JPH02182976A - Textile treating agent - Google Patents

Abstract

PURPOSE:To provide a textile treating agent composed of three specific organopolysiloxane components and capable of imparting a textile material with durable softness, smoothness, deodorizing property and shrink resistance. CONSTITUTION:The objective treating agent capable of giving durable softness and smoothness, etc.. can be produced by compounding (A) 5-100 pts.wt. of an organopolysiloxane expressed by formula I (R<1> to R<3> are univalent hydrocar bon group; R<4> is bivalent hydrocarbon group: R<5> is H or univalent hydrocarbon group: a is 0-10: A is H and/or 1-10C univalent hydrocarbon group), containing one R<4>-(-NHCH2CH2)a-NHR<5> group and two or more OH and/or alkoxy groups in one molecule and having a viscosity of 100-1,000, at 25 deg.C, (B) 100-5 pts.wt. of an organopolysiloxane expressed by formula II (R<6> is univalent hydrocarbon group; b is 1.5-2.5), having OH groups at both terminals of the molecular chain and having a viscosity of 50-1,000,000cS at 25 deg.C and (C) 1-30 pts.wt. of an organopolysiloxane expressed by formula III (R<7> is univalent hydrocarbon group: 0<=c<=3; 0<=d<=3; 1<=c+d<3, preferably 1.9<=c+d<2.1) and having a viscosity of 10-100,000cS at 25 deg.C.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a miscellaneous treatment agent.

Furthermore, in detail, it has excellent stability at room temperature, and hardens at room temperature by removing moisture to become an elastomer.
The present invention relates to a fiber treatment agent for imparting durable flexibility, smoothness, wrinkle resistance, and shrink resistance to fiber materials.

[Conventional technology]

Conventionally, various processing agents have been proposed to impart flexibility, smoothness, wrinkle resistance, and shrink resistance to fiber materials.

In order to impart flexibility and smoothness to the fibers, dimedylbolysiloxane oil or its emulsion is required to impart flexibility and smoothness to the fibers. A treatment agent consisting of an organopolysiloxane having epoxy groups and an organopolysiloxane having an amine group was published in Japanese Patent Publication No. 51-37.
No. 996 discloses that a treatment agent consisting of highly polymerized dimethylpolysiloxane and aminoalkoxysilane was disclosed in Japanese Patent Publication No. 53
In Japanese Patent Publication No. 53-19715, Japanese Patent Publication No. 53-19715 discloses a treatment agent consisting of a diorganopolysiloxane with hydrogen groups at both ends, an organosilane having an amino group and an alkoxy group in one molecule, and/or a partial hydrolyzate and condensate thereof.
No. 53-19716 proposes a treatment agent comprising an aminoalkyltrialkoxysilane and an epoxy group-containing organopolysiloxane.

However, these conventionally known processing agents have some drawbacks, and processing agents containing dimedylbolysiloxane oil as a main component lack flexibility, smoothness, wrinkle resistance, and durability.

Furthermore, processing agents containing alkoxysilanes as essential components tend to be hydrolyzed and have a hard texture when emulsified, and processing agents containing epoxy group-containing organopolysiloxanes and amino group-containing organopolysiloxanes as main ingredients have the disadvantage that they are easily hydrolyzed and have a hard texture. However, it has the disadvantage that it falls off when washed repeatedly in dry cleaning and has poor durability.

The inventors of the present invention have made intensive studies to solve the above-mentioned drawbacks of fiber treatment agents, and as a result, they have developed an elastomer that cures at room temperature by removing moisture, and provides durable flexibility and flexibility to fiber materials [l].
We have now invented a fiber treatment agent that can impart smoothness, anti-wrinkle properties, and anti-shrink properties.

[Structure of the invention]

The present invention is a fiber treatment agent containing the following three types of organopolysiloxanes as main ingredients: (A), (B), and (C). % [In the formula, R', R2, R3 are the same or different substituted or unsubstituted monovalent hydrocarbon groups, R4 is a divalent carbon 1 arsenic group, R5 is a hydrogen atom or 1@carbon f arsenic group, a is 0-1
0, A is a hydrogen atom and/or a monovalent hydrocarbon group having 1 to 10 carbon atoms, +an is a positive number] At least one -R'-+NHCH2CHz''rVN in one molecule
HR' W=: Contains two or more hydroxyl groups and/or alkoxy groups, and has a viscosity of 10 at 25°C
5 to 100 parts by weight of an organopolysiloxane which is 0 to 1, OOO, 0OOcS B)
b is a positive number of 1.5 to 2.5], both ends of the molecular chain are blocked with hydroxyl groups, and the viscosity at 25°C is 50 to 1.
000,000 cS diorganopolysiloxane
100 to 5 parts by weight
is O<c≦3. d is 0≦d≦3, and c+d is 1≦c+d
1 to 30 parts by weight of an organopolysiloxane having a viscosity of 10 to 100,000 cS at 25°C and D) a nonionic emulsifier E) water This is a fiber processing agent characterized by:

That is, the fiber treatment agent of the present invention comprises (A) (B) (C) 3
It is characterized by being composed of a variety of organopolysiloxanes.

(A), (B), (C) Each organopolysiloxane alone, or (A) and (B), (A) and (C), (B
) and (C), the organopolysiloxane fiber treatment agent has durable flexibility, smoothness, wrinkle resistance,
Although it cannot impart shrink-proofing properties, the fiber treatment agent consisting of three types of organopolysiloxanes cures at room temperature or higher by removing moisture and becomes an elastomer, which not only improves the above-mentioned effects but also imparts durability. They discovered that it is possible to do this and completed the present invention.

However, this does not preclude the use of a catalyst in the treatment agent of the present invention, since the reaction between the diorganopolysiloxane and the organohydrodiene polysiloxane, both ends of which are blocked with hydroxyl groups, may require a catalyst.

Durability here means that it can withstand water washing and dry cleaning well and lasts a long time.

The organopolysiloxane of component (A) is represented by the general formula described above, where R', R2, and R3 are a methyl group, an ethyl group, a propyl group, a dodecyl group, a vinyl group,
Phenyl group, cyclohexyl group, chloromethyl group, 3.
3.3-Identical or different substituted or unsubstituted monovalent hydrocarbon groups selected from 1-lifluoropropyl group, cyanomethyl group, etc., -R'→N HC)I 2 CH,
') R4 of the TN HR' group is a divalent hydrocarbon group, -
CH2-1-CH, CH2--CH□CH2CH2-1
Alkylene groups such as CI (2CI-1(CH2)CH, --(CH,), -(CH□) 2 Cs H4-
alkylenearylene group such as R5, R5 is a hydrogen atom or R1. Monovalent hydrocarbon group similar to R2, R3,
a is an amino group-containing organic group having a number of 0 to 10, A is a hydrogen atom or the same monovalent hydrocarbon group as R1 described above, a
+ and n are assumed to be positive numbers, but this product is required to contain at least one amino group-containing organic group and two or more hydroxyl groups and/or alkoxy groups in one molecule. .

If the viscosity at 25°C is less than 100cS, this Surganoborisiloxane will not be able to impart sufficient flexibility, smoothness, wrinkle resistance, and shrinkage resistance to the fiber material.
If it is more than 0.0OOcS, emulsification and dispersion will be difficult,
Preferably it is in the range of 300 to 100.000 cS.

In addition, the amino group-containing organic group described above has flexibility, smoothness,
It imparts wrinkle resistance and shrink resistance, and at least one or more is required in one molecule of component (A), and the hydroxyl group and alkoxy group are crosslinked with component (B) or component (C). In order to impart durability and form a cured film on fiber materials, it is necessary to contain two or more molecules in one molecule, and both ends of the molecular chain are blocked with hydroxyl or alkoxy groups. It is preferable to use siloxane.

The diorganopolysiloxane of component (B) is represented by the above-mentioned general formula, and in the present invention, this diorganopolysiloxane is a conventionally known diorganopolysiloxane as long as both ends of its molecular chain are blocked with hydroxyl groups. A variety of organopolysiloxanes can be used.

In the formula, R6 is a substituent selected from methyl group, ethyl group, propyl group, dodecyl group, vinyl group, phenyl group, cyclohexyl group, chloromethyl group, 3.3.3-trifluoropropyl group, cyanmethyl group, etc. Or it is an unsubstituted monovalent hydrocarbon group.

Specifically, there are dimethylpolysiloxane, methylphenylpolysiloxane, methylvinylpolysiloxane, dimethylpolysiloxane/methylvinylsiloxane copolymer, etc. in which the molecular chain terminals are capped with hydroxyl groups. Viscosity is 50cS
If the molecular weight is lower than that, the molecular weight will be small, and the hard coating formed by using (A) and (C) in combination will become brittle.

On the other hand, if it is 1,000,000 cS or more, emulsification and dispersion become difficult, and preferably 100 to 100°000 cS.
It is good to have something within this range.

The organopolysiloxane of component (C) is represented by the above-mentioned formula, in which R7 is a substituted or unsubstituted monovalent carbon-monohydrogen group, and is represented by the same thing as the above-mentioned example of R8. It will be done.

Specifically, there are methylhydrodienepolysiloxane, ethylhydrodienepolysiloxane, phenylhydrodienepolysiloxane, methylhydrodienepolysiloxane/dimethylpolysiloxane co-FFI, etc., and these organopolysiloxanes have a viscosity at 25°C. is preferably in the range of 10 to 10°000 cS.

The nonionic surfactants (D>) used in the present invention include glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene (POE) alkyl ether, POE sorbita> fatty acid ester, PO
Examples include E-glycerin fatty acid ester, POE alkylphenyl ether, POE arekyl ester, and POE polyoxypropylene block copolymer.

The amount of component (D) to be used may be a sufficient amount to emulsify the composition of the present invention, specifically (A), (B), (
The amount is in the range of 2 to 30 parts by weight per 100 parts by weight of component C).

The blending ratio of water in (E) is (A) CB) (C) components (
D) is required when emulsifying with component, and (
A>50 to 1.0 per 100 parts by weight of components (B) and (C)
00 parts by weight, preferably 100 to 500 parts by weight. If it is less than 1 part by weight, it is difficult to obtain a water-soluble fiber treatment agent, and if it exceeds 1,000 parts by weight, the curability is poor and the fiber It becomes difficult to impart durable flexibility, smoothness, wrinkle resistance, and shrink resistance to the material.

In preparing the fiber treatment agent composition according to the present invention: A, examples include a method of emulsifying components (A), (B), and (C) and components (D) and (E) using a homogenizer or the like.

In addition, the treatment of fiber materials with this composition is applied by spraying, rolling, dipping, etc., and the composition is applied in an amount of 0.1 to 3.0% by weight based on the fiber material Fl, preferably 0°2 to 2x26
It is best to wear one inch.

Then, by removing moisture by leaving it at room temperature or heat treatment, a crosslinking reaction occurs, resulting in an elastomer that can provide durable flexibility, smoothness, wrinkle resistance, and shrink resistance.

Furthermore, as described above, an appropriate hardening catalyst may be added if necessary.

The fiber materials treated with this treatment agent include natural fibers such as wool, silk, linen, and cotton, recycled fibers such as rayon and acetate, and synthetic materials such as polyester, polyamide, polyacrylonidonyl, and vinylon. Examples include fibers, glass fibers, carbon fibers, etc., and the shape may be stable, filament, tow, thread, woven fabric, knitted fabric, nonwoven fabric, etc.

Next, examples of the present invention will be described in detail. In addition, the steel part is heavy 1
The evaluation criteria for durable flexibility, smoothness, wrinkle resistance, and shrink resistance in steel are as follows. The results show the results of repeating each of dry cleaning and dry cleaning 10 times.

[The feel of the fiber material treated with the softness/smoothness treatment agent is evaluated by touch.

◎...Retains an extremely elegant softness and slimy texture.

O: Maintains good soft texture.

△...Slightly dry and squeaky texture.

×...A dry, squeaky, angry m-ki.

(Washing method and conditions) Wash in a 2 g/l neutral detergent aqueous solution at 40°C for 15 minutes under strong conditions in a household automatic rotating electric washing machine, then
Wash with water (room temperature running water for 10 minutes), dehydrate and dry.
times.

[Wrinkle resistance/shrink resistance] After drying the fiber material treated with a processing agent to a size of 25c#A vertically and horizontally, marking the inside of it to a size of 20cII vertically and horizontally,
Wash with water under the following conditions, and then measure the shrinkage rate. Wrinkle resistance is evaluated by visual judgment.

O: No shrinkage, no wrinkles.

△...Some wrinkles appear.

×: Significant shrinkage and wrinkles.

(Washing method and conditions) In accordance with JIS L-0217103 method, wash in a 2 g/l neutral detergent aqueous solution at 40°C for 5 minutes in a household automatic reversing spiral electric washing machine at 1"F, then wash for 5 minutes. , wash with water (twice for 2 minutes at room temperature), dehydrate and air dry.

This is considered to be one time.

[Dry cleaning method and conditions] Wash at 40°C for 30 minutes using perchlorethylene, an anionic activator, and a nonionic activator in accordance with JIS L-086 Or dye fastness test method for dry cleaning, then perchlorethylene. Rinse at 60°C
Dry at , this is one time.

[Example 1] Both ends are blocked with hydroxyl groups, and the viscosity at 25'C is 3
15 parts of an amine group-containing organopolysiloxane having 0.000 cS, and 25 parts of amine group-containing organopolysiloxane having a
12 parts of diorganopolysiloxane with a viscosity of 13.00 OcS at 0C, a viscosity of 30OcS at 25C
Add 3 parts of methylhydrodiene polysiloxane having cS, 5 parts of polyoxyethylene 8 mol addition alkyl ether, 10 mol polyoxyethylene (2 parts of -f addition alkylphenyl ether), and 63 parts water, and stir using a high-speed stirring device. This was milked and used as a processing agent. 1. 1 part of acetic acid was added to this to obtain a stable processing agent A.

[Example 2] 20 parts of an amino group-containing organopolysiloxane with both ends capped with alkoxy groups and having a viscosity of 350 cS at 25°C, 10 parts of the diorganopolysiloxane used in Example 1, and the same as that used in Example 1. 3 parts of the methylhydrodiene polysiloxane prepared above, 17 parts of the same nonionic surfactant used in Example 1, and 60 parts of water were added and emulsified in the same manner as in Example 1 to obtain a stable processing agent B.

Incidentally, when the treatment agents of Examples 1 and 2 obtained above were allowed to stand for 3 days after evaporating water at room temperature, a cured film made of silicone elastomer was not obtained. Further, when this treatment agent was stored in a sealed state at room temperature for 30 days, no abnormality was observed.

As a comparative example, 15 parts of the amine group-containing organopolysiloxane shown in Example 1, 3 parts of alkyl ether added with 8 moles of polyoxyethylene, 2 parts of alkylphenyl ether added with 10 moles of polyoxyethylene, and 80 parts of water were added, and the mixture was stirred at high speed. This was emulsified by stirring using a device to obtain processing agent C.

Further, 15 parts each of the amino group-containing organopolysiloxane shown in Example 2, the diorganopolysiloxane shown in Example 1, and methylhydrodiene polysiloxane alone, and the same amount of nonionic surfactant 5M as described above. 80 parts of water was added and emulsified by stirring using a high-speed stirring device to obtain three types of processing agents, E and F.

Furthermore, 10 parts of the amino group-containing organopolysiloxane shown in Example 1, 10 parts of the diorganopolysiloxane shown in Example 1, 10 parts of the amino group-containing organopolysiloxane shown in Example 2, and 10 parts of the amino group-containing organopolysiloxane shown in Example 1 were added. 10 parts of the diorganopolysiloxane shown in Example 1, 15 parts of the amino group-containing organopolysiloxane shown in Example 1, 5 parts of the methylhydrodiene polysiloxane shown in Example 1, and 15 parts of the amine group-containing organopolysiloxane shown in Example 2. 5 parts of the methylhydrodiene polysiloxane shown in Example 1, 15 parts of the diorganopolysiloxane shown in Example 1 and 5 parts of the methylhydrodiene polysiloxane shown in Example 1,
These three SFs were added with 4 parts of alkyl ether added with 8 moles of polyoxyethylene, 2 parts of alkylphenyl ether added with 10 moles of polyoxyethylene, 1 part of sorbitan fatty acid ester, 1 part of sorbitan fatty acid ester added with 20 moles of polyoxyethylene, and 72 parts of water. , emulsify these by stirring using a high-speed stirring device, and add five types of processing agents G, H, and I.
, J, and K were obtained.

Data obtained by treating fiber materials with the treatment agents A and B of the examples described above and treatment agents C, D, E, F, G, If, I, J, and K of the untreated or comparative examples under the following conditions. The first
It is shown in Table 2.

(Treatment of nylon cotton) A nylon staple cotton of 3 d x l O 2 mm (d is denyl) was immersed in the treatment agent obtained above in a bath such that the adhesion of the treatment agent was 0.4% by weight in terms of solid content. After centrifugal dehydration, the treated cotton was completely dried at 1006c, and the durable flexibility, smoothness, and dry cleaning resistance of the treated cotton were examined, and the results shown in Table 1 below were obtained.

Table 1 (Wool treatment) Treatment bath: Solution of each treatment agent diluted 5 times in water; Fabric to be treated;
Woolnitz I. Treatment method: The treated fabric was immersed in the above treatment bath at 40'C for 20 minutes, centrifuged to dehydrate, dried at 100'C for 5 minutes, and heated at 150°C.
Heat treatment is performed at C for 2 minutes.

Test method: Durable flexibility, smoothness, wrinkle resistance, and shrink resistance evaluation result is the above-mentioned rating 2! The results were as shown in Table 2.

Table 2 shows that the treatment agent of the present invention imparts durable flexibility and smoothness, and is a treatment agent for fibers with excellent wrinkle resistance and shrink resistance.

Claims (1)

[Claims] A) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R^1, R^2, R^3 are the same or different substituted or unsubstituted monovalent hydrocarbon groups , R^4 is a divalent hydrocarbon group, R^5 is a hydrogen atom or a monovalent hydrocarbon group, a is 0 to 10, A is a hydrogen atom and/or a carbon number of 1 to 10
monovalent hydrocarbon group, mn is a positive number] Contains at least one ▲ mathematical formula, chemical formula, table, etc. ▼ group and two or more hydroxyl groups and/or alkoxy groups , 5 to 100 parts by weight of an organopolysiloxane having a viscosity of 100 to 1,000,000 cS at 25°C monovalent hydrocarbon group, b is 1
．． 5 to 2.5], both ends of the molecular chain are blocked with hydroxyl groups, and the viscosity at 25°C is 50 to 1,000,
000cS diorganopolysiloxane 100-5
Weight part C) General formula R^7_c-H_dSiO_(_4_-_c_-_d_
)_/_2 [wherein, R^7 is a substituted or unsubstituted monovalent hydrocarbon group, c is 0<c≦3, d is 0≦d≦3, and c+d
is 1≦c+d<3, preferably 1.9<c+d<2.1
], and the viscosity at 25°C is 10 to 100,00
1 to 30 parts by weight of an organopolysiloxane having a molecular weight of 0 cS; D) a nonionic emulsifier; and E) water.