtained above, a treatment liquid b was prepared in the same manner as in Example 1, and the knitted fabric was treated. The measurement was performed in exactly the same manner as in Example 1. The results are shown in Table 1.

[0018]

Comparative Example 1 715 g of dimethylpolysiloxane having hydroxyl groups blocked at both ends having a viscosity of 100 centipoise (degree of polymerization 58) and γ-glycidoxypropyldimethoxymethylsilane 8
5 g was charged into a 1-liter reaction vessel, and 1.6 g of acetic acid was added thereto while stirring them. Then, the temperature was raised to 120 ° C. and reacted for 4 hours in a nitrogen gas atmosphere to obtain the formula:

Embedded image The epoxy group-containing diorganopolysiloxane having a viscosity of 110 centipoise was obtained.

Using the epoxy-containing diorganopolysiloxane obtained above, a treatment liquid c was prepared in the same manner as in Example 1, and the knitted fabric was treated. The measurement was performed in exactly the same manner as in Example 1. The results are shown in Table 1.

[0020]

Comparative Example 2 A dimethylsiloxane / methylhydrogensiloxane copolymer blocked by a trimethylsiloxy group (dimethylsiloxane unit: methylhydrogensiloxane unit = 60:
2) 756 g and allyl glycidyl ether 44 g were charged into a 1 liter reaction vessel, and the temperature was raised to 80 ° C. with stirring. Next, 0.016 g of chloroplatinic acid hexahydrate was added thereto, and the mixture was reacted at a temperature of 120 ° C. for 2 hours. Excess allyl glycidyl ether was removed under a reduced pressure of 30 mmHg to obtain a compound represented by the formula:

Embedded image The epoxy group-containing diorganopolysiloxane having a viscosity of 150 centipoise was obtained.

Using the epoxy group-containing diorganopolysiloxane obtained above, a treatment liquid d is prepared in the same manner as in Example 1, and the knitted fabric is treated. The measurement was performed in exactly the same manner as in Example 1. The results are shown in Table 1.

[0022]

[Table 1] <Hand> Very good: flexibility, smoothness and rebound resilience were very excellent. Good: Flexibility, smoothness and rebound resilience were excellent. Somewhat poor: flexibility, smoothness and rebound resilience were slightly insufficient. Poor: flexibility, smoothness and rebound resilience were insufficient, and the material was coarse and hard.

[0023]

Example 3 760 g of dimethylpolysiloxane having hydroxyl groups blocked at both ends and having a viscosity of 85 centipoise (degree of polymerization: 50) and 40 g of β- (3,4-epoxycyclohexyl) -ethyldimethoxymethylsilane were charged into a 1-liter reaction vessel. After heating to 80 ° C. while stirring, 50
0.32 g of a 30% aqueous potassium hydroxide solution was added. Thereafter, while maintaining the temperature at 80 ° C., nitrogen was continuously flowed at a flow rate of 200 ml / min from the capillary immersed in the liquid. This state is 4
After holding for a time, 0.24 g of acetic acid was added to neutralize. After further holding the reaction solution for 30 minutes,
Stripping under the condition of 0 mmHg, the formula:

Embedded image The epoxy group-containing diorganopolysiloxane having a viscosity of 4,100 centipoise was obtained. The amount of the siloxane oligomer contained in the diorganopolysiloxane was 3% as measured by GPC.

The above-obtained 40 parts of the epoxy-containing diorganopolysiloxane, 1 part of polyoxyethylene (20 mol) nonylphenyl ether, 2 parts of polyoxyethylene (6 mol) lauryl ether and 4 parts of water were obtained. After mixing and emulsifying using a colloid mill emulsifier, 5
A stable emulsion was prepared by dispersing in 3 parts of water. Further, 390 g of water was added to 10 g of this emulsion to prepare a treatment liquid e having a siloxane concentration of 1%. Then 1
After adjusting the pH of the treatment liquid e to 10 using a 0% aqueous sodium hydroxide solution, a plain woven cloth of 100% silk having a size of 20 cm × 40 cm is immersed therein for 30 seconds.
It was squeezed using a mangle roll so that the squeezing ratio became 100% and dried at room temperature for 24 hours. Thereafter, the mixture was further heated at a temperature of 130 ° C. for 5 minutes. The cloth thus treated was bisected, and one was washed for 10 minutes using an automatic reversing washing machine (the detergent used was a 0.5% aqueous Munsell soap solution), and then washed for 5 minutes. This is one wash,
Washing was repeated three times in total. The stiffness of the treated cloth before and after washing is measured by JIS-L-1096 General Fabric Test Method 6.19 Rigidity, 6-19.1 (45 ° cantilever method), and the wrinkle resistance is measured by the same method as in JIS-L-1096. 22 Wrinkle resistance was measured by the B method (Monsanto method). The residual ratio (%) and feeling of the epoxy-containing diorganopolysiloxane were measured in the same manner as in Example 1. Table 2 shows the results.

[0025]

Example 4 760 g of dimethylpolysiloxane having hydroxyl groups at both ends and having a viscosity of 85 centipoise (degree of polymerization: 50) and γ-glycidoxypropyldimethoxymethylsilane 40
g was charged into a 1-liter reaction vessel, and the temperature was raised to 80 ° C. while stirring. Then, barium hydroxide was added to 0.1.
4 g was added, and the pressure was reduced to 30 mmHg over 20 minutes.
After keeping the reaction solution under the conditions of 80 ° C./30 mmHg for 2 hours, the reaction solution was cooled, and barium hydroxide was removed by filtration to obtain a compound represented by the following formula:

Embedded image The epoxy group-containing diorganopolysiloxane having a viscosity of 900 centipoise was obtained.

Using the epoxy group-containing diorganopolysiloxane obtained above, a treatment liquid f is prepared in the same manner as in Example 3 to treat the clothes, and the anti-wrinkle property, rigidity and softness before and after washing are determined. The feeling and the siloxane residual ratio were measured in exactly the same manner as in Example 3. Table 2 shows the results.

[0027]

Example 5 760 g of dimethylpolysiloxane having a hydroxyl group at both ends and having a viscosity of 85 centipoise (degree of polymerization: 50), γ-
38 g of glycidoxypropyldimethoxymethylsilane and 2 g of γ-glycidoxypropyltrimethoxysilane
Was charged into a 1-liter reaction vessel, and the mixture was heated to 80 ° C. with stirring, and then 0.32 g of a 50% aqueous potassium hydroxide solution was added. While maintaining the reaction solution at 80 ° C., nitrogen was continuously flowed at a flow rate of 200 ml / min from a capillary immersed in the solution. After maintaining this state for 4 hours, 0.24 g of acetic acid was added to neutralize. After further holding for 30 minutes, stripping was performed under the conditions of 120 ° C./20 mmHg to obtain the formula:

Embedded image The epoxy group-containing diorganopolysiloxane having a viscosity of 8,050 centipoise was obtained.

Using the epoxy group-containing diorganopolysiloxane obtained above, a treatment liquid g is prepared in the same manner as in Example 3 to treat the cloth, and the wrinkle resistance before and after washing, the softness before and after washing, The feeling and the siloxane residual ratio were measured in exactly the same manner as in Example 3. Table 2 shows the results.

[0029]

COMPARATIVE EXAMPLE 3 Both ends hydroxyl-blocked dimethylpolysiloxane having a viscosity of 10,000 centipoise (degree of polymerization 520) 79
1 g and 9 g of γ-glycidoxypropyldimethoxymethylsilane were charged into a 1-liter reaction vessel, and 1.6 g of acetic acid was added thereto while stirring them. Then this is 1
The temperature was raised to 20 ° C., and the reaction was performed for 4 hours under a nitrogen gas atmosphere.

Embedded image The epoxy group-containing diorganopolysiloxane having a viscosity of 10,800 centipoise was obtained.

Using the epoxy group-containing diorganopolysiloxane obtained above, a treatment liquid h is prepared in the same manner as in Example 3 to treat the clothes, and the anti-wrinkle property, rigidity and softness before and after washing are determined. The feeling and the siloxane residual ratio were measured in exactly the same manner as in Example 3. Table 2 shows the results.

[0031]

Comparative Example 4 Dodecylbenzenesulfonic acid 3 was added to 55 parts of water.
Was dissolved uniformly, and then a separately prepared mixture of 38 parts of cyclic dimethylsiloxane and 2 parts of γ-glycidoxypropyldimethoxymethylsilane was added thereto with stirring. Using a homogenizer emulsifier,
After emulsifying by passing twice at a pressure of 50 kg / cm ² ,
The mixture was heated at a temperature of 80 ° C. for 2 hours. Further, the reaction solution was kept at 20 ° C. for 3 hours, and then neutralized with an aqueous potassium hydroxide solution. Isopropyl alcohol and hexane were added to the thus obtained emulsion to separate into an aqueous layer and an oil layer. GPC measurement of the oil layer revealed that the content was 12% with respect to all organopolysiloxanes.
Of a siloxane oligomer.

To 10 g of the emulsion obtained above was added water 3
90 g was added to prepare a treatment liquid i, and the cloth was treated with the treatment liquid i in the same manner as in Example 3 and the wrinkle resistance, bristles, hand feeling and siloxane residual ratio before and after washing were measured. 3
The measurement was performed in exactly the same manner as described above. Table 2 shows the results.

[0033]

[Table 2]

[0034]

Example 6 755 g of a dimethylpolysiloxane having a hydroxyl group at both ends and having a viscosity of 85 centipoise (degree of polymerization: 50) was charged into a 1-liter reaction vessel, and this was charged at 80 ° C / 30 mmH.
It dehydrated under reduced pressure under the condition of g. Then, under normal pressure, 45 g of γ-glycidoxypropyldiethoxymethylsilane and 2.4 g of distilled water were blended.
0.32 g of an aqueous potassium hydroxide solution was added. While maintaining the reaction solution at 80 ° C., the pressure was gradually reduced under a reduced pressure gradient of 60 mmHg / 10 minutes, and finally reduced to 30 mmHg. Next, this was kept under the condition of 80 ° C./30 mmHg for 2 hours and then neutralized by adding 0.24 g of acetic acid. After holding for another 30 minutes, 120 ° C / 20mmH
Stripping under the conditions of g, the formula:

Embedded image The epoxy group-containing diorganopolysiloxane having a viscosity of 1,050 centipoise was obtained.

1 part of the epoxy-containing diorganopolysiloxane obtained above, dibutyltin dilaurate 0.05
Parts, and 98.95 parts of toluene are uniformly mixed, and a processing solution j
Was prepared. Next, a woven or knitted fabric made of 65% polyester and 35% rayon and having a size of 20 cm × 20 cm and subjected to only fluorescent brightening was soaked therein for 10 seconds, and then squeezed with a mangle roll so as to have a squeezing ratio of 100%. 3
Left for hours. Further, a heat treatment was performed at a temperature of 150 ° C. for 3 minutes. On the other hand, as a comparison, a treatment liquid was prepared in the same manner as described above using the epoxy group-containing diorganopolysiloxane obtained in Comparative Example 2, and using this, a woven or knitted fabric composed of 65% polyester and 35% rayon was used. And treated exactly as described. The two treated fabrics thus obtained had fairly similar softness, wrinkle resistance and rebound resilience. However, when these treated cloths were washed in the same manner as in Example 1, the cloth treated with the treatment liquid j had sufficiently good flexibility and wrinkle resistance even after washing. The treated cloth of the example had impaired flexibility and wrinkle resistance.

[0036]

Example 7 760 g of dimethylpolysiloxane having a hydroxyl group at both ends and having a viscosity of 85 centipoise (degree of polymerization: 50), γ-
40 g of glycidoxydimethoxymethylsilane and 16 g of isopropyl alcohol were charged into a 1-liter reaction vessel, and the temperature was raised to 70 ° C. while stirring them. Next, 0.32 g of a 50% aqueous solution of potassium hydroxide was added, and the mixture was kept at 70 ° C. for 3 hours. Furthermore, this is heated at 90 ° C /
After maintaining for 2 hours under the condition of 30 mmHg, the pressure was returned to normal pressure, and 0.24 g of acetic acid was added to neutralize. After neutralization, 120 ° C
/ 20 mmHg, stripping to give the formula:

Embedded image The epoxy group-containing diorganopolysiloxane having a viscosity of 700 centipoise was obtained.

1 g of the epoxy-containing diorganopolysiloxane obtained above and 0.1 g of dibutyltin dioleate were used.
05 g was dissolved in 40 g of toluene to prepare a treatment liquid k. Next, the treatment liquid k was uniformly sprayed onto 100 g of the polyester gauntlet defibrated using the defibrating machine using a simple spray. After drying this at room temperature, it was further subjected to a heat treatment at 150 ° C. for 5 minutes. The thus-prepared kamushi cotton was divided into two equal parts, and one was packed in a 100% cotton kamboo bag. This was washed in the same manner as in Example 1 and then taken out of the bag and dried. When I evaluated the texture of this kamushi cotton,
There was almost no difference in feeling before and after washing, and the feeling was feather-like and rich in compression elasticity. Thus, it has been found that the epoxy group-containing diorganopolysiloxane obtained by the production method of the present invention is also suitable as a treatment agent for a cotton bun.

[0038]

According to the production method of the present invention, the above-mentioned diorganopolysiloxane capped with hydroxyl groups at both ends and the epoxy group-containing alkoxysilane or its partial hydrolyzate are subjected to polycondensation using a basic catalyst. It is characterized in that an epoxy group-containing diorganopolysiloxane having a viscosity and containing an arbitrary amount of epoxy group can be produced with high productivity. In addition, the fiber treating agent of the present invention containing an epoxy group-containing diorganopolysiloxane obtained by this production method as a main component imparts excellent flexibility, smoothness, wrinkle resistance, and rebound resilience to various fibers. Has features.

Continuing from the front page (72) Inventor Isao Ona 2-2 Chigusa Beach, Ichihara-shi, Chiba Dow Corning Silicone Co., Ltd.

Claims (3)

[Claims] 1. General formula (A): HO (R ₂ SiO) _x H (where R is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, at least 5
0% is a methyl group, and x is an integer of 5 or more. A diorganopolysiloxane represented by), the general formula ^{(B): Q-R 1} -SiR 2 n (OR 3) 3-n ( wherein, R ¹ is a divalent hydrocarbon of 1 to 5 carbon atoms And Q is of the formula: Wherein R ² is a group having 1 to ² carbon atoms.
0 is an unsubstituted or halogen-substituted monovalent hydrocarbon group, R ³ is an alkyl group, and n is 0 or 1. A method for producing an epoxy group-containing diorganopolysiloxane, comprising subjecting an epoxy group-containing alkoxysilane represented by the formula (1) or a partial hydrolyzate thereof to polycondensation using a basic catalyst. 2. An epoxy group-containing diorganopolysiloxane having a viscosity of 100 to 100,000 centipoise at 25 ° C. and having a molecular chain end blocked with at least one alkoxy group. The production method described in 1. 3. A fiber treating agent comprising an epoxy group-containing diorganopolysiloxane obtained by the method according to claim 1 or 2 as a main component.