JPH02154076A - Textile treating agent - Google Patents

Abstract

PURPOSE:To obtain a softening treating agent useful for wadding without causing yellowing due to heat or with time by blending three specific organopolysiloxanes with an epoxy group-containing organoalkoxysilane and organic monoepoxy compound. CONSTITUTION:A softening treating agent for wadding consisting of (a) 40-90pts. wt. organopolysiloxane, containing aminoalkyl group-containing siloxy groups expressed by formula I [R<1> to R<4> are 1-20C hydrocarbon; Z is aminoalkyl expressed by formula II (R<6> and R<7> are H, etc.; a is 0-4); X is H, etc.] and having >=10,000g/mol amine equiv. and hydroxyl groups, (B) 5-50pts.wt. organopolysiloxane which is a reaction product of an aminoalkyl group- containing organopolysiloxane expressed by formula III (Z is same as described above; R<8> is hydrocarbon; 0<=b<=1; 0<c<2; b + c = 1.9-2.1), (C) 5-50pts.wt. aminoalkyl group-containing organopolysiloxane, (D) an epoxy group-containing organoalkoxysilane and (E) a monoepoxy compound expressed by formula IV (G is epoxy; R<9> is hydrocarbon; X is H, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a fiber treatment agent, particularly a softening treatment agent for synthetic AA fibers for stuffed wire, which improves yellowing of treated synthetic fibers due to heat or aging. It is something.

[Prior art and issues to be solved] Synthetic fibers for stuffing wire made of polyester fibers, acrylic fibers, etc. are required to have good flexibility and smoothness, so various processing agents have been proposed. There is.

That is, regarding this type of treatment agent, for example, there are three types: epoxysiloxane and aminosiloxane, epoxysiloxane and amino compound, and aminosiloxane and epoxy compound.
Processing of synthetic fibers using a combination of seeds (Special Publication No. 1973)
7514), a treatment agent made of a combination of highly polymerized dimethylpolysiloxane and aminoalkoxysilane (see Publication No. 7514);
(see Japanese Patent Publication No. 51-37996), processing agents based on a combination of epoxysiloxane and aminoalkoxysilane (Japanese Patent Publication No. 53-19715, Japanese Patent Publication No. 53-19716)
All of these give flexibility and smoothness to synthetic fiber stuffed cotton, giving it a feather-like feel. However, there is a major drawback in that the treated cotton changes color and yellows when left for a long time, thereby impairing its commercial value, and this improvement is strongly desired by the industry.

[Means for Solving the Problems] The present invention relates to a fiber treatment agent that solves such disadvantages, and is composed of A) a general formula [where R1, R2, R
3, R4 is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, Z is the formula -R' (NHCH2
C)+2) -NR'R'(R' is a divalent hydrocarbon group having 1 to 10 carbon atoms, R6 and R7 are hydrogen atoms or the same or different unsubstituted or substituted monovalent hydrocarbons having 1 to 20 carbon atoms) group, a is an aminoalkyl group represented by O≦a≦4),
where Amine equivalent is the average molecular weight per N atom) containing a siloxy group containing an aminoalkyl group and two or more hydroxyl groups and/or alkoxy groups, at 25 ° C.
Substantially linear organopolysiloxane 40-90 having a viscosity of 100-1,000,000 cS
Parts by weight, B) a) General formula 2bR'cSIJ-b-c
"' (2) [where Z is the same aminoalkyl group as above, R8 is an unsubstituted or substituted monovalent hydrocarbon group, o<b≦
1, O<c<2, b + C=1.9-2.1]; and b) an organopolysiloxane modified with the aminoalkyl group. Containing amine alkyl group 1
5 to 50 parts by weight of an organopolysiloxane, which is a reaction product with an organic epoxy compound containing at least one epoxy group in the molecule, in an amount of 0.01 to 20 moles of epoxy groups per mole; C) amine; Equivalent weight is 100 to 5,00
5 to 50 parts by weight of the aminoalkyl group-containing organoborisiloxane described in B) a), which is 081 mol;
D) 1 to 50 parts by weight based on 100 parts by weight of the above-mentioned A), B) and C) components of the epoxy group-containing organoalkoxysilane, and E) General formula G-R9-OX
...(3) [In the formula, G is an epoxy residue, R9 is a divalent hydrocarbon group, and X is a hydrogen atom, an acyloxy group, (
meth)acryloxy group and a group selected from 1 to 50 parts by weight based on a total of 100 parts by weight of the above-described components A), B) and C) of the organic monoepoxy compound represented by the following. That is.

That is, the inventors impart flexibility and smoothness to the product,
As a result of various studies to develop a processing agent that does not change color, especially yellowing, even with heat and time, we found that the main ingredient, organopolysiloxane, is an organic group containing an amino group and a hydroxyl group represented by the above general formula (1). and/or a product containing an alkoxy group, to which a reaction product of an organopolysiloxane containing an aminoalkyl group represented by the above general formula (2) and an organic epoxy compound is added; ) is added to the organopolysiloxane containing an aminoalkyl group, and further an organoalkoxysilane containing an epoxy group and an organic monoepoxy compound are added to the synthetic fiber for stuffed wire treated with this. In addition to providing superior softness and smoothness to the texture provided by conventionally known processing agents, the resulting fibers do not yellow due to heat or aging, and are natural fibers. We have discovered that synthetic fibers and their blended products can be given voluminous, smooth, and excellent flexibility and repellency to knitted fabrics. The present invention was completed by conducting research on fil, compounding amount, etc.

[Work] This will be explained in further detail below.

The organopolysiloxane as component A) constituting the treatment agent for synthetic fibers of the present invention is not shown by the general formula, and this R1,
R2, R3, R4 are methyl group, ethyl group, propyl group,
Alkyl groups such as butyl groups, alkenyl groups such as vinyl groups and allyl groups, aryl groups such as phenyl groups and tolyl groups, cycloalkyl groups such as cyclohexyl groups, or some or all of the hydrogen atoms bonded to these carbon atoms. The same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms selected from chloromethyl group, trifluoropropyl group, cyanomethyl group, etc. substituted with halogen atom, cyan group, etc., Z is the formula -R' (NIIC
H2C1b)-NR6R', R5 is a divalent hydrocarbon group having 1 to 10 carbon atoms such as a methylene group, ethylene group, propylene group, butylene group, R6 and R7 are a hydrogen atom or the above nl, R2 , R3, a monovalent hydrocarbon group having 1 to 20 carbon atoms similar to R4, a is an aminoalkyl group with 0≦a≦4, X is a hydrogen atom, or 1 having 1 to 10 carbon atoms as in 81 described above. valence hydrocarbon group, J2. m is a positive integer, and n is O or a positive integer, which has at least one aminoalkyl group as a Z group and two or more hydroxyl groups and/or alkoxy groups in one molecule. group is required.

This organopolysiloxane has a viscosity of 1 at 25°C.
If the fiber is less than 1,000,000
cS or more, it becomes difficult to prepare a processing agent by means such as emulsification or dissolution;
The preferred range is 1,000 to 100,000 cS. In addition, this product is said to contain one or more of the above-mentioned aminoalkyl groups, and if the content of this aminoalkyl group increases, it may cause undesirable yellowing in textile products treated with this aminoalkyl group. Therefore, it is necessary to have an amine equivalent of 10.000 g or more than 1 mole, and the hydroxyl group and alkoxy group react with the epoxy group-containing alkoxysilane used in combination to achieve the durability of the treatment effect. Since it is necessary to form a crosslinked and cured film on the surface of the fiber, it is necessary to contain two or more in one molecule, but from the viewpoint of flexibility, two or more is preferable. The polysiloxane is preferably one whose molecular chain ends are blocked with hydroxyl groups or alkoxy groups.

This type of organopolysiloxane can be produced by using, for example, octamethylcyclotetrasiloxane, hexamethyldisiloxane, or an aminoalkyldialkoxysilane in place of the formula San as an amino group source. A polysiloxane can be obtained, and if α,ω-dihydroxydimethylpolysiloxane oligomer is used, an organopolysiloxane in which both ends of the molecule are blocked with hydroxyl groups can be obtained.

The organopolysiloxane as component B) used in the present invention is a reaction product of the above-mentioned a) organopolysiloxane containing an aminoalkyl group and b) an organic epoxy compound containing an epoxy group. The aminoalkyl group-containing organopolysiloxane can be synthesized by heating and polymerizing the hydrolysis product of the aminosilane represented by the formula using a strong alkaline compound such as potassium hydroxide as a catalyst. It is represented by methyldisiloxy, and 2 is the same aminoalkyl group as above. Furthermore, R6 in the above formula is a monovalent hydrocarbon group having 1 to 20 carbon atoms similar to R6 and R7 described above, and this includes a halogen atom or an ethylenically unsaturated group for some or all of its hydrogen atoms. They may be substituted with organic groups, aryl groups, or even contain polyoxyalkylene groups, but it is desirable that at least 50% of them be methyl groups. Note that this b is o<b≦1, and C is 0
Since <c<2 and b+c is in the range of 1°9 to 2°l, this organopolysiloxane is considered to be substantially linear, but it contains -partially engineered siloxane bonds. Furthermore, this terminal is a trialkylsilyl group, but this is a hydroxyl group or 10CH3, -0C2)
It may contain an alkoxy group such as 15.

This aminoalkyl group-modified organopolysiloxane is produced by polycondensing three components, for example, octamethyltetracyclosiloxane, a hydrolyzate of aminoalkylmethoxysilane represented by the formula %, and hexamethyldisiloxane in the presence of potassium hydroxide. can be produced by a so-called alkali re-equilibration reaction, but in addition to the above, the siloxane units containing aminoalkyl groups include St (CH2CH2C)12NHCH2C82N)+
2) Osz□, 5l(CH2CH2CHaNth)Os
/z, etc. are shown. This aminoalkyl group-modified organopolysiloxane is liquid at room temperature, and can be used with a viscosity ranging from OcS to 1,000,000 C5, but in terms of workability, it is 100 to 100,000,000 C5.

It is preferable to use a range of cS.

On the other hand, the organic epoxy compound as component b) that reacts with this aminoalkyl group-modified organopolysiloxane is not particularly limited as long as it has at least one epoxy group in its molecule; ) 12-CHR' \1 (where 89 is an organic group) is preferably a monoepoxy compound. R9 in this formula is a straight or branched hydrocarbon group, but it may also contain a polyoxyalkylene group, and this monoepoxy compound has the following formula, CH2-CHCl120C)I2C1(-CH2CH2 The following compounds are exemplified.The amount of the organic epoxy compound added to the aminoalkyl-modified organopolysiloxane is preferably 0.01 to 20 moles of epoxy group per nitrogen atom contained in the organopolysiloxane. may be in a range of 0.1 to 10 moles.

The reaction between components a) and b) is carried out by mixing them and heating them to carry out the reaction according to the following formula (% formula %), and then block modifying the active hydrogen groups with an epoxy compound. good.

Next, the liquid organopolysiloxane as component C) constituting the composition of the present invention is of the same kind as the aminoalkyl group-containing organopolysiloxane as component 8) a) described above and represented by the above general formula (2). However, in order to impart excellent flexibility and smoothness, it is necessary that the amine equivalent is in the range of 100 to 5,000 g/mol.

In addition, the terminal functional aminosiloxane as component 8), the aminosiloxane modified with an epoxy compound as component B, and the aminosiloxane as component C) are used in order to obtain a more improved soft and smooth texture. These three types of aminosiloxanes with different structures can be combined and used in combination with component D) and component E), which will be described later. It is possible to impart superior flexibility, smoothness, anti-elasticity, voluminous feel, etc. to textile products. In addition, the blending ratio of this ^) component, B) component and C) component is ^) : B) : C) = 40 to 90:5
~50:5~50 (weight ratio) is required, but in order to obtain a more desirable texture, A):B
) : C)=50-80:10-30:It is preferable to set it as the range of 10-30.

Next, the epoxy group-containing organoalkoxysilane as component D) constituting the composition of the present invention may be any organosilane that simultaneously contains both an epoxy group and an alkoxy group in one molecule. This product is called carbon functional silane in the industry and is widely used as a surface treatment agent for various base materials. . If the blending amount of this epoxy group-containing organoalkoxysilane is less than 1 part by weight based on the total 100 parts of organopolysiloxane as component ^), component B), and component C), the durability will be insufficient. If the amount is 50 parts or more, the resulting synthetic fiber texture becomes hard, so the amount must be 1 to 50 parts by weight, but the preferred range is 10 to 30 parts by weight.

The epoxy group-containing organoalkoxysilane used here is usually used in the form of a filtrate, but a pre-hydrolyzed version can also be used.

Furthermore, the organic monoepoxy compound as component E) constituting the composition of the present invention prevents the yellowing of fibers derived from the aminoalkyl groups in components A), B), and C) described above, and improves the texture of the fibers. It is said to contain one epoxy group in one molecule, but at the same time, there is a hydroxyl group in the molecular chain as well as an epoxy group.
It may contain an acetoxy group, a methacryloxy group, an acryloxy group, a trimethylsilyl group, or a trimethylsilylated low-molecular dimethylsilicon group, and examples of these compounds include the following.

CHz Cl4CH20H \1 C1(.

C)13 C)13 CH3\1 The amount of this organic monoepoxy group-containing compound is 1 part by weight per 100 parts by weight of the organopolysiloxane as the total amount of component A), component B) and component C). If it is less than 1 part by weight, the anti-yellowing effect and the effect of improving texture will be insufficient, and if it is more than 50 parts by weight, flexibility and smoothness will decrease, so it is necessary to use 1 to 50 parts by weight.
This preferred range is 10 to 30 parts by weight.

The fiber MIIA filler of the present invention is as described above ^), B), C),
D).

E) It can be obtained by uniformly mixing predetermined amounts of the components, but in actual use, it can be obtained by mixing it with a suitable organic solvent, such as an aromatic solvent such as benzene, toluene, xylene, or an industrial solvent. diluted with gasoline, petroleum solvents such as kerosene, chlorinated solvents such as trichlorethylene, perchlorethylene, trichloroethane, and various fluorinated solvents, or with appropriate emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl ether, etc. It is often used as an emulsion in water using a nonionic emulsifier such as ethylene alkylphenyl ether or a cationic emulsifier such as a quaternary ammonium salt or an ethylene oxide adduct of a quaternary ammonium salt. In this case, if necessary, for the purpose of stabilizing the emulsion, an organic carboxylic acid such as formic acid, acetic acid, or glycolic acid may be added to neutralize a portion of the amino groups.

Fibers can be treated with this composition by dipping, oiling roller, spraying, etc. using this organic solvent solution or emulsion. It is optional to add organic acid salts of metals, such as, as catalysts, and it is also optional to add other processing agents, such as water repellents, flame retardants, antistatic agents, etc.

The adhesion of this treatment agent to the fibers is due to the fact that it contains 0.0% as an active ingredient.
01 to 5.0% by weight, preferably 0.05 to 2.0% by weight, and after the adhesion treatment, the 1a fibers are heat-treated at 100 to 200°C for about 1 to 30 minutes. This may be crosslinked and fixed on the t#l fiber.

There are no particular restrictions on the fibers that can be treated with the treatment agent of the present invention, but these include polyester fibers, acrylic fibers,
It is said to be useful for treating synthetic fibers such as nylon 1a fibers and polypropylene fibers, and the treated fibers are soft and smooth, giving them a so-called feather touch. It has the advantage of not discoloring or yellowing over time.

[Example] Next, examples of the present invention will be given.

Example (Synthesis of aminosiloxane) In a glass reactor with an internal volume of 1j2 equipped with a stirring device, a thermometer, a reflux condenser, and a nitrogen gas inlet, (1) xg of octamethylcyclotetrasiloxane was placed.

Organosiloxane yg, C)1*0-5l-0-C)Is (hereinafter abbreviated as Z-2), CH3 The amount remaining after heating at 105°C for 3 hours, the viscosity is 25
Measured values are shown in °C.

(Here, X is = (CH2) 3NH(CH2) 2NH
2, and Y represents -(CL)3NH2) and zg of organosiloxane or aminoalkoxysilane represented by zg of potassium hydroxide as a polymerization catalyst.
After heating and stirring at 140°C for 6 hours while purging the inside with nitrogen gas, ethylene chlorohydrin OJ
g was added and stirred at 100°C for 2 hours to neutralize the potassium hydroxide, and then stripped under reduced pressure of 130°C/10 mmHg to remove low fractions. I listed in Table 1 according to the amount of preparation of y%2
, II, III, IV, and V aminosiloxanes were obtained.

In addition, the amine equivalent in this table is the value measured by neutralization titration with 0.1N hydrochloric acid, and the nonvolatile content is the value measured by the stirring device, thermometer, reflux condenser, and nitrogen gas inlet (reaction of aminosiloxane and epoxy compound). Aminosiloxane II+ obtained above was placed in a glass reactor with an internal volume of 1°C.
When 300 g and the formula (1.5 times the mole based on the N atoms in aminosiloxane III) were charged and reacted at 60°C for 5 hours under nitrogen gas, the non-volatile content was 7.6%.
A reaction product (hereinafter abbreviated as organopolysiloxane Vl) having a viscosity of 49.300 cS was obtained.

In addition, when 9.6 g of the aminosiloxane epoxy compound obtained above (0.5 times the mole of N atoms in the aminosiloxane) was reacted in the same manner as above, the non-volatile content was 9.
A reaction product (hereinafter abbreviated as organopolysiloxane (2)) having a viscosity of 9.0% and a viscosity of 630 cS was obtained.

Preparation of buried bath) Organopolysiloxane V! obtained above. , ■ and aminosiloxanes 1 to V, 50 g of polyoxyethylene nonylphenyl ether as an emulsifier and 550 g of water were added and emulsified with a homomixer to make emulsions ■ to ■.Octamethylcyclotetrasiloxane was added for comparison. 300 g of dodecylbenzenesulfonic acid, 10 g of dodecylbenzenesulfonic acid, and 690 g of water were emulsified using a high-speed stirrer, stirred at 60°C for 16 hours, and the resulting emulsion was neutralized to p) 17 with a 10% aqueous sodium carbonate solution. 1
An emulsion of dimethylpolysiloxane containing a silanol group at the end of the molecular chain (hereinafter abbreviated as emulsion ■) with a non-volatile content of 27% at 05°C for 73 hours was prepared, and then this emulsion was mixed with an epoxy group-containing alkoxysilane and an alkoxysilane containing an epoxy group. Various treatment baths were made by combining with organic epoxy compounds.

(Processing of polyester cotton) Polyester stable cotton of 6' x 64 mm (d is denier) was immersed in the treatment bath obtained above so that the amount of the treatment agent attached was 0.1% in terms of solid content, and then centrifuged. Excess liquid is removed using a separator, and then heat treatment is performed at 150°C for 10 minutes to produce treated cotton.
The smoothness and dry cleaning resistance were examined, as well as yellowing when heated, and the results shown in Table 2 below were obtained.

In addition, the flexibility of the polyester cotton obtained by the above treatment,
Smoothness, yellowing and dry cleaning resistance were measured using the following methods.

(Flexibility, smoothness) The texture of the synthetic fibers treated with the treatment agent was evaluated by touch.

◎...Extremely good feather-like texture was exhibited.

O: Good feather-like texture was exhibited.

△...Slightly rough and hard texture with little slippage.

×: The texture was rough and hard with little slippage at all.

(Yellowing) The synthetic fibers treated with the processing agent were heated at 200° C. for 30 minutes and then taken out, and the degree of yellowing was visually evaluated.

O: No yellowing.

△...Slight yellowing.

×: Extremely strong yellowing.

(Dry Cleaning Resistance) The above characteristics were evaluated after washing using perchlorethylene, an anionic surfactant, and a nonionic surfactant according to JIS L-086Or "Dyeing Fastness Test Method for Dry Cleaning".

(remarks) Epoxysilane KBE-402 [Made by Shin-Etsu Chemical Co., Ltd.] Product name] Epoxysilane KPM-403 [Made by Shin-Etsu Chemical @ Product name] Epoxysilane KBM-303 [Made by Shin-Etsu Chemical Co., Ltd.] Product name] 8M-ft02 to silane [Manufactured by Shin-Etsu Chemical Aji Glycidyl alcohol... CH2-CHCH20H \1 Glycidyl methacrylate... Hs DBTDL emulsion... emulsion of

Claims (1)

[Claims] 1. A) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [Here, R^1, R^2, R^3, R^4 are the same or different carbon numbers 1 to 20 unsubstituted or substituted monovalent hydrocarbon group, Z is of the formula -R^5(NHCH_2CH_2)_aNR
^6R^7 (R^5 is a divalent hydrocarbon group having 1 to 10 carbon atoms, R^6 and R^7 are hydrogen atoms or the same or different unsubstituted or substituted monovalent hydrocarbons having 1 to 20 carbon atoms group, a is an aminoalkyl group represented by 0≦a≦4), X is a hydrogen atom and/or a monovalent hydrocarbon group having 1 to 10 carbon atoms, l
, m is a positive integer, n is 0 or a positive integer],
Containing a siloxy group containing an aminoalkyl group with an amine equivalent of 10,000 g/mol or more (here, the amine equivalent is the average molecular weight per N atom) and two or more hydroxyl groups and/or alkoxy groups, 40 to 90 parts by weight of a substantially linear organopolysiloxane having a viscosity of 100 to 1,000,000 cS at 25°C, B) a) General formula Z_bR^6_cSiO_4_-_b_
-_C_/_2 [where Z is the same aminoalkyl group as above, R^6 is an unsubstituted or substituted monovalent hydrocarbon group, 0<b
≦1, 0<c<2, b+c=1.9-2.1], and b) the aminoalkyl group-modified organopolysiloxane. Organopolysiloxane 5 to 50, which is a reaction product of an organic epoxy compound containing at least one epoxy group in the molecule, in an amount of 0.01 to 20 moles of epoxy group per mole of aminoalkyl groups contained in
Parts by weight, C) 5 to 50 parts by weight of the aminoalkyl group-containing organopolysiloxane described in B) a) above, having an amine equivalent of 100 to 5,000 g/mol, D) Epoxy group-containing organoalkoxysilane A), B
) and C) 1 to 5 parts per 100 parts by weight of the total amount of components
0 parts by weight, E) General formula G-R^9-OX [where G is an epoxy residue, R^9 is a divalent hydrocarbon group, and X is a hydrogen atom, an acyloxy group, a (meth)acryloxy group and ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (e is an integer from 0 to 5) A group selected from ▼ (e is an integer from 0 to 5) 1 to 50 parts by weight of a fiber treatment agent.