JP2002194677A - Fiber treatment agent - Google Patents

Abstract

(57) [Summary] [Problem] Does not cause yellowing problem and has good flexibility,
Provided is a fiber treating agent which can impart smoothness, has good adhesion to fibers, and has excellent durability. SOLUTION: (A) General formula HO [(R ¹ ) ₂ SiO]
_m [(R ¹ ) (Z) SiO] _n OH (wherein, Z is an epoxy group-containing organic group, R ¹ is the same or different, substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, m is an integer of 1 or more, n is an integer of 1 or more (provided that
m / n ≧ 10). The epoxy group-containing organosiloxane (B) represented by the general formula (R ² ) ₂ (R ³ ) Si (R ⁴ ) wherein R ² is the same or different and is a monovalent alkoxy group having 1 to 20 carbon atoms. Or a hydroxyl group and R ³ have 1 to 20 carbon atoms
A substituted or unsubstituted monovalent hydrocarbon group, R ⁴ is N-
(Β-aminoethyl) -γ-aminopropyl group) A fiber treatment agent comprising an aminosilane containing an aminosilane (C) having an epoxy group or an alkylammonium halide containing at least one epoxy residue.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber treatment agent, particularly a treatment agent for synthetic fibers such as polyester.

[0002]

BACKGROUND OF THE INVENTION Conventionally, synthetic fibers for wadding made of polyester fiber, acrylic fiber and the like are required to have good flexibility and smoothness, and thus have been treated with various silicone-based treating agents. I have.

For example, Japanese Patent Publication No. 48-17514 proposes a fiber treating agent comprising three kinds of combinations of epoxysiloxane and aminosiloxane, epoxysiloxane and amino compound, or aminosiloxane and epoxy compound. No. 19715, Japanese Patent Publication No. 5
JP-A-3-19716 proposes a fiber treatment agent comprising a combination of an epoxy siloxane and an aminoalkoxysilane, and these treatment agents impart flexibility and smoothness to synthetic fibers. Has a drawback that the treated fiber is yellowed by heating in the treatment step or standing for a long time based on the presence of an amino group.

In order to solve the problem of yellowing, amino-containing polyorganosiloxanes, reaction products of aminoalkyl-containing polyorganosiloxanes and epoxy compounds, aminoalkyl-containing polyorganosiloxanes, epoxy-containing polyorganosiloxanes And a fiber treating agent in combination with an epoxy compound (Japanese Patent Publication No. 5-15827), a fiber treating agent in combination with a polyorganosiloxane, an alkoxysilane and an aminosiloxane (Japanese Unexamined Patent Publication No.
No. 61653) has been proposed, and these treatment agents do not cause the problem of yellowing, but have a problem of lacking in flexibility and smoothness.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to avoid yellowing and to provide good flexibility and smoothness.
Another object of the present invention is to provide a fiber treatment agent having good adhesion to fibers and excellent durability.

[0006]

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that an epoxy-containing organosiloxane,
The present inventors have found that it is extremely effective to use a specific amino group-containing organosilane and an alkylammonium halide containing at least one epoxy group or epoxy residue, and have completed the present invention.

That is, the present invention relates to (A) the general formula HO
[(R ¹ ) ₂ SiO] _m [(R ¹ ) (Z) SiO] _n OH (wherein Z is an epoxy group-containing organic group, and R ¹ is the same or different and has 1 to 20 carbon atoms, substituted or unsubstituted) A is a monovalent hydrocarbon group, m is an integer of 1 or more, and n is an integer of 1 or more (provided that
m / n ≧ 10). (B) an epoxy group-containing organosiloxane represented by the general formula (R ² ) ₂ (R ³ ) Si (R ⁴ ) (wherein R ² is the same or different and is a monovalent alkoxy group having 1 to 6 carbon atoms) Or a hydroxyl group, R ³ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ⁴ is N- (β
-Aminoethyl) -γ-aminopropyl group) (C) A fiber treating agent comprising an alkylammonium halide containing at least one epoxy group or epoxy residue. It is.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the fiber treating agent of the present invention will be described in detail. The epoxy group-containing organosiloxane of the component (A) used in the present invention is represented by the above-mentioned general formula. As the substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms for R ¹ , (R ¹ ) 1) alkyl groups such as methyl, ethyl, propyl, butyl, hexyl,
(2) cycloalkyl groups having 4 to 7, preferably 6, carbon atoms such as octyl and decyl; and (3) alkenyl groups having 2 to 8, preferably 2 to 3 carbon atoms, such as cyclohexyl. , allyl, (4) an aralkyl group, an aryl moiety is (up to C ₄ about) phenyl or lower alkyl, especially substituted phenyl, the alkyl moiety of up to about C _4, for example, 2-phenylethyl,
And 2-phenylpropyl, (5) aryl group, especially phenyl or substituted phenyl (substituents include an alkyl group of up to about C _4), for example, a phenyl group, a tolyl group, and (6) substituted hydrocarbon group, In particular, those in which the substituent is halogen, such as 3,3,3-trifluoropropyl, are exemplified. The method for preparing the component (A) is as follows:
It can be obtained using a known technique, and can also be obtained as an emulsion using an emulsion polymerization method. Also, (A)
Has a viscosity range of 100 to 2,000,000 cP, preferably 1,000 to 1,000,000 cP.

The amino group-containing organosilane of component (B) is represented by the general formula (R ² ) ₂ (R ³ ) Si (R ⁴ ) (wherein R ² is the same or different and is a monovalent having 1 to 6 carbon atoms). R ³ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ⁴ is N- (β
-Aminoethyl) -γ-aminopropyl group). Specifically, N- (β-aminoethyl)-
γ-aminopropylmethyldimethoxysilane, N- (β
-Aminoethyl) -γ-aminopropylmethyldiethoxysilane and the like are preferred as the component (B).

The alkylammonium halide having one or more epoxy groups or epoxy residues as the component (C) includes those represented by the following general formula.

[0011] _{^{G p -N + (Cl -)}} (R 2) q (R 3) 4-pq ( where, G is an epoxy group or epoxy residues containing
A monovalent organic group, R ² is 1 to 30 carbon atoms, preferably linear or branched alkyl group is 1 to 18, an alkenyl group and an aliphatic dienyl groups, alkylphenyl, R ³
Represents a group having the same meaning as R ² or a monovalent hydrocarbon group having 1 to 6 carbon atoms. p is 1-3 and q is 0-2 (however, p + q
Represents an integer of 1 ≦ p + q ≦ 3). Specific examples include glycidyltrimethylammonium chloride, glycidyltridecyldimethylammonium chloride, 3-chloro-2-hydroxypropylmethylammonium chloride, and 3-chloro-2-hydroxypropyldodecyldimethylammonium chloride.

The mixing ratio of each component in the treating agent of the present invention is not particularly limited, but 100 parts by weight of component (A), 1 to 10,000 parts by weight of (B) + (C), (however, , (B) / (C) ≧ 10)
Is suitable, preferably based on 100 parts by weight of the component (A).
(B) + (C) 10 to 1000 parts by weight (provided that (B) / (C) ≧ 50).

The fiber treating agent of the present invention is emulsified and dispersed in water using an appropriate surfactant to form an emulsion, and if necessary, diluted with water to adjust to a desired concentration, immersion, spraying, etc. Is attached to the fiber, dried and heat-treated.

At the time of preparation, the siloxane raw material is emulsion-polymerized using a surfactant such as dodecylbenzene sulfonic acid, and then polymerized by adding an epoxy group-containing silane.
On the other hand, (B) an amino group-containing organosilane and (C) an alkylammonium halide containing at least one epoxy group or an epoxy residue are separately mixed to form an emulsion, and this is mixed with the above emulsion. And a method of preparing the solution by further diluting with water. The equipment used for emulsification and the emulsification conditions may be the same as those used in ordinary methods.

[0015]

Industrial Applicability The fiber treating agent of the present invention imparts good flexibility and smoothness to synthetic fibers such as polyester cotton wadding, and solves the problem of yellowing of fibers. It is suitably used for treating various fibers.

[0016]

The present invention will be described below with reference to examples. In Examples, all parts are parts by weight. Example 1 octamethyltetrasiloxane 34 parts, 0.5 parts of dodecylbenzenesulfonic acid and 60 parts of water was added, this was the primary emulsification with a homomixer under a pressure of 400 kg / cm ² using a high pressure homogenizer 2 Next emulsify and at 80 ° C 3
The polymerization was carried out for 3 hours at room temperature for a total of 6 hours. Then
3.3 parts of γ-glycidoxymethyldimethoxysilane was added, and polymerization was carried out at room temperature for 1 hour. Subsequently, after neutralization with 0.2 parts of triethanolamine, 2 parts of γ-glycidoxytrimethylammonium chloride was added,
Emulsion A containing an epoxy group-containing siloxane having a polymer viscosity of 100,000 cP was obtained.

Next, a treatment liquid B containing 3.7% by weight of the solid content of the emulsion A, 0.3% by weight of N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane and 96% by weight of water was prepared. This treatment liquid B was added to 20 g of a 6-denier × 64 mm polyester-fiber stuffed cotton at a concentration of 0.1%.
After spraying so as to be 4% by weight, the mixture was cured at 170 ° C. for 10 minutes.

The smoothness and the flexibility of the obtained treated cotton were evaluated by the following criteria. The appearance of yellowing was visually evaluated according to the following criteria. As a result, the treated cotton was ○ in all of the smoothness, flexibility and yellowing. Comparative Example 1 Emulsion C having a polymer viscosity of 100,000 cP was obtained in the same manner as in Example 1 except that γ-glycidoxytrimethylammonium chloride was removed from Emulsion A. Emulsion C instead of Emulsion A
A treatment liquid D was prepared in the same manner except that the above-mentioned was used, and treated cotton was obtained and evaluated in the same manner. As a result, the smoothness was Δ, the flexibility was Δ, and the yellowing was Δ. Comparative Example 2 Emulsion E having a polymer viscosity of 100,000 cP was obtained in the same manner as in Example 1 except that γ-glycidoxymethyldimethoxysilane was removed from Emulsion A. A processing solution F was prepared in the same manner except that emulsion E was used in place of emulsion A, and a treated cotton was obtained and evaluated in the same manner. Was. Comparative Example 3 Using the emulsion A prepared in Example 1 as a treatment liquid, a treated cotton was obtained and evaluated in the same manner. As a result, the yellowing was ○, the smoothness was △, and the flexibility was △. Comparative Example 4 In the treatment liquid B of Example 1, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane was used in place of N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane. Except for the above, a treatment liquid G was prepared in the same manner, and a treated cotton was obtained and evaluated in the same manner. As a result, the smoothness was poor, the flexibility was good, and the yellowing was good.

Claims (2)

[Claims] (A) The general formula HO [(R ¹ ) ₂ SiO]
_m [(R ¹ ) (Z) SiO] _n OH (wherein, Z is an epoxy group-containing organic group, R ¹ is the same or different, substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, m is an integer of 1 or more, n is an integer of 1 or more (provided that
m / n ≧ 10). (B) an epoxy group-containing organosiloxane represented by the general formula (R ² ) ₂ (R ³ ) Si (R ⁴ ) wherein R ² is the same or different and is a monovalent alkoxy group having 1 to 20 carbon atoms. Or a hydroxyl group and R ³ have 1 to 20 carbon atoms
A substituted or unsubstituted monovalent hydrocarbon group, R ⁴ is N-
(Β-aminoethyl) -γ-aminopropyl group-containing organosilane (C) A fiber comprising an alkylammonium halide containing one or more epoxy groups or epoxy residues Processing agent. 2. The fiber treating agent according to claim 1, which is a treating agent for cotton wool made of polyester fiber.