JP2001011186A - Nitrogen atom-containing polysiloxane, its production and textile treating agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polysiloxane imparting slight yellowing to fibers or textile products and also having high imparting effect of flexibility and smoothness on them when formulated as the main ingredient of a textile treating agent composition by including specific polymer end(s). SOLUTION: This polyiloxane is obtained by including at least one polymer end of formula I [R1 is a nitrogen atom-free (substituted) 1-20C monovalent organic group; R2 is a monovalent organic group containing at least one nitrogen atom; R3 is an organooxy of the formula OR1; 2<=p<=2,000]. The polysiloxane is shown, for instance, by an average structural formula of formula II (A is a group CH2CH2CH2NHCH2CH2NH2), and is obtained by dealcoholization reaction between an organopolysiloxane of formula III (e.g. a compound of formula IV) and organosilane of formula V [e.g. N-β-(aminoethyl)-γ- aminopropolymethyldimethoxysilane].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a nitrogen atom which can be synthesized from inexpensive raw materials and which is effective as a main component of a fiber treatment composition which imparts excellent flexibility and washing resistance to various fibers or fiber products. The present invention relates to a polysiloxane containing the same, a method for producing the same, and a fiber treatment composition.

[0002]

2. Description of the Related Art
Various organopolysiloxanes such as dimethylpolysiloxane, epoxy group-containing polysiloxane, aminoalkyl group-containing polysiloxane are widely used as treatment agents for imparting flexibility and smoothness to various fibers or fiber products. Among them, an aminoalkyl group-containing organopolysiloxane that can impart particularly good flexibility to various fibers or fiber products is most often used. Particularly aminoalkyl _{groups, -C 3 H 6 NH 2,} -C 3 H 6 NH
C ₂ H ₄ NH ₂ fiber treatment agent to the base resin of organopolysiloxane having a like (JP-B-48-1480, JP-B-54-43614, JP-B-57-43673, JP-60-185879, JP 60-185880
And JP-A-64-61576) are widely used because of their excellent flexibility.

_{However, -C 3 H 6 NH 2,} -C 3 H 6 NHC 2
Fibers treated with an organopolysiloxane having H ₄ NH ₂ may cause amino groups to be degraded by heat treatment, drying or aging heat or ultraviolet rays, and particularly white or light-colored fibers or fiber products. The color changes to yellow,
It has the serious disadvantage of reduced flexibility.

In order to prevent the above-mentioned yellowing, an aminoalkyl group-containing organopolysiloxane and an organic acid anhydride or chloride (Japanese Patent Application Laid-Open No. 57-110046), an epoxy compound (Japanese Patent Application Laid-Open No. 59-179888), A method of modifying an aminoalkyl group by reacting with a higher fatty acid (JP-A-1-306683), a carbonate (JP-A-2-47371) and the like has been proposed.

[0005] However, although improvement in the effect of preventing yellowing is observed in these compounds as compared with unmodified aminoalkyl group-containing organopolysiloxanes, the effect is still insufficient and the flexibility to fibers is improved. There is a drawback that it is inferior to an unmodified product in terms of imparting properties and smoothness.

The present invention has been made in view of the above circumstances,
A novel nitrogen atom-containing polysiloxane having a small yellowing effect on a fiber or a fiber product and a large effect of imparting flexibility and smoothness when compounded as a main component of a fiber treatment composition, a method for producing the same, and a method for producing the same. It is an object of the present invention to provide a fiber treatment composition containing siloxane as a main component.

[0007]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies to achieve the above object, and as a result, as shown below, selectively introduce a nitrogen atom-containing group into a polymer terminal group. By using the nitrogen-containing polysiloxane, the reaction with the fiber surface is performed efficiently, the durability is improved, and the number of nitrogen atoms not adsorbed on the fiber surface is reduced. It has been found that the yellowing due to is small, the fiber or fiber product is hardly yellowed, and excellent flexibility can be obtained. Further, this compound is prepared by a conventional method for synthesizing a nitrogen-containing polysiloxane, that is, dimethyl cyclics such as 1,1,3,3,5,5,7,7-octamethylcyclotetrasiloxane and dialkoxy containing nitrogen atoms. It was not possible to selectively introduce a nitrogen atom-containing group at the polymer terminal by equilibration with an alkali such as silane or a nitrogen-containing cyclopolysiloxane, but α, ω-dihydroxydimethylsiloxane and nitrogen atom-containing The present inventors have found that by reacting an alkoxysilane with an alcohol while removing the alcohol from the system, the trialkoxysilane containing a nitrogen atom acts as a dealcoholation catalyst, and as a result, it can be easily obtained without a catalyst. Was.

Japanese Patent Application Laid-Open No. 9-137061 discloses a polysiloxane containing nitrogen atoms by a dealcoholation reaction using α, ω-dihydroxydimethylsiloxane as a raw material.
In a system that does not use a catalyst such as barium hydroxide, there is a drawback that the reaction is very slow.In addition, when a catalyst is used, there is a problem that the neutralization or removal of the catalyst is required and the process becomes complicated. Was. In the present invention, although there is a description about the average structure, no description is given of the details of the structure, and as shown in the present invention, a nitrogen atom having a nitrogen atom-containing group selectively at the polymer terminal as shown in the present invention It was not intended to obtain a contained polysiloxane.

That is, the present invention provides a nitrogen atom-containing polysiloxane having at least one polymer terminal represented by the following general formula (1), and an organopolysiloxane represented by the following general formula (5) and the following general formula (6) The method for producing a nitrogen-containing polysiloxane characterized by subjecting a nitrogen-containing organosilane represented by the above) to a dealcoholation reaction, and a fiber treating agent composition containing the nitrogen-containing polysiloxane as a main component are provided. I do.

[0010]

Embedded image (Wherein, R ¹ is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms containing no nitrogen atom, R ² is a monovalent organic group containing at least one nitrogen atom, and R ³ is —OR An organooxy group represented by ¹ , and p represents a positive number satisfying 2 ≦ p ≦ 2,000.)

[0011]

Embedded image (In the formula, R ¹ , R ² , R ³ and p have the same meaning as described above.)

Hereinafter, the present invention will be described in more detail.
The nitrogen-containing polysiloxane of the present invention contains at least one polymer terminal represented by the following general formula (1).

[0013]

Embedded image (Wherein, R ¹ is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms containing no nitrogen atom, R ² is a monovalent organic group containing at least one nitrogen atom, and R ³ is —OR An organooxy group represented by ¹ , and p represents a positive number satisfying 2 ≦ p ≦ 2,000.)

In this case, even if the other terminal of the nitrogen atom-containing polysiloxane of the present invention is a hydroxyl group, OSiR ¹ R ²
It may be R ³ groups, or OSiR ¹ _3, OSiR ¹ ₂
R ³ may also be used, and examples of the polysiloxane of the present invention include those represented by the following general formula (I).

[0015]

Embedded image (However, R is -OH, -OSiR ¹ _3, -OSiR
¹ ₂ R ^3, or -OSiR ¹ R ² R ^3. )

Examples of the organic group represented by R ¹ include an unsubstituted or substituted monovalent hydrocarbon group.
~ 3. Specific examples of R ¹ in the organopolysiloxane of the present invention include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
Octyl, decyl, dodecyl, tetradecyl,
Alkyl groups such as octadecyl group and eicosyl group, alkenyl groups such as vinyl group, allyl group, propenyl group, butenyl group and hexenyl group, aryl groups such as phenyl group and tolyl group, benzyl group, phenylethyl group and phenylpropyl group Aralkyl group, cyclopentyl group, cycloalkyl group such as cyclohexyl group, or halogen such as chloromethyl group, trifluoropropyl group, chlorophenyl group or the like in which part or all of the hydrogen atoms bonded to these carbon atoms are substituted with halogen atoms And a halogenated aryl group such as a halogenated alkyl group and a halogenated phenyl group. Among them, it is particularly preferable that 90 mol% or more is a methyl group, a phenyl group, or a trifluoropropyl group.

R ² is a monovalent organic group containing at least one nitrogen atom, and examples thereof include groups represented by the following formulas (2), (3) and (4).

[0018]

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In the formula, R ⁴ is a divalent hydrocarbon group having 1 to 6 carbon atoms, specifically, an alkylene group such as a methylene group, a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Among them, a trimethylene group is preferable.

R ⁵ and R ⁶ are an unsubstituted or hydroxyl-substituted monovalent hydrocarbon group having 1 to 50 carbon atoms which may intervene a hydrogen atom or an oxygen atom, particularly an unsubstituted or hydroxyl-substituted alkyl group. Specific examples include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and an octyl group, and a monovalent hydrocarbon group having 1 to 8 carbon atoms such as a phenyl group. , COR (R represents a carbon number of 1 to 1)
0 group) or CHC (OH)
HCH ₂ O (C ₂ H ₄ O) _n R ⁹ (R ⁹ is a hydrogen atom or a monovalent hydrocarbon group such as an alkyl group having 1 to 8 carbon atoms;
Which is a positive number). R ⁵ and R ⁶ , and two R ^{6 s} may be the same or different, but among them, a hydrogen atom and a methyl group are preferable. R ⁷ is -CH =, - N =, - OCH =, - O
A group selected from N =. R ⁸ is a hydrogen atom or a methyl group.

In the formula (2), a is an integer of 0 to 4, and specific examples of R ² represented by the formula (2) are -C ₃ H ₆ NH ₂ -C ₃ H ₆ NHC ₂ H ₄ NH _2, or _{-C 3 H 6 NHC 2 H 4} NHC 2 H 4 NH 2 and the like.

In the groups shown as the above specific examples, one or two of the hydrogen atoms of NH or NH ₂ are COR.
(R is an alkyl group having 1 to 10 carbon atoms)
Alternatively, CHC (OH) HCH ₂ O (C ₂ H ₄ O) _n R ⁹ (R ⁹
Is a hydrogen atom or a monovalent hydrocarbon group such as an alkyl group having 1 to 8 carbon atoms, and n is a positive number of 0 to 10).

R ³ is an organooxy group represented by —OR ¹ , particularly preferably an alkoxy group having 1 to 6 carbon atoms. Specific examples of R ³ include a methoxy group,
Examples thereof include an ethoxy group and a propoxy group, and a methoxy group is most preferable.

P represents a positive number of 2 ≦ p ≦ 2,000, and preferably p is a positive number of 10 ≦ p ≦ 300.

Examples of the nitrogen-containing polysiloxane having at least one polymer terminal represented by the general formula (1) include the following.

[0026]

Embedded image

In the above compound, NH or NH
One or _two of the hydrogen atoms of COR are COR (R is a carbon atom having 1 to
Compound substituted with 10 alkyl groups) or CHC
(OH) HCH ₂ O (C ₂ H ₄ O) _n R ⁹ (R ⁹ is a hydrogen atom or a monovalent hydrocarbon group such as an alkyl group having 1 to 8 carbon atoms, and n is a positive number of 0 to 10) And a compound substituted with

The nitrogen-containing polysiloxane of the present invention comprises
It can be obtained by a dealcoholation reaction between an organopolysiloxane having hydroxyl groups blocked at both ends represented by the following general formula (5) and a nitrogen atom-containing organosilane represented by the following general formula (6).

[0029]

Embedded image (In the formula, R ¹ , R ² , R ³ , and p have the same meaning as described above.)

In the general formula (5), p is 2 as described above.
≤ p ≤ 2,000. If p is less than 2, the silanol is unstable, and a condensation reaction occurs in parallel with the reaction with the component (B). As a result, cyclics are by-produced. ), The reactivity with the nitrogen-containing diorganooxysilane is reduced. Preferably, 10 ≦ p ≦ 500. R ¹ is as described above, and it is particularly preferable that 90 mol% or more is a methyl group, a phenyl group, or a trifluoropropyl group. Specifically, those represented by the following formulas are exemplified.

[0031]

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[0032] In the general formula (6), R ^1, R ^2, R ³ are the same as those represented by the general formula (1), as R ^2, in that shown by the general formula (2) ( Those having high catalytic activity in the reaction with A) and R ⁶ being H are preferred. R ¹ is most preferably a methyl group. R ³ is most preferably a methoxy group in which the dealcoholization reaction easily proceeds, and specific examples include those shown below.

[0033]

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As R ² , among those represented by the general formula (3), R ² having high catalytic activity in the reaction with (A)
It is preferred that ⁵ and R ⁸ are hydrogen atoms. R ¹ is most preferably a methyl group. R ³ is most preferably a methoxy group in which the dealcoholization reaction easily proceeds, and specific examples include those shown below.

[0035]

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As R ² , among those represented by the general formula (4), those having high catalytic activity in the reaction with (A)
It is preferred that R ⁵ and R ⁸ are hydrogen atoms. R ¹ is most preferably a methyl group. R ³ is most preferably a methoxy group in which the dealcoholization reaction easily proceeds, and specific examples include those shown below.

[0037]

Embedded image

In the formula (6), R ² is the same as the formula (2)
In the case of (4), R ⁵ and R ⁶ are preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms such as an alkyl group and a phenyl group.

The reaction conditions of the components (A) and (B) are as follows:
Although it depends on the reactivity of the silanol of the component (A) and the reactivity of the organooxy group, particularly the alkoxy group of the component (B), the reaction is generally preferably performed at a reaction temperature of 50 to 180 ° C. for 3 to 20 hours. By this reaction, a nitrogen atom-containing polysiloxane represented by the general formula (1) can be easily obtained. Since the by-product alcohol inhibits the progress of the reaction,
It is necessary to carry out the reaction while removing the alcohol under a stream of nitrogen. A solvent is not particularly necessary, but when the viscosity of the component (A) is high, the reaction may be performed using a solvent such as toluene or xylene. If the reaction is slow, a catalyst such as triethylamine or tetramethyleneethylenediamine can be used if necessary.

If the molar ratio (A) / (B) of the reaction between the component (A) and the component (B) exceeds 1.0, a large amount of nitrogen-free polysiloxane remains, which is not preferable. If it is less than 0.5, the raw material dialkoxysilane will remain.
It is necessary that 5 ≦ (A) / (B) ≦ 1.0, and more preferably 0.6 ≦ (A) / (B) ≦ 1.0.

In the reaction of 0.5 <(A) / (B), a nitrogen atom-containing polysiloxane having a nitrogen atom-containing group at one end and a silanol group at one end is obtained as a part of the product. This polysiloxane is relatively reactive, and bonds with the fiber more strongly, so that excellent flexibility, long-lasting flexibility, and washing resistance can be obtained. When storage is required, the viscosity may increase over time depending on the storage conditions. Therefore, if necessary, trimethylsilanol, N.I. O-
By reacting with a silylating agent such as (bistrimethylsilyl) acetamide or a bifunctional alkoxysilane such as dimethyldimethoxysilane, the other end has no functionality such as trimethylsilyl group or dimethylmethoxysilyl group. It is possible to convert to a lower group. Further, by adding an alcohol compound such as methanol, ethanol, propanol, and ethylene glycol or a glycol compound, it is possible to suppress an increase in viscosity.

It is customary to modify a conventional nitrogen-containing polysiloxane by reacting it with an organic acid, an inorganic acid, or an epoxy compound. Or one or two hydrogen atoms of NH ₂ are substituted with COR (R is an alkyl group having 1 to 10 carbon atoms), or CHC (O
_{H) HCH 2 O (C 2} H 4 O) n R 9 (R 9 is a monovalent hydrocarbon group such as an alkyl group of 1 to 8 carbon hydrogen or C, n represents 0
Organic acid, inorganic acid,
Modification with an epoxy compound is optional. As the organic acid, formic acid, acetic acid, acetic anhydride, propanoic acid and the like are exemplified, and acetic acid and acetic anhydride are preferable. Examples of inorganic acids include hydrochloric acid, phosphoric acid, and the like.

Examples of the epoxy compound include those represented by the following general formula (7).

[0044]

Embedded image (In the formula, R ⁹ is a hydrogen atom or a monovalent hydrocarbon group such as an alkyl group having 1 to 8 carbon atoms, and n is a positive number of 0 to 10.) Note that R ⁹ is a hydrogen atom or a butyl group. It is preferred that

The fiber treatment composition containing the organopolysiloxane of the present invention as a main component includes toluene,
It may be dissolved in an organic solvent such as xylene, n-hexane, n-heptane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, mineral turbene, or nonionic, anionic, cationic or amphoteric. An emulsion is formed using a surfactant or the like. Although there is no particular limitation on these emulsifiers, examples of nonionic surfactants include ethoxylated higher alcohols, ethoxylated alkylphenols, polyhydric alcohol fatty acid esters, ethoxylated polyhydric alcohol fatty acid esters, ethoxylated fatty acids, and ethoxylated fatty acids. Amides, sorbitol, sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, sucrose fatty acid esters and the like,
Preferably, the HLB is in the range of 5-20,
In particular, it is preferably in the range of 10 to 16. Also,
Examples of anionic emulsifiers include higher alcohol sulfates, alkyl phenyl ether sulfates,
Alkylbenzene sulfonates, higher alcohol phosphates, ethoxylated higher alcohol sulfates, ethoxylated alkylphenyl ether sulfates, ethoxylated higher alcohol phosphates, and the like,
Examples of the cationic emulsifier include alkyl trimethyl ammonium chloride, alkyl amine hydrochloride, coconut amine acetate, alkyl amine acetate, alkyl benzene dimethyl ammonium chloride and the like. Examples of the amphoteric surfactant include N-acylamidopropyl-N, N-dimethylammoniobetaines, N-acylamidopropyl-N, N′-dimethyl-N′-β-hydroxypropylammoniobetaines, and the like. Is exemplified. Further, the use amount thereof is preferably 5 to 50 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the organopolysiloxane. The amount of water used for emulsification may be such that the organopolysiloxane pure concentration is 10 to 80% by weight, and preferably 20 to 60% by weight.

The above-mentioned emulsion can be obtained by a conventionally known method. The organopolysiloxane of the present invention is mixed with a surfactant, and the mixture is mixed with a homomixer, a homogenizer, a colloid mill, a line mixer, a universal mixer (product). ), An ultra mixer (trade name), a planetary mixer (trade name), a combimix (trade name), and a three-roll mixer.

Further, the fiber treatment composition of the present invention may contain dimethylpolysiloxane,
Silicon compounds such as α, ω-dihydroxydimethylsiloxane and alkoxysilane, and other additives such as anti-wrinkle agents, flame retardants, antistatic agents, antioxidants, preservatives, rust inhibitors, etc. No problem.

When various fibers or fiber products are treated with the fiber treating agent composition of the present invention, the emulsion of this composition is adjusted to a predetermined concentration, and then immersed, sprayed, roll-coated or the like to give a fiber. Attach. The amount of adhesion varies depending on the type of the fiber and is not particularly limited, but is generally in the range of 0.01 to 10% by weight as the amount of organopolysiloxane attached. Then, it may be dried by hot air blowing, a heating furnace or the like. Drying depends on the type of fiber, but 100
The heat treatment may be performed at a temperature of 150 ° C. for 2 to 5 minutes.

The fibers or fiber products that can be treated with the fiber treatment composition of the present invention are not particularly limited.
It is also effective for natural fibers such as silk, hemp, wool, angora and mohair, and synthetic fibers such as polyester, nylon, acrylic and spandex. Also, there is no limitation on the form and shape, staples, filaments, tows,
Not only raw materials such as yarn, but also various processed forms such as woven fabric, knitted fabric, wadding, and non-woven fabric can be treated with the fiber treating agent composition of the present invention.

[0050]

Industrial Applicability The nitrogen atom-containing polysiloxane of the present invention is a fiber treating agent composition which imparts excellent softness and washing resistance to various fibers or textiles with little yellowing due to heat or ultraviolet rays after treatment. It is widely used.

[0051]

EXAMPLES The present invention will be described below in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples, the viscosities were all 25.
It is a value at ° C. <Structural analysis by ²⁹ Si-NMR> Sample 1.5 g,
Toluene 1.35 g, benzene -d ⁶ 0.15 g, Tris as palliative reagent - (2,4-pentanedionate)
0.04 g of chromium was uniformly dissolved and filled in a sample tube having a diameter of 10 mm, and Lambda 300WB was used.
Using (JEOL), the peak of ²⁹ Si-NMR was observed by integrating 600 to 3,000 times.

[Synthesis Example 1] (A) was placed in a 500 ml glass flask equipped with an ester adapter, a condenser, and a thermometer.
Α, ω- represented by the following average structural formula (8) as a component
476.5 g of dihydroxydimethylsiloxane (0.0
30 mol) and 12.4 g (0.060 mol) of N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane as the component (B) were charged and reacted at 120 ° C. for 12 hours under a nitrogen stream. Distillation of methanol by demethanol reaction was observed in the ester adapter. After the completion of the reaction, the obtained product (A-1)
^The structure was identified by ²⁹ Si-NMR. As a result, the peak of the raw material N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane (-2.7 ppm)
Has disappeared and all silanes have reacted. The chart was as shown in FIG. 1 and the attribution was as follows.

[0053]

Embedded image

[0054]

[Table 1]

From the results of the analysis and the reaction route, it was found that the compound was represented by the following average structural formula (9). Table 2 shows the measurement results of volatile components and rotational viscosity.

[0056]

Embedded image

[Synthesis Example 2] N-β- (amino
Ethyl) -γ-aminopropylmethyldimethoxysilane
Synthesized except that the amount of was 6.2 g (0.030 mol)
The same operation as in Example 1 was performed. After completion of the reaction, the product (A-
2) was obtained. About the obtained product, ²⁹Si-N
When the structure was identified by MR, the following average structural formula was obtained.
It turned out to be shown by (10). Volatiles,
Table 2 shows the measurement results of the rotational viscosity.

[0058]

Embedded image

Synthesis Example 3 Except that 9.8 g (0.060 mol) of γ-aminopropylmethyldimethoxysilane was used instead of N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane in Synthesis Example 1. Was performed in the same manner as in Synthesis Example 1. After the completion of the reaction, a viscous colorless and transparent oily substance (A-3) was obtained. The obtained product was subjected to structure identification by ²⁹ Si-NMR, and was found to be represented by the following average structural formula (11). Table 2 shows the measurement results of volatile components and rotational viscosity.

[0060]

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[Synthesis Example 4] Instead of N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane in Synthesis Example 1, 9.9 g (0.060 mol) of 3-piperazinopropylmethyldimethoxysilane was used. Then, the same operation as in Synthesis Example 1 was performed except that the reaction conditions were set to 120 ° C. for 12 hours. After completion of the reaction, a viscous, colorless and transparent oil (A
-4) was obtained. About the obtained product, ²⁹ Si-
The structure was identified by NMR, and it was found that the compound was represented by the following average structural formula (12). Volatiles,
Table 2 shows the measurement results of the rotational viscosity.

[0062]

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Synthesis Example 5 (Comparative Example) 1,586.8 g of octamethylcyclotetrasiloxane was placed in a flask equipped with a 2,000 ml reflux tube and a thermometer.
(21.4 mol) and 1,3,5,7-tetra- [N
-Β- (aminoethyl) -γ-aminopropyl] -1,
3,5,7-tetramethylcyclotetrasiloxane 1
6.0 g (0.10 mol) were charged and 1
Dehydration was performed at 20 ° C. for 2 hours. Next, 20.6 g (0.10 mol) of N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane was added, and then 1.08 g (0.000 g of a catalyst represented by the following average structural formula (13))
20 mol), and the mixture was reacted at 150 ° C. for 6 hours to carry out polymerization. After the polymerization is completed, the mixture is cooled to 90 ° C.
3.22 g of ethylene chlorohydrin (0.040 mo
l) was added, and the mixture was reacted at 90 ° C. for 2 hours for neutralization. After completion of the reaction, a viscous, colorless and transparent oil (A
-5) was obtained. About the obtained product, ²⁹ Si-
When the structure was identified by NMR, it was found to be represented by the following average structural formula (14). Volatiles,
Table 2 shows the measurement results of the rotational viscosity.

[0064]

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Synthesis Example 6 α, ω-dihydroxydimethylsiloxane 344. represented by the following average structural formula (15) as a component (A) was placed in a 1,000 ml glass flask equipped with an ester adapter, a condenser and a thermometer. 8g
(0.10 mol) and N-β- as component (B)
41.3 g (0.20 mol) of (aminoethyl) -γ-aminopropylmethyldimethoxysilane was charged and reacted at 120 ° C. for 8 hours under nitrogen. Distillation of methanol by demethanol reaction was observed in the ester adapter. After the completion of the reaction, 30 g of isopropyl alcohol and an epoxy compound 20 represented by the following average structural formula (16)
4.4 g (0.60 mol) was added after cooling to 80 ° C.
The reaction was performed at 80 ° C. for 8 hours. Thereafter, by stripping at 120 ° C. for 2 hours under a reduced pressure of 5 mmHg, a colorless and transparent oil (A-6) having a viscosity of 1,018 cp was obtained. When ¹ H-NMR observation was performed on the obtained oil, it was confirmed that all the epoxy groups had reacted. As a result of structural analysis by ²⁹ Si-NMR, it was confirmed that the compound had the following average structural formula (17). Table 2 shows the measurement results of volatile components and rotational viscosity.

[0066]

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[Synthesis example 7] (Comparative example) 370.8 g of octamethylcyclotetrasiloxane (5.
0 mol) and 1,3,5,7-tetra- [N-β-
(Aminoethyl) -γ-aminopropyl] -1,3,
5,7-tetramethylcyclotetrasiloxane 16.0
g (0.25 mol) at 120 ° C. under nitrogen aeration.
For 2 hours. Then, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane 2
0.6 g (0.10 mol) was added, and then 0.54 g (0.001 g) of the catalyst represented by the above average structural formula (13) was added.
0 mol) and reacted at 150 ° C. for 6 hours to carry out polymerization. After completion of the polymerization, the mixture was cooled to 90 ° C., and 1.61 g (0.020 mol) of ethylene chlorohydrin was added.
Was added and reacted at 90 ° C. for 2 hours to perform neutralization. After completion of the reaction, 12 g of isopropyl alcohol and the epoxy compound 20 represented by the above average structural formula (16)
4.2 g (0.60 mol) was added after cooling to 80 ° C.
The reaction was performed at 80 ° C. for 8 hours. Thereafter, by stripping at 120 ° C. for 2 hours under a reduced pressure of 5 mmHg, a colorless and transparent oil (A-7) having a viscosity of 1,018 cp was obtained. When ¹ H-NMR observation was performed on the obtained oil, it was confirmed that all the epoxy groups had reacted. As a result of structural analysis by ²⁹ Si-NMR, it was confirmed that the compound had the following average structural formula (18). Table 2 shows the measurement results of volatile components and rotational viscosity.

[0068]

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[0069]

[Table 2]

Example 1 To 150 g of the nitrogen-containing polysiloxane (A-1) synthesized in Synthesis Example 1, 90 g of polyoxyethylene tridecyl ether (number of moles of ethylene oxide added: 10 mol, HLB = 13.6) was added. After the addition and mixing, 150 g of deionized water was added, and high-speed stirring was performed at a high speed with a homomixer for 15 minutes to perform phase inversion and kneading. Further, 610 g of deionized water was added, and the mixture was stirred for 15 minutes at 2,000 rpm with a homomixer to perform dilution, whereby a milky white emulsion was obtained.

To this emulsion was added 3.0 g of acetic acid.
After thorough stirring, heat treatment was performed at 80 ° C. for 4 hours. Further, this solution was diluted 100 times with deionized water to prepare a test solution.

Polyester / cotton blend (50% / 50%)
After immersing the broad cloth and the cotton broad cloth in the test solution for 1 minute, squeezing using a roll under the condition of a squeezing rate of 100%, 10
After drying at 0 ° C. for 2 minutes, heat treatment was further performed at 150 ° C. for 2 minutes to prepare a treated cloth. The flexibility of the polyester / cotton blended broad cloth, the washing resistance of the cotton broad cloth and the yellowing were evaluated according to the following criteria. Table 3 shows the results.

Example 2 In Example 1, the nitrogen-containing polysiloxane (A-1) was synthesized in Synthesis Example 2 (A
Example 1 except that the amount of acetic acid was changed to 1.35 g instead of -2).
The same operation as in Example 1 was performed to prepare a treated cloth, and the flexibility, washing resistance, and yellowing were evaluated in the same manner as in Example 1. Table 3 shows the results.

Comparative Example 1 The nitrogen atom-containing polysiloxane (A-1) of Example 1 was synthesized in Synthesis Example 5 (A
Except that the amount of acetic acid was changed to 3.4 g, the same operation as in Example 1 was carried out to prepare a treated cloth, and the flexibility, washing resistance and yellowing were evaluated in the same manner as in Example 1. . Table 3 shows the results
Shown in Flexibility evaluation: Three panelists evaluated by hand. ○: good, Δ: slightly poor, ×: bad. Evaluation of washing resistance: Washing was performed 10 times under the same conditions, and the repellency of water of the treated cloth was compared with the initial state. ○ is good,
△ is slightly defective, and × is defective. Evaluation of yellowing: The b value was measured using a colorimeter (ZE2000, Nippon Denshoku Industries Co., Ltd.), and the relative evaluation of the degree of yellowing was performed.は indicates good with little yellowing, and △ indicates poor yellowing.

[0075]

[Table 3]

Example 3 To 300 g of the nitrogen-containing polysiloxane (A-6) synthesized in Synthesis Example 6, 50 g of polyoxyethylene tridecyl ether (the number of moles of ethylene oxide added: 10 mol, HLB = 13.6) was added. After the addition and mixing, 100 g of deionized water was added, and high-speed stirring was performed at a high speed with a homomixer for 15 minutes to perform phase inversion and kneading. Further, 550 g of deionized water was added, and the mixture was diluted with a homomixer at 2,000 rpm for 15 minutes to obtain a transparent microemulsion. The test solution was prepared by further diluting this solution 68 times with deionized water.

To 2.2 g of this emulsion was added 1 part of deionized water.
A polyester / cotton blend (50% / 50%) broad cloth (for evaluating flexibility) and a fluorescent dye-treated cotton broad cloth (for evaluating yellowing) were added to the treatment liquid containing 47.8 g for 2 minutes. After immersion, it was squeezed using a roll under the condition of a squeezing rate of 100%, dried at 100 ° C. for 2 minutes, and further heat-treated at 150 ° C. for 2 minutes to prepare a treated cloth. Regarding yellowing, a treated cloth was prepared by further performing a heat treatment at 200 ° C. for 2 minutes. Flexibility and yellowing were evaluated according to the same criteria as above, and washing resistance was evaluated according to the following criteria. Table 4 shows the results.

Comparative Example 2 In Example 6, a nitrogen atom-containing polysiloxane (A-6) was synthesized in Synthesis Example 7 (A
Except for changing to -7), the same operation as in Example 1 was carried out to prepare a treated cloth, and the flexibility, washing resistance and yellowing were evaluated in the same manner as in Example 3. Table 4 shows the results. Evaluation of washing resistance: Washing was performed once under the same conditions, and the flexibility was evaluated by comparing three panelists. ○: good, Δ: slightly poor, ×: bad.

[0079]

[Table 4]

[Brief description of the drawings]

FIG. 1 is an NMR spectrum of the compound obtained in Synthesis Example 1.

Continued on front page F term (reference) 4J002 CP091 EC066 EJ016 FD316 GK02 4J035 BA02 CA181 CA191 EA01 EB01 LB08 4L033 AC02 AC09 AC15 BA96 CA59 CA64

Claims (10)

[Claims] 1. A nitrogen-containing polysiloxane having at least one polymer terminal represented by the following general formula (1). Embedded image (Wherein, R ¹ is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms containing no nitrogen atom, R ² is a monovalent organic group containing at least one nitrogen atom, and R ³ is —OR An organooxy group represented by ¹ , and p represents a positive number satisfying 2 ≦ p ≦ 2,000.) Is wherein R ^2, the following general formula ^{(2) -R 4 (NR 5} CH 2 CH 2) a NR 6 2 (2) ( wherein, R ⁴ is a divalent hydrocarbon of 1 to 6 carbon atoms The group, R ⁵ and R ⁶ each have 1 carbon atom which may intervene a hydrogen atom or an oxygen atom.
~ 50 unsubstituted or hydroxyl-substituted monovalent hydrocarbon groups, which may be the same or different. a represents an integer of 0 ≦ a ≦ 4. The nitrogen-containing polysiloxane according to claim 1, which is a monovalent organic group represented by the formula: 3. R ² is represented by the following general formula (3): (Wherein, R ⁴ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and R ⁷ is-
CH =, - N =, - OCH =, - a group selected from the ON =, R ⁵ is a monovalent hydrocarbon group having 1 to 8 carbon hydrogen or C, R ⁸ is hydrogen atom or a methyl group. The nitrogen-containing polysiloxane according to claim 1, which is a monovalent organic group represented by the formula: 4. R ² is represented by the following general formula (4): (In the formula, R ⁴ is a divalent hydrocarbon group having 1 to 6 carbon atoms, R ⁵ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁸ is a hydrogen atom or a methyl group.) The nitrogen atom-containing polysiloxane according to claim 1, which is a monovalent organic group shown. 5. The method according to claim ² , wherein R ² is —C ₃ H ₆ NH ₂ —C ₃ H ₆ NHC ₂ H ₄ NH ₂ or —C ₃ H ₆ NHC ₂ H ₄ NHC ₂ H ₄ NH ₂ . Nitrogen atom-containing polysiloxane. 6. The nitrogen-containing polysiloxane according to claim 1, wherein R ³ is OCH ₃ . (A) The following general formula (5): (Wherein R ¹ and p have the same meanings as described above) and (B) the following general formula (6): (In the formula, R ¹ , R ² and R ³ have the same meanings as described above.)
2. The method for producing a nitrogen atom-containing polysiloxane according to claim 1, wherein a dealcoholation reaction is performed with the organosilane represented by the formula (1). 8. The nitrogen atom-containing composition according to claim 7, wherein the molar ratio of the component (A) to the component (B) is 0.5 <mol of (A) / mol of (B) ≦ 1.0. Method for producing polysiloxane. 9. The method for producing a nitrogen atom-containing polysiloxane according to claim 7, wherein the component (A) and the component (B) are subjected to a dealcoholation reaction and then modified with an organic acid, an inorganic acid or an epoxy compound. Method. 10. A fiber treatment composition comprising the nitrogen atom-containing polysiloxane according to claim 1 as a main component.