JPS6037228B2 - Textile treatment agent - Google Patents

Description

[Detailed description of the invention] The present invention relates to a treatment agent for fibers.

More specifically, the present invention relates to a fiber treatment agent for imparting durable antistatic properties, moisture and sweat absorption properties, antifouling properties, flexibility, smoothness, wrinkle resistance, compression recovery properties, etc. to fiber materials. Conventionally,
Various treatment agents made of organopolysiloxanes and compositions thereof have been provided or proposed in order to impart flexibility, smoothness, wrinkle resistance, recovery properties, etc. to fiber materials. for example,
Dimethylpolysiloxane oil or its emulsion is used to impart flexibility, while methylhydrogen polysiloxane, dimethylpolysiloxane with both hydroxyl groups endblocked, and condensation are used to impart durable flexibility, wrinkle resistance, and recovery properties. Treatment agents comprising reaction catalysts, methylhydrogen polysiloxanes, vinyl group-containing diorganopolysiloxanes, and addition reaction catalysts are known.

A new and specific example is Special Publication No. 48-17514.
In the publication, a treatment agent consisting of an organopolysiloxane having at least two epoxy groups per molecule and an organopolysiloxane having an amino group is used to smooth organic synthetic fibers, while in the publication No. A treatment agent consisting of a blocked diorganopolysiloxane, an organosilane having an amino group and an alkoxy group in one molecule, and/or its partial hydrolyzate and condensate is disclosed in Japanese Patent Publication No. 19715 and Samurai Publication No. 53-
No. 19716 discloses a treatment agent consisting of an aminoalkyltrialkoxysilane and an epoxy group-containing organopolysiloxane, while Hakamakai No. 53-Satoshi No. 49y uses a treatment agent consisting of a triorganosiloxy group at both ends having two or more aminoalkyl groups in one molecule. Blocked diorganopolysiloxanes have been proposed. However, these conventionally known processing agents have certain drawbacks.

For example, treatment agents based on dimethylpolysiloxane oil have the drawbacks of insufficient wrinkle prevention and recovery properties, and lack of durability in terms of flexibility and smoothness. Treatment agents containing alkoxysilanes as an essential component have the disadvantage that when used in the form of an emulsion, the alkoxysilane is easily hydrolyzed and the life of the treatment is short, and that the texture is too hard. Treatment agents that require methylhydrogen polysiloxane have the disadvantage that they do not undergo a sufficient curing reaction unless a catalyst is used, and if a catalyst is used, the life of the treatment will be shortened, and a large amount of hydrogen gas, which is dangerous and can cause a fire or explosion, is generated. There is a drawback that it does. Treatment agents based on eboxy group-containing organopolysiloxane and amino group-containing organopolysiloxane often generate static electricity due to friction, oily stains tend to adhere, and moisture and sweat absorption properties decrease when underwear is treated. There is a point. To improve this, hydrophilic surfactants such as ricinolenic acid sulfate ester salt, funnel oil, polysiloxane/polyoxyalkylene copolymers, and polyoxyethylene adducts of higher alcohols have been added to treatment agents. . However, these surfactants have the drawback of being easily soluble in water or organic solvents used for dry cleaning, and easily falling off after repeated washing, resulting in poor durability. The inventors of the present invention have conducted intensive studies to resolve the drawbacks of the conventionally known fiber treatment agents as described above, and have found that the fiber materials have durable antistatic properties, moisture and sweat absorption properties, antifouling properties, flexibility, We have now invented a treatment agent for fibers that can impart smoothness, wrinkle resistance, and compression recovery properties. That is, the present invention is a fiber treatment agent containing 1, leg, or wind and (C') as main ingredients among the following three types of organopolysiloxanes: 1, 'B' and 2. Organopolysiloxane has the general formula W [wherein R is a substituted or unsubstituted monovalent hydrocarbon group, A
is a group selected from R and -RI-COOR2, RI
is a divalent hydrocarbon group, R2 is a hydrogen atom or a monovalent hydrocarbon group, 1 is 0 to 2000, m is 0 to 200 (if m is 0, both A and -RI-COOR are also vines, m is 1, at least one of A is -RI-COOR2 group), and 10m is 1 to 2000.

], at least two -RI-C in one molecule
Organopolysiloxane having two OOR groups, general formula [wherein R is a substituted or unsubstituted monovalent hydrocarbon group, B
is a group selected from R, 1R3-(NHCH2CH2)a-NHR4 and G, R3 is a divalent hydrocarbon group, R4 is a hydrogen atom or a monovalent hydrocarbon group, a is 0 to 10, G is 1(R5 ) b 101 (C2 days 40) C- (C3 days 60) d
-R6 (here, R5 is a divalent organic group, R6 is a hydrogen atom or a terminal capping group, b is 0 or 1, c and d are 0-
50, however, c + d is 1 to 100), p is 0 to 1
000, q and r are 0 to 100, provided that p+q+r is 2 to 1000.

], and at least two 1R31(
NHC ratio CH2) a-organopolysiloxane having NHR4 groups and at least one polyoxyalkylene group, and [C} general formula [wherein R is a substituted or unsubstituted monovalent hydrocarbon group, D
is a group selected from R, E and G, E is an epoxy group-containing monovalent organic group, and G is -(R5)b-○-(C2day○)c
-(C340)d-R6 (wherein, R5 is a divalent organic group, R6 is a hydrogen atom or a terminal capping group, b is 0 or 1,
c and d are 0 to 50, provided that c+d is 1 to 100), x is 0 to 100u, y and z are 0 to 100, but ×10 y+z is 2 to 1000.

], and is an organopolysiloxane having at least two epoxy group-containing organic groups and at least one polyoxyalkylene group in one molecule. That is,
The fiber treatment agent of the present invention is based on an organopolysiloxane consisting of a combination of {circle around (1)}, [B], and [C'].

■, 'B- and 'C} organopolysiloxanes have antistatic properties, moisture absorption and
Although it merely imparts sweat absorption, flexibility, smoothness, wrinkle resistance, and compression recovery properties, heat treatment is performed by roughly combining wind and two types of organoborisiloxanes {B', ■, and 'C}. Since the cross-linking reaction occurs between the carboxyl group and the amine/group, and between the carboxyl group and the epoxy group (in this case, it is better to use a catalyst), the above-mentioned effects are not only improved, but also durability can be imparted. This is based on confirmation that it is possible. Note that durability here means that it can withstand water washing and dry cleaning well and last a long time. The organopolysiloxane as the harmful component is represented by the general formula described above, where R is a substituted or unsubstituted monovalent hydrocarbon group, such as a methyl group, an ethyl group, a propyl group, a dodecyl group, a pinyl group, or a phenyl group. , 8-phenylethyl group, 3,3,3-trifluoropropyl group, and the like. All R's in one molecule need not be the same.

R is most commonly a methyl group, but combinations of methyl and other groups are also common. -RI-COOR2 groups of RI
is a divalent hydrocarbon group, -C ratio-, 1CQC day 2-,
Alkylene groups such as 1CH to CH2, 1CQC day (CH3) CH2 1, 1 (C stop) 41, 1 (C ratio) 2-C
An alkylene arylene group such as 6-4 is exemplified.

Among these, alkylene groups are the most common. R5 is a hydrogen atom or a monovalent hydrocarbon group, and examples of the latter include methyl group, ethyl group, propyl group, hexyl group, and phenyl group. In addition, A is the above-mentioned R and -RI-
A group selected from COOR2. 1 is 0-2000
, m is 0 to 200 (however, since at least two -RI-COOR2 groups are required in one molecule, if m is 0, both A are -RI-COOR2 groups, and m is 1
(in which case at least one of A is -RI-COOR2 group), 10m is 1 to 2000.

The carboxy group or carboxyl ester group of the component {B} is crosslinked with the amino group of the component {B} or the epoxy group of the component (C} to impart durable antistatic properties to the fiber material.
In order to impart moisture/sweat absorption, stain resistance, flexibility, smoothness, wrinkle resistance, and compression recovery properties, at least two -RI-COOR2 groups are required in one molecule of component (2).

At least two -RI-COOR2 groups may be present anywhere in the molecular structure of the organopolysiloxane. In addition, if the value of 10 m (especially 1) is small, the effect of imparting flexibility and smoothness to the fiber material will be reduced, and if it is large, the emulsification will become thick, so the preferable range is 10 to 1.
It is 1000. This leg component is, for example,
It can be produced using the addition reaction described in Japanese Patent Publication No. 6 and Japanese Patent Publication No. 36-11293. The organopolysiloxane of component [B} is represented by the above-mentioned general formula, where R is a substituted or unsubstituted monovalent hydrocarbon group, and the same examples as R mentioned above are exemplified.
All R's in one molecule need not be the same.

R is most commonly a methyl group, but combinations of methyl and other groups are also common. -R3-(NHCH2CH
2) R3 in a-NHR4 is a divalent hydrocarbon group, and as in the above RI, -CH2-, 1CWC2-, 1CH2CQ
CH2-,1CH2CH(CH3)CH2-,1(CH
2) Alkylene groups such as 4- and alkylenearylene groups such as 1 (C ratio) 2-C6 and 4- are exemplified. Among these, alkylene groups are the most common. R4 is a hydrogen atom or a monovalent hydrocarbon group, and like R2 above, monovalent hydrocarbon groups include methyl group, ethyl group, propyl group,
Examples include hexyl group and phenyl group. a is a number from 0 to 10. G is -(R5)b-○-(C2day○)c-(
C3 is ○) d-R6 (in the formula, R5 is a divalent organic group,
Examples include an alkylene group having 1 to 5 carbon atoms, an alkylene group, and a group in which a -C group, one CO group, or one NHCO group is bonded through an alkylene group bonded to an elementary atom. R
6 is a hydrogen atom or a terminal blocking group; examples of the terminal blocking group include a monovalent hydrocarbon group, an acyl group, and a carbonate monoester group; examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, and a dodecyl group. , cyclohexyl group, phenyl group, B-phenylethyl group, etc., and examples of the acyl group include acetyl group, propylonyl group, benzoyl group, etc. b is 0 or 1, c and d are 0~
50, where c+d is 1-100. ). In addition, B is the above-mentioned R, -R3- (NHC
H2CH2)a-NHR4 and G. p is from 0 to 100, q and r are from 0 to 100, but p+q+r is from 2 to 1000. The amino group of the 'B} component is cross-linked with the carboxyl group or carboxyl ester group of the harmful component, giving the fiber material durable antistatic properties, moisture and sweat absorption properties, antifouling properties, flexibility, smoothness, In order to impart wrinkle resistance and compression recovery properties, at least two -R3-(NHCH2CH2
) Requires 4 a-NHR groups.

At least one polyoxyalkylene group is required in the same molecule in order to impart antistatic properties, moisture absorption/sweat absorption properties, and stain resistance to the fiber material. at least two -R3
-(NHCQC Day 2) a-NHR4 groups and at least one polyoxyalkylene group may be present anywhere in the molecular structure of the organopolysiloxane.

In addition, if the value of c0d of the polyoxyalkylene group is too small, the solubility or self-emulsifying property in aqueous systems will be poor, and the effects of antistatic properties, moisture absorption/sweat absorption, and antifouling properties will also be poor.
If the value of +d is too large, there is a risk that the polyoxyalkylene group will branch during production, so a range of 5 to 50 is preferable. Further, the preferable range of each siloxane unit is that p is 1.
0 to 500, q is 2 to 40 r is 1 to 30, p + q + r
is 10-500. This Tsukuda ingredient is, for example, JP-A-53
It can be manufactured according to the method described in Publication No.-9844. The organopolysiloxane of component 'C} is represented by the above general formula, in which R is a substituted or unsubstituted monovalent hydrocarbon group, and this includes the same examples of R as explained in component is exemplified.

The epoxy group-containing monovalent organic group represented by E has the general formula or Residue, chloroethylene group, fluoroethylene group, C ratio OCH2C ratio CH2 -,1 CQC day 20
CQC day 21, CH20CH2CH20CH2CH2-
is exemplified.

). The polyoxyalkylene group represented by G is the same as described in the explanation of the Tsukuda component. D is a group selected from R, E and G, and x is 0 to 10
00 y and z are 0 to 10, but x+y+z is 2
~1000. The preferred range of the polyoxyalkylene unit and each siloxane unit is the same as in the case of component (B). In one molecule of component 'C), component ■ and (B)
For the same reasons as explained in the component section, at least two epoxy group-containing organic groups and at least one polyoxyalkylene group are required.

The epoxy group-containing organic group and polyoxyalkylene group may be present anywhere in the organopolysiloxane structure. This component (C), like the wind component, can be produced using, for example, the addition reaction described in Japanese Patent Publication No. 33-996y and Japanese Patent Publication No. 36-1293. Examples of the two types of organopolysiloxanes consisting of A treatment solution may be prepared by dissolving it in an organic solvent such as Ben, perchlorethylene, or chlorocene, and may be applied to the fiber material by spraying, roller, dipping, etc., or it may be self-emulsified as it is, or it may be applied as appropriate. emulsifier,
For example, emulsification with higher alcohol sulfate ester salts, alkylbenzene sulfonates, higher alcohol polyoxyalkylene adducts, higher fatty acid polyoxyalkylene adducts, alkylphenol polyoxyalkylene adducts, and higher fatty acid solpitan esters. spray,
It may be applied to the fibrous material by a method such as a roller or dipping method.

At this time, both components may be dissolved or emulsified separately, mixed together, and then applied to the fiber material.

Alternatively, a method may be used in which a solution or emulsion of one of the components is applied to the fiber material, and then a solution or emulsion of the other component is applied. In short, any treatment method that allows both components to coexist on the fiber material can be used. From the viewpoint of uniformity of the treatment effect, it is preferable to treat the fiber material with a treatment agent that is a mixture of both components in advance. 0.1 to 4% by weight of both components together based on the fiber material
Generally, it is attached. Next, after removing the organic solvent or water by leaving at room temperature, blowing hot air, heat treatment, etc., a further heat treatment quickly causes a crosslinking reaction between the two organopolysiloxanes, resulting in durable antistatic properties and moisture absorption.・Exhibits sweat absorption, stain resistance, especially oil stain resistance, flexibility, smoothness, wrinkle resistance, and compression recovery. It is preferable to carry out hot air blowing or heat treatment rather than leaving it permanently in the sense that working efficiency and durability are further increased. A suitable curing catalyst may be added if necessary. In addition, other additives such as well-known antistatic agents, softeners, anti-wrinkle agents, heat-resistant agents, and elutriation agents may be used in combination. The fiber materials treated with this treatment agent include natural fibers such as wool, silk, hemp, cotton, and asbestos, recycled fibers such as rayon and acetate, polyester, polyamide, vinylon, and polyacrylonitrile. Examples include synthetic fibers such as polyethylene, polypropylene, and spandex, glass fibers, carbon fibers, and silicon carbide fibers, and in terms of shapes, staples, filaments, tow yarns, woven fabrics, knitted fabrics, nonwoven fabrics, resin-treated fabrics, and synthetic fibers. Although any material such as leather may be used, it is more efficient to process the material continuously in sheet form such as woven, knitted, nonwoven, or futon wire.

Next, examples and comparative examples will be given and explained, in which parts and % indicate parts by weight and % by weight, and the viscosity is the value at 2500.

Example 1 0.4 part of a carboxyl group-containing organopolysiloxane represented by the formula '1} and having a viscosity of 3300 centistokes, and an epoxy group-containing organic group represented by the formula 2 having a viscosity of 3500 centistokes A treatment solution was prepared by dissolving 0.6 part of Olga/polysiloxane having a polyoxyalkylene group and a polyoxyalkylene group in 9 parts of toluene.

After soaking a white polyester/cotton (65/35) lawn material (no resin treatment or antistatic treatment) in this treatment solution, it was pulled up and squeezed with a mangle roll to air dry so that the amount of organopolysiloxane adhesion was 1%. . Then 1 at 170℃
The crosslinking reaction between the two types of organopolysiloxanes was completed by heat treatment for 0 minutes. As a comparative example, a treatment solution containing 1 part of a carboxyl group-containing organopolysiloxane represented by the formula [1} and 9 parts of toluene, and a treatment liquid containing an epoxy group-containing organic group and a polyoxyalkylene group represented by the formula {21] were used. A treatment solution containing 1 part of organopolysiloxane and 9 parts of toluene was prepared, and lawn land was treated under the same conditions as above.

Using these treated cloths, the following tests on antistatic properties, residual organopolysiloxane ratio after cleaning, and antifouling properties were conducted. First, in order to examine the antistatic properties, each treated fabric and the treated fabric were immersed in perchlorethylene, soaked for 15 minutes, and then dried to provide an alternative to dry cleaning.

This operation was repeated twice. Furthermore, it was cleaned for 15 minutes in a 0.5% Marcel soap aqueous solution under strong conditions in a self-reversing electric washing machine, and then washed with water and dried. This operation was repeated twice. Cleaned untreated fabric and treated fabric, and uncleaned untreated fabric and treated fabric.
After leaving it for one week at 0°C and 65% humidity, use a Kyoto University Chemical Research rotary static tester to test the cloth to be rubbed with cotton cloth (
60 by rotating at 800 times/min using Kanakin No. 3).
The frictional voltage was measured after seconds. In addition, the residual organoborisiloxane rate of the cleaned treated cloth was measured using a fluorescent X-ray device (manufactured by Rigaku Denki Kogyo Co., Ltd.). Next, in order to examine the stain resistance against oil-based stains, we tested the ASTM standard. An artificial contamination solution prepared by thoroughly grinding and mixing 300 parts of oil, 3 parts of coal tar, 5 parts of dry region soil powder, 5 parts of Portland cement, and 5 parts of sodium dodecylbenzenesulfonate in a mortar. A 5% Marcel soap aqueous solution of LOOO' was placed in a 450' glass bottle and cleaned (2 times dry cleaning and 2 times washing with soap) 5 x 10
The treated and untreated fabrics were each placed in the glass bottle, a steel ball was added to each bottle, the test fabrics were immersed in the artificial contamination solution, and treated at 60 oo for 3 minutes.

After gently washing with water and drying, the cloth was washed for 10 minutes using a 0.5% Marcel soap aqueous solution on high strength in an automatic reversing electric washing machine. Using a reflectance meter, the test cloth after washing and drying was measured at 55%.
The reflectance at the wavelength of blood was measured. The results of each measurement value are shown in Table 1. As is clear from each measurement value, the fabric treated with the treatment agent of the present invention has excellent antistatic properties and antifouling properties as well as durability compared to the comparative example. Table 1 Example 2 1 part of a carboxyl group-containing organopolysiloxane represented by the formula {31 and having a viscosity of 3500 centistokes;
0.5 part of an organopolysiloxane containing an amino group and a polyoxyalkylene group and having a viscosity of 4,000 centistokes was added to 98% of perchlorethylene.
A treatment solution was prepared by dissolving the mixture in 5 parts.

A 100% cotton knitted underwear was soaked in this treatment solution, the liquid was removed using a centrifugal dehydrator so that the amount of organopolysiloxane attached was 1.5%, and the material was air-dried at room temperature for 24 hours. then 1
2000 for 5 minutes. As a comparative example, carboxyl group-containing organopolysiloxane 1.5 shown in formula
Department and Park Chlorethyren Group. A treatment solution consisting of 1.5 parts of organopolysiloxane containing an amino group and a polyoxyalkylene group represented by the formula (4-) and .5 parts of perchlorethylene group was prepared. 100% cotton knitted undergarments were treated under the same conditions. Each treated and untreated fabric was cleaned in a 0.5% aqueous Marcel soap solution for 15 minutes on high in a self-turning vortex electric washer. This operation was repeated 5 times.The treated and untreated fabrics that were cleaned and the treated and untreated fabrics that were not cleaned were treated in the same manner as in Example 1 to determine the organopolysiloxane residual rate and 55 skin. Tests were conducted on the reflectance of mountains.

In addition, the texture of each treated fabric and untreated fabric after cleaning was examined by manual sensory testing. These results are shown in Table 2. It was shown that those treated with the treatment agent of the present invention were the most excellent in antifouling properties and texture. Table 2

Claims (1)

[Scope of Claims] 1 Among the following three types of organopolysiloxanes (A), (B) and (C), (A) and (B) or (A) and (C) are used as main ingredients. A treatment agent for fibers. (A) General formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, R is a substituted or unsubstituted monovalent hydrocarbon group, A
is a group selected from R and -R^1-COOR^2,
R^1 is a divalent hydrocarbon group, R^2 is a hydrogen atom or a monovalent hydrocarbon group, 1 is 0 to 2000, m is 0 to 200 (if m is 0, both A are -R^1- COOR^2 groups, and when m is 1, at least one of A is -R^1-C
OOR^2 groups), 1+m is 1 to 2000. ], and at least two -R^1- in one molecule
Organopolysiloxane having 2 COOR^ groups, (B
) General formula ▲ Numerical formula, chemical formula, table, etc. are available ▼ [In the formula, R is a substituted or unsubstituted monovalent hydrocarbon group, B
is R, -R^3-(NHCH_2CH_2)a-NHR
A group selected from ^4 and G, R^3 is a divalent hydrocarbon group, R^4 is a hydrogen atom or a monovalent hydrocarbon group, a is 0 to
10, C is -(R^5)b-0-(C_2H_4O)c
-(C_3H_6O)d-R^6 (here, R^5 is 2
a valent organic group, R^6 is a hydrogen atom or a terminal capping group, b is 0 or 1, c and d are 0 to 50, where c+d is 1
~100), p is 0 to 1000, q and r are 0
~100, but p+q+r is 2-1000. ], and at least two -R^3- in one molecule
(NHCH_2CH_2) Organopolysiloxane having a-NHR^4 groups and at least one polyoxyalkylene group, and (C) General formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is substituted or unsubstituted] Substituted monovalent hydrocarbon group, D
is a group selected from R, E and G, E is an epoxy group-containing monovalent organic group, and G is -(R^5)b-O-(C_2H_
4O)c-(C_3H_6O)d-R^6(here, R
^5 is a divalent organic group, R^6 is a hydrogen atom or a terminal capping group, b is 0 or 1, c and d are 0 to 50, where c
+d is 1-100), x is 0-1000, y and z are 0-100, with x+y+z being 2-1000. ] An organopolysiloxane having at least two epoxy group-containing organic groups and at least one polyoxyalkylene group in one molecule.