JPH11263844A - Chromogenic-group-containing polyorganosiloxane and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a chromogenic-group-containing polyorganosiloxane capable of dyeing a textile product and of imparting softness thereto by selecting a polyorganosiloxane having at least one chromogenic-group-containing siloxane unit and having the specified or larger number of silicon atoms in the molecule. SOLUTION: A chromogenic-group-containing polyorganosiloxane is provided comprising chromogenic-group-containing siloxane units represented by formula I and siloxane units represented by formula II and having 2-3,000 silicon atoms in the molecule. This is obtained by reacting a siloxane-unit-containing amino- containing polyorganosiloxane represented by formula III with a reactive dye containing a chromogenic group such as of a type of azo, anthraquinone, or the like and a reactive group such as substituted pyrimidyl. In the formulae, R<1> is a monovalent hydrocarbon group; R<2> is H or an alkyl; Q is a divalent group represented by Q<1> NH or Q<1> NHQ<2> NH; Q<1> is a 3-6C divalent hydrocarbon group; Q<2> is a 2-4C alkylene; Z is azo, anthraquinone, or the like; a is 0-2; b is 1 or 2; c is 0-2; d and e are each 0-3, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyorganosiloxane having a coloring group in a molecule and a method for producing the same, and more particularly, to a polyorganosiloxane bonded to a silicon atom through a specific divalent organic group in one molecule. The present invention relates to a chromogenic group-containing polyorganosiloxane having at least one chromogenic group-containing organic group and a method for producing the same. Furthermore, the present invention relates to a fiber treating agent and a polishing agent containing such a coloring group-containing polyorganosiloxane.

[0002]

2. Description of the Related Art Various polyorganosiloxanes including polymethylsiloxane and polymethylhydrogensiloxane have been used for imparting water repellency and flexibility to fibers. Among them, amino group-containing polyorganosiloxane is widely used as a main component constituting a fabric softening agent.

On the other hand, in the dyeing process of textile products, various kinds of organic dyes such as acid dyes, basic dyes and direct dyes are used. However, such dyes are generally processed into fibers by a dyeing step in an aqueous medium, and in some cases, are further colored by an aqueous processing step with a dyeing aid. Therefore, using a hydrophobic polymer such as polyorganosiloxane to impart flexibility to fibers requires a separate process from dyeing,
In addition, since a washing step needs to be interposed between the softening step and the dyeing step, the steps become complicated.

[0004] A color-forming polyorganosiloxane obtained by introducing a color-forming group of these organic dyes into a polyorganosiloxane, and a fiber treating agent containing the same have not been known.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyorganosiloxane into which a coloring group is introduced, which can be applied to dyeing of fibers and the like, and a method for producing the same. Another object of the present invention is to provide a fiber treating agent and a polishing agent capable of simultaneously dyeing fibers and the like and imparting flexibility.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, the amino group-containing polyorganosiloxane has a specific coloring group and a specific reactive group. The inventors have found that the object can be achieved by reacting the compounds, and have completed the present invention.

That is, the present invention provides a compound represented by the general formula:

Embedded image (Wherein R ¹ may be the same or different,
A substituted or unsubstituted monovalent hydrocarbon radical; Q is Q ¹
NH or Q ¹ NHQ ² NH represents a divalent group, Q ¹ represents a divalent hydrocarbon group having 3 to 6 carbon atoms,
² represents an alkylene group having 2 to 4 carbon atoms, wherein Q is bonded to the silicon atom via the carbon atom of Q ¹ ; Z may be the same or different, and may be azo, anthraquinone, A monovalent group containing a coloring group selected from the group consisting of phthalocyanine and azo complex salts and a hydrogen atom, and at least one in the molecule is a group containing a coloring group; R ² is the same or different; A hydrogen atom or a substituted or unsubstituted alkyl group,
Is an integer of 0 to 2, b is 1 or 2, c is an integer of 0 to 2, and a + b + c is an integer of 1 to 3). And the remaining siloxane units have the general formula:

Embedded image (Wherein R ¹ and R ² are each as described above; d and e are each an integer of 0 to 3, and d +
e is an integer of 0 to 3); and a coloring group-containing polyorganosiloxane having 2 to 3,000 silicon atoms in one molecule.

Further, the process for producing the color-forming group-containing polyorganosiloxane of the present invention comprises the steps of:

Embedded image (Wherein R ¹ , R ² , Q, a, b, and c are each as described above), and the amino group-containing polyorganosiloxane having at least one amino group-containing siloxane unit; A chromogenic group selected from the group consisting of azo, anthraquinone, phthalocyanine and azo complex salts; and substituted pyrimidinyl group, substituted pyrazinyl group,
Reacting a reactive dye having a reactive group selected from the group consisting of a substituted triazinyl group, a halo-substituted acetamido residue, an unsubstituted or halo-substituted acrylamide residue, a vinyl sulfone group and a glycidyl group and a precursor thereof. Features.

Further, the fiber treating agent and the polishing agent of the present invention are characterized in that they each contain the above-mentioned color-forming group-containing polyorganosiloxane.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The siloxane skeleton of the color-forming group-containing polyorganosiloxane of the present invention may be any of linear, branched, cyclic, and network-like. 000, preferably 10 to 1,000. The effect of imparting flexibility to the fiber is better as the number of silicon atoms is larger, but those having more than 3,000 silicon atoms are difficult to synthesize and handle.

In the present specification, the molecular structural formula of a polyorganosiloxane containing a plurality of types of siloxane units simply indicates the number of siloxane units, and does not necessarily mean a block copolymer. These polyorganosiloxanes may be random copolymers.

The polyorganosiloxane having a coloring group is represented by the following general formula:

Embedded image (Wherein R ¹ , Q and Z are each as described above; A ¹ may be the same or different from each other;

Embedded image (Wherein R ¹ is as described above; R ³ may be the same or different, and is R ² or -S
It is a triorganosilyl group represented by the iR ¹ _3; r is 0
Or a positive integer);
² may be the same or different, and R ¹ , OR
² or A ¹ ; p is a positive integer, q is 0 or a positive integer, and p, q, and r are numbers that satisfy the number of silicon atoms in one molecule described above) Having a linear or branched siloxane skeleton. Such a coloring group-containing polyorganosiloxane is,
It is preferable because it is easy to synthesize and gives the fiber excellent flexibility.

Further, other types of polyorganosiloxanes having a color-forming group include those represented by the general formula:

Embedded image (Wherein, R ¹ , Q and Z are as described above), a monofunctional chromophoric group-containing or amino group-containing siloxane unit, provided that at least one siloxane unit having a color-forming group in the molecule is bonded to each other And a siloxane unit containing -QZ is

Embedded image (Wherein, R ^2, d and e are as described above, respectively, provided that d + e is an integer from 0 to 2; or R ⁴ may be the same with or different from each other, it is R ¹ above,
-QZ), through one or more siloxane units containing or not containing a color-forming group, which are present as at least part of the terminal groups of the polyorganosiloxane or Those having a branched siloxane skeleton are shown.

Further, the coloring group-containing polyorganosiloxane is represented by the following general formula:

Embedded image (Wherein R ¹ , A ² , Q and X are each as described above; m is a positive integer, n is 0 or a positive integer, and m + n is a number from 3 to 6). As shown, those having a cyclic siloxane skeleton are shown.

As described above, the polyorganosiloxane of the present invention has a general formula: -QZ bonded to a silicon atom, wherein Z has at least one color group-containing group containing a color group in the molecule. . Here, Q is Q ¹ NH or Q ¹ N
HQ ² NH represents a bond to a silicon atom via the carbon atom of Q ¹ . Q ¹ is a divalent hydrocarbon group having 3 to 6 carbon atoms, and includes a linear alkylene group such as trimethylene, tetramethylene, pentamethylene, and hexamethylene; and a branched group such as 2-methyltrimethylene. And a cyclic hydrocarbon group such as cyclohexane-1,4-diyl and 1,4-phenylene, and a trimethylene group is preferred because of easy synthesis and chemical stability. Q ² is an alkylene group having 2 to 4 carbon atoms, and examples thereof include ethylene, trimethylene, and tetramethylene. An ethylene group is preferable because of easy synthesis. That is, Q is Q ¹ NH and Q ¹
Is a trimethylene group and Q ¹ NHQ ² NH, wherein Q ¹ is a trimethylene group and Q ² is an ethylene group.

As described above, Z is selected from a group containing a coloring group and a hydrogen atom, and at least one in the molecule is a group containing a coloring group. The coloring group-containing group is an organic group bonded to a silicon atom via Q, and includes one or two or more coloring groups selected from the group consisting of azo, anthraquinone, phthalocyanine, and azo complex salts. Including. The coloring group is represented by the formula:

Embedded image

Embedded image An azo coloring group represented by the formula:

Embedded image An anthraquinone-based coloring group represented by the formula:

Embedded image And a phthalocyanine-based coloring group represented by the formula:

Embedded image And an azo complex-based coloring group represented by the following formula: These coloring groups include the residue of a reactive group described below, a divalent hydrocarbon group such as methylene and ethylene; a divalent substituted hydrocarbon group such as 2-hydroxypropane-1,3-diyl; And to the nitrogen atom of Q via one or more groups such as groups and amide groups. Such a coloring group-containing group may have another reactive group bonded to the coloring group.

Examples of the organic group R ¹ bonded to the silicon atom include an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl and dodecyl; a cycloalkyl group such as cyclohexyl; Allyl, 1-butenyl, 1-pentenyl,
Alkenyl groups such as 1-hexenyl; aralkyl groups such as 2-phenylethyl and 2-phenylpropyl; aryl groups such as phenyl, tolyl and xylyl; and 3-aminopropyl, N- (2-aminoethyl)- 3-
Substituted hydrocarbon groups such as aminopropyl, 3-chloropropyl, 3,3,3-trifluoropropyl are exemplified, are easy to synthesize and handle, and impart flexibility to fibers, a characteristic of polyorganosiloxanes. A methyl group is most preferred because it exhibits the best properties.

R ² is a hydrogen atom constituting a silicon-functional hydroxy group together with an adjacent oxygen atom; similarly, methyl, ethyl, propyl,
Examples include an alkyl group such as butyl; and a substituted alkyl group such as 2-methoxyethyl and 2-ethoxyethyl which constitute a substituted alkoxy group, and a methyl group and an ethyl group which can be synthesized and handled relatively stably. preferable.

In these siloxane units having a color-forming group and amino-containing siloxane units having R ¹ , QZ and OR ² , b is 1 or 2. However, b is preferably 1 because of easy synthesis. a and c are each an integer of 0 to 2; and when b is 1, the siloxane unit is at the molecular terminal when a + c is 2, at the branch point of the siloxane skeleton when a + c is 0, and when a + c is 1 Exists at other intermediate positions.

In the linear or branched polyorganosiloxane, R ³ present at the terminal of the molecular chain may be a group constituting a silicon functional group such as R ² described above, or a stable monofunctional siloxane unit. And triorganosilyl groups such as dimethyl (tert-butyl) silyl, dimethylphenylsilyl and dimethylvinylsilyl, and the above-mentioned methyl and ethyl groups, and a trimethylsilyl group are preferred.

A ¹ is the aforementioned R ³ when r is 0. When r is a positive integer, it is a silyl group or (poly) siloxanyl group in which R ¹ and OR ³ are bonded to a silicon atom. A ² is R ¹ , OR ² or A ¹
It is. In these A ¹ and A ² , R ¹ and R ³ are the same as those described above. Similarly, R ¹ is a methyl group; OR ² is a methoxy group and an ethoxy group; OR ³ is a methoxy group; Ethoxy and trimethylsiloxy groups are preferred.

The color-forming group-containing polyorganosiloxane of the present invention can be obtained, for example, as follows. That is, first, in the molecule (A) corresponding to the polyorganosiloxane to be synthesized, a general formula:

Embedded image (Wherein R ¹ , R ² , Q, a, b and c are as described above), and an amino-containing polyorganosiloxane having at least one amino-containing siloxane unit having a primary amino group. Prepare Here, R ¹ has -Q which reacts with the reactive dye (B).
It is shown as not including the H group. When a siloxane unit other than the amino group-containing siloxane unit in the molecule is present, the unit is the same as the remaining siloxane unit in the color-forming group-containing polyorganosiloxane of the present invention.

Such (A) is synthesized by, for example, the following method, but the production method is not limited to these.

(1) In the presence of an amino-containing alkoxysilane in which an amino-substituted hydrocarbon group such as 3-aminopropyl or N- (2-aminoethyl) -3-aminopropyl is bonded to a silicon atom, A cyclic diorganosiloxane oligomer such as methylcyclotetrasiloxane is subjected to ring-opening polymerization to synthesize an amino group-containing polyorganosiloxane having an alkoxy group at a molecular terminal.

(2) The amino group-containing polyorganosiloxane obtained in the above (1) is reacted with a silylating agent such as hexamethyldisilazane to form an amino group-containing polyorganosiloxane having a triorganosiloxane unit at a molecular terminal. Synthesize organosiloxane.

(3) A haloalkyl group such as chloropropyl is introduced by subjecting a polyorganosiloxane containing a hydrosilyl group such as polymethylhydrogensiloxane to a hydrosilylation reaction with a halo-substituted alkene such as allyl chloride. Thereafter, the resultant is treated with an amino compound such as ammonia or ethylenediamine to synthesize an amino group-containing polyorganosiloxane.

The primary and / or secondary amino groups present in (A) are reacted with a reactive dye (B). Due to the excellent reactivity of the reactive dyes with the reactive groups, the reaction takes place preferentially over primary amino groups.
The color-forming group in (B) is one or two selected from the group consisting of azo-type, anthraquinone-type, phthalocyanine-type and azo-complex-salt type, which are the same as the objective color-group-containing polyorganosiloxane of the present invention. Including the above, similar ones are exemplified.

The reactive group present in (B) and reacting with (A) includes a group represented by the formula:

Embedded image A substituted pyrimidinyl group as shown by the formula:

Embedded image A substituted pyrazinyl group as shown by the formula:

Embedded image A substituted triazinyl group as shown by the formula:

Embedded image A halo-substituted acetamido residue as shown by the formula:

Embedded image An unsubstituted or substituted acrylamide residue and a precursor thereof as shown by the formula:

Embedded image A vinyl sulfone group and a precursor thereof as shown by
And the formula:

Embedded image Are exemplified.

In (B), the above-mentioned coloring group may be directly bonded to the above-mentioned reactive group, and may be a divalent hydrocarbon group such as methylene or ethylene; 2-hydroxypropane-1,3- It may be bonded via one or more divalent substituted hydrocarbon groups such as diyl; one or more groups such as an imino group and an amide group.

Examples of (B) include, among reactive dyes for wool or nylon, Lanasol dye (Ciba-Geigy)
Co., Ltd.), Hostalan dye (Hoechst Co., Ltd.), Verofi
x Dye (Beyer Co., Ltd.), Procinyl dye (ICI Co., Ltd.)
And those having a reactive group showing sufficient reactivity with an amino group such as Drimararan dye (manufactured by Sandoz Co., Ltd.) and Realan dye (manufactured by Dystar Japan Co., Ltd.).

In the production method of the present invention, the amount of (B) used is not particularly limited. However, in order to give a satisfactory color developing property to the polyorganosiloxane, the amount of (B) relative to 100 parts by weight of (A) is usually 10 parts by weight or less is sufficient, and unreacted amino group-containing polyorganosiloxane may remain. In the case where (B) has two or more reactive groups in the molecule, if the amount of (B) exceeds 10 parts by weight, (B) acts as a cross-linking agent for (A), which is remarkable. It may cause an increase in viscosity and formation of a gel.

In the production method of the present invention, the reaction between (A) and (B) proceeds at room temperature, and the reaction temperature is not particularly limited, but a side reaction such as thermal decomposition of (A) or (B) is performed. In order to prevent the reaction, the reaction temperature is preferably 100 ° C. or lower. Further, since the progress of the reaction is extremely slow without a catalyst, it is preferable to use a dyeing aid and glacial acetic acid as a reaction catalyst. As the dyeing aid, a dyeing aid used for reactive dyes for wool can be used, and Albegal B
, Albegal SET (manufactured by Ciba-Geigy Corporation), Avolan REN
(Dyestar Japan Co., Ltd.) and the like.

In the production method of the present invention, it is not necessary to use an organic solvent. When the reactive dye (B) is a solid at room temperature, it is preferable to dissolve (B) in water before use.

When it is necessary to purify the color-forming group-containing polyorganosiloxane of the reaction product or the composition containing the polyorganosiloxane, low-boiling components such as water and acetic acid are distilled off under reduced pressure, and then filtration is performed. By this, unreacted reactive dye can be removed.

The fiber treating agent of the present invention is characterized by containing the color-forming group-containing polyorganosiloxane of the present invention. In order to impart particularly excellent flexibility, it is preferable to include an amino group-containing polyorganosiloxane together with the color-forming group-containing polyorganosiloxane. The mixing ratio of the color-forming group-containing polyorganosiloxane and the amino group-containing polyorganosiloxane is not particularly limited. Any of the following may be used as the amino-containing polyorganosiloxane.

(1) In synthesizing the color-forming group-containing polyorganosiloxane of the present invention, (A) is used in excess with respect to (B), and the system in which (A) remains is used as it is as a fiber treating agent or a component thereof. Used as

(2) An amino group-containing polyorganosiloxane is added to the color-forming group-containing polyorganosiloxane obtained by the synthesis. The amino group-containing polysiloxane to be added may be the same as or different from that used in the synthesis as (A).

The fiber treating agent of the present invention can be prepared by using the above-mentioned color-forming group-containing polyorganosiloxane or, preferably, a mixture of the polyorganosiloxane and the amino-group-containing polyorganosiloxane as it is, depending on the mode of use. It may be used in the form of a solution, an emulsion or the like. When used as a solution, alcohols such as isopropyl alcohol and butanol; ketones such as acetone and methyl ethyl ketone can be used as the solvent. When used as an emulsion, it can be emulsified with water in the presence of a suitable nonionic, anionic or cationic surfactant.

The polishing agent of the present invention is obtained by converting the above-mentioned polyorganosiloxane containing a color-forming group into a polyorganosiloxane containing no color-forming group, such as polydimethylsiloxane or amino-containing polyorganosiloxane, or various waxes. , Liquid paraffin, a foaming agent, an organic solvent, water and the like, and prepared in an arbitrary form, that is, a form such as a wax, a solution, a cream, and an emulsion. In order to prepare the polish emulsion, other surfactants may be blended according to the purpose, or the emulsifiability of the color-forming group-containing polyorganosiloxane itself may be used.

[0040]

The color-forming group-containing polyorganosiloxane of the present invention has a dyeing function, has the property of imparting flexibility to fibers, a characteristic of polyorganosiloxane, and is easily emulsified to form an aqueous emulsion. Can be formed. Therefore, the fiber treating agent of the present invention containing the same can impart excellent flexibility to the textile at the same time as dyeing the textile by a single treatment bath. It greatly contributes to the rationalization of textile product dyeing and soft finishing processes, and is extremely useful in the textile processing industry.

The polishing agent of the present invention, which contains the color-forming group-containing polyorganosiloxane of the present invention, can be easily applied to the surface of various articles, and has gloss and repellency excellent in persistence and weather resistance as well as coloring. It has the effect of giving water and hiding scratches on the substrate. Therefore, it is useful as a car wax, shoe cream, leather treatment agent and the like.

In addition, the color-forming group-containing polyorganosiloxane of the present invention has a lipophilic portion such as a polysiloxane portion and a hydrophilic portion in the molecule, and can be used as a surfactant. Further, by utilizing the properties of polyorganosiloxane together with its coloring properties, it is used as an ink for inkjet printers and the like, an additive thereof, a color toner and a additive thereof. It is also used as an additive for aqueous and oily paints and inks; plastics; rubber; cosmetics such as lipsticks, foundations, eye shadows, and nail polish. In addition, coloring of light diffusing plates such as backlights of liquid crystal displays, fluorescent lighting fixtures, advertising displays, television image projectors, and copiers; surface treatment of powders, metals, plastics, and other various applications Useful.

[0043]

The present invention will be described in more detail with reference to the following examples. The present invention is not limited by these examples. In the examples, all parts are parts by weight.

Example 1 A reaction vessel was charged with the formula (I):

Embedded image Amino group-containing polyorganosiloxane 100 represented by
Part and zwitterionic dyeing assistant (Albeg manufactured by Ciba-Geigy Co., Ltd.)
al B) A mixture was prepared by charging 0.02 parts. Then

Embedded image 0.2 parts of an azo yellow reactive dye represented by
The resulting mixture was mixed with an aqueous solution of a dye prepared in advance, and stirred at room temperature for 10 minutes. Then, 0.1 part of a 10% aqueous acetic acid solution was added, and the mixture was further stirred for 10 minutes to obtain a clear yellow oily substance. While the yellow reactive dye before the reaction was water-soluble and did not dissolve in the amino-containing polyorganosiloxane, the yellow oil was stable and dispersed in water but did not dissolve. After the yellow oil was washed with water and dried, unreacted reactive dye was filtered off. The obtained oil has an infrared absorption spectrum (shown in FIG. 1).
From the UV-visible absorption spectrum (shown in FIG. 2),
The mixture was found to be a mixture of a polyorganosiloxane containing a coloring group and a polyorganosiloxane containing an amino group.

A yellow emulsion obtained by emulsifying with 2 parts of polyoxyethylene (5) lauryl ether and 83 parts of water with 15 parts of the oily substance using a homogenizer was further diluted 50-fold with water. A treatment bath was prepared.
When the polyester taffeta was dyed using this treatment liquid, a yellow dyed product was obtained.

Example 2 Instead of a yellow reactive dye, the formula:

Embedded image A red oily substance was obtained in the same manner as in Example 1 except that the azo red reactive dye represented by the following formula was used. From the infrared absorption spectrum and ultraviolet-visible absorption spectrum (shown in FIG. 3) of the obtained oily substance, it was found that it was a mixture of a polyorganosiloxane containing a coloring group and a polyorganosiloxane containing an amino group.

From the oil, a treatment bath was prepared in the same manner as in Example 1 and dyed with polyester taffeta, whereby a red dyed product was obtained.

Example 3 An amino group-containing polyorganosiloxane represented by the formula (I)
I):

Embedded image Was used in the same manner as in Example 1 except that a blue reactive dye (Lansol Blue 3G manufactured by Ciba-Geigy Co., Ltd.) was used instead of the yellow reactive dye to obtain a blue oily substance. . From the infrared absorption spectrum and the ultraviolet-visible absorption spectrum (shown in FIG. 4) of the obtained oily substance, it was found that the oily substance was a mixture of a chromogenic group-containing polyorganosiloxane and an amino group-containing polyorganosiloxane.

Example 4 Instead of a blue reactive dye, a black reactive dye (Ciba-Geigy
A black oily substance was obtained in the same manner as in Example 3 except that Lansol Black B (manufactured by Corporation) was used. From the infrared absorption spectrum and the ultraviolet-visible absorption spectrum (shown in FIG. 5) of the obtained oily substance, it was found that it was a mixture of a chromogenic group-containing polyorganosiloxane and an amino group-containing polyorganosiloxane.

Example 5 As an amino group-containing polyorganosiloxane, Example 3 was used.
Using 100 parts of (II) used as a reactive dye,
Using 2 parts of the yellow reactive dye used in Example 1, the amount of the dyeing aid was 0.03 parts, the amount of water was 4 parts, and the amount of the 10% acetic acid aqueous solution to be added was 0.2 part. Reaction was carried out under the same procedures and conditions as in 1 to obtain a yellow oil. The obtained oily substance was found to be a color-forming group-containing polyorganosiloxane from its infrared absorption spectrum and ultraviolet-visible absorption spectrum.

To 15 parts of the thus obtained polyorganosiloxane containing a yellow coloring group, 2 parts of polyoxyethylene (5) lauryl ether and 83 parts of water were added.
A premix was obtained by stirring with a homomixer. This was emulsified using a homogenizer to prepare a fiber treating agent as a yellow aqueous emulsion. 2 parts of this emulsion was taken and diluted with 98 parts of water to prepare a treatment bath of Example 5.

Example 6 As the polyorganosiloxane, 7.5 parts of the yellow color-forming group-containing polyorganosiloxane obtained in Example 5 and the same amino acid as used in Example 5 as a raw material for synthesizing the polyorganosiloxane were used. A fiber treatment agent was prepared in the same manner as in Example 5 except that a mixture with 7.5 parts of the group-containing polyorganosiloxane (II) was used, and a treatment bath was prepared in the same manner.

Comparative Example 1, Evaluation Example 1 Polyester taffeta and cotton broad were immersed in each of the treatment baths prepared in Examples 5 and 6, and the amount of the active ingredient of the fiber treatment agent was reduced to 0.3%. After being squeezed with a mangrol and then air-dried, it is dried by heating to 100 ° C. for 2 minutes in a hot air drier.
After heating at 2 ° C. for 2 minutes, each treated cloth sample was obtained. For comparison, the yellow reactive dye used in Example 1 was used instead of the color-forming group-containing polyorganosiloxane to carry out dyeing by a conventional method to obtain a sample of Comparative Example 1.

The following evaluation was performed on these samples. (1) Sliminess: The texture of the treated cloth was evaluated by finger touch. (2) Flexibility: The bending stiffness and recoverability of the treated cloth were measured using a Kawabata Pure Bending Tester KES-FB2 (trade name of Kato Tech Co., Ltd.), and the average value was determined. The smaller the value, the softer it is. (3) Color fastness: The color fastness to rubbing of the treated cloth in the wet state was evaluated by a wet test method of JIS L0849, and recorded based on the criteria for discoloration described in JIS L0801. The results of these evaluations are as shown in Table 1.

[0055]

[Table 1]

Examples 7 to 10 and Comparative Example 2 According to the composition shown in Table 2, the mixture of the color-forming group-containing polyorganosiloxane and the amino group-containing polyorganosiloxane obtained in Examples 1 to 4 had a viscosity at 25 ° C. 20cS
t), mixed homogeneously with a homomixer together with polydimethylsiloxane, acetic acid and ethyl alcohol, and then, through a homogenizer, prepared emulsion car wax of Examples 7 to 10, and then diluted 20-fold with ethyl alcohol to obtain a treatment solution. did. For comparison, a car wax of Comparative Example 2 containing no coloring group-containing polyorganosiloxane was prepared in the same manner.

Examples 11 to 14, Comparative Example 3 According to the composition shown in Table 2, half of the mixture containing the color-forming group-containing polyorganosiloxane obtained in Examples 1 to 4 was replaced with the color-forming group-containing polyorganosiloxane in Example 1. Emulsion car waxes of Examples 11 to 14 and Comparative Example 2 were prepared in the same manner as described above except that the same amino group-containing polyorganosiloxane (I) used as a raw material for the synthesis of siloxane was used. A liquid was prepared.

[0058]

[Table 2]

Evaluation Example 2 The painted surfaces of the yellow, red, blue and black baked steel sheets were coated in one direction with a towel to which aluminum oxide was adhered.
It was rubbed 0 times to make a fine scuff, and then washed with water.
Examples 7-1 on the painted surface in a wet state without water drying
The treatment liquid of the car wax of each corresponding color prepared in 4 was sprayed uniformly using a trigger pump. For comparison, the treatment liquids prepared in Comparative Examples 2 and 3 were applied to the painted surfaces of the above-described four-color painted steel plates, respectively. Next, excess treatment liquid on the surface of the base material was washed away with tap water and dried naturally to obtain an evaluation sample.

The following evaluation was performed on these evaluation samples.

(1) Scratch concealing property: The degree of concealing a scratch on the treated surface was visually observed to determine the initial scratch concealing property.
Next, the degree of concealment after watering was continued for 90 seconds was visually observed to determine the durability of the wound concealing property. ：: The scratch is remarkably concealed as compared with the untreated one. Δ: Scratch is slightly concealed as compared with untreated. X: The scratches appear to be substantially the same as those in the case of no treatment.

(2) Water repellency: Water was sprayed, and the shape of water droplets was visually observed to determine the initial water repellency. Then, the shape of the water drop after continuing watering for 90 seconds was visually observed,
The water repellency was maintained. ：: The shape of the water droplet is almost spherical. Δ: Spherical and irregular shaped water droplets are mixed. ×: The shape of the water droplet is almost irregular.

Gloss: The gloss of the treated surface was visually observed. ：: Gloss is remarkable as compared with untreated. Δ: Gloss is slightly recognized as compared with untreated. ×: Compared with untreated, the gloss is the same or inferior.

(4) Unevenness: The gloss and color tone of the treated surface were visually observed. ：: uniform, no difference in shade Δ: There is a slight difference in shading. X: There is a clear difference in shading.

The results are shown in Table 3. The painted surfaces sprayed with the treatment liquids of Comparative Examples 2 and 3 did not differ depending on the coating color, and are collectively shown in Table 3, respectively.

[0066]

[Table 3]

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of the polyorganosiloxane obtained in Example 1.

FIG. 2 is an ultraviolet-visible absorption spectrum of the polyorganosiloxane obtained in Example 1.

FIG. 3 is an ultraviolet-visible absorption spectrum of the polyorganosiloxane obtained in Example 2.

FIG. 4 is an ultraviolet-visible absorption spectrum of the polyorganosiloxane obtained in Example 3.

FIG. 5 is an ultraviolet-visible absorption spectrum of the polyorganosiloxane obtained in Example 4.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09B 69/10 C09B 69/10 Z C09D 5/00 C09D 5/00 ED06M 15/643 D06M 15/643

Claims (7)

[Claims] 1. A compound represented by the following general formula: (Wherein R ¹ may be the same or different,
A substituted or unsubstituted monovalent hydrocarbon radical; Q is Q ¹
NH or Q ¹ NHQ ² NH represents a divalent group, Q ¹ represents a divalent hydrocarbon group having 3 to 6 carbon atoms,
² represents an alkylene group having 2 to 4 carbon atoms, wherein Q is bonded to the silicon atom via the carbon atom of Q ¹ ; Z may be the same or different, and may be azo, anthraquinone, A monovalent group containing a coloring group selected from the group consisting of phthalocyanine and azo complex salts and a hydrogen atom, and at least one in the molecule is a group containing a coloring group; R ² is the same or different; A hydrogen atom or a substituted or unsubstituted alkyl group,
Is an integer of 0 to 2, b is 1 or 2, c is an integer of 0 to 2, and a + b + c is an integer of 1 to 3). And the remaining siloxane units have the general formula: (Wherein R ¹ and R ² are each as described above; d and e are each an integer of 0 to 3, and d +
e is an integer of 0 to 3); and a chromogenic group-containing polyorganosiloxane having 2 to 3,000 silicon atoms in one molecule. 2. The polyorganosiloxane according to claim ¹ , wherein Q is Q ¹ NH and Q ¹ is a trimethylene group. 3. The polyorganosiloxane according to claim 1, wherein Q is Q ¹ NHQ ² NH, Q ¹ is a trimethylene group, and Q ² is an ethylene group. 4. A compound represented by the general formula: ## STR3 ## (Wherein R ¹ , R ² , Q, a, b, and c are each as described above), and the amino group-containing polyorganosiloxane having at least one amino group-containing siloxane unit; A chromogenic group selected from the group consisting of azo, anthraquinone, phthalocyanine and azo complex salts; and substituted pyrimidinyl group, substituted pyrazinyl group,
Reacting a reactive dye having a reactive group selected from the group consisting of a substituted triazinyl group, a halo-substituted acetamido residue, an unsubstituted or halo-substituted acrylamide residue, a vinyl sulfone group and a glycidyl group and a precursor thereof. A method for producing a color-forming group-containing polyorganosiloxane. 5. A fiber treatment agent comprising the color-forming group-containing polyorganosiloxane according to claim 1. 6. The fiber treating agent according to claim 5, further comprising an amino group-containing polyorganosiloxane. 7. A polishing agent comprising the color-forming group-containing polyorganosiloxane according to claim 1.