JP3290560B2 - Synthetic fiber treatment agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic fiber treating agent which imparts a stable dark color effect and a softening effect to synthetic fibers, especially polyester synthetic fibers.

[0002]

2. Description of the Related Art One of the drawbacks of synthetic fibers, especially polyester synthetic fibers, is that the color density of the synthetic fibers, when dyed, is lower than that of natural fibers such as wool and silk and other synthetic fibers such as nylon and acrylic. It is pointed out that they are low, inferior in clarity, and inferior in flexibility and texture as compared with natural fibers. Various methods have conventionally been proposed as methods for solving these disadvantages. For example, a method of adsorbing a cationic dye having a sulfonic acid group in the polymer of the fiber in order to increase the color of the dyeing, removing the microporous forming agent by alkali-treating the polyester fiber added with the microporous forming agent (See JP-A-54-120728), a method of forming fine irregularities by plasma etching the fiber surface (see JP-B-59-11709 and JP-B-60-37225), After forming unevenness by etching, a method of treating with a low-refractive-index resin such as silicone or a method of plasma-etching after treating with a low-refractive-index resin (JP-B-60-37225, JP-A-61-97490, JP
JP-A 1-239179, JP-A-2-99668, JP-A-3-180571), a method of treating the fiber surface with an enzyme and then silicone treatment (see JP-A-2-54082), non-phase with different refractive index A method of treating with a soluble resin (see JP-A-2-91773), a method of treating a polyester fiber with an epoxy resin, and then treating with an aminosilicone (see JP-A-3-269174 and JP-A-4-214482) , A method of treating with a low refractive index compound such as aminosilicone (see JP-A-3-104986 and JP-A-3-152276), a method of treating with an epoxy group-containing silsesquioxane and an aminosiloxane (Japanese Patent Publication No.
4-78657) and the like.

[0003]

However, the method of introducing a sulfonic acid group or the like into the fiber polymer has an insufficient dark color effect. A method involving an alkali treatment, a plasma treatment, an enzyme treatment, an epoxy resin treatment, or the like requires a special device and has a problem that the process is not simple.
In the case of treatment with a resin with a different refractive index or a compound with a low refractive index,
There are problems such as insufficient dark color effect and insufficient durability (stability). In addition, treatment with epoxy group-containing silsesquioxane and aminosiloxane
There is a problem such as insufficient flexibility.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems in the prior art, and as a result, by combining an amino-modified siloxane having terminal reactivity with an alkyl polysilicate, The cross-linking reaction on the fiber proceeds, and the durability (stability) of the effect of the treating agent is improved. Furthermore, when the organopolysiloxane is used in a specific range, the darkening effect can be enhanced. Also, the present invention was completed by discovering that it is possible to enhance the dark color effect by treating a dyed cloth with an aqueous emulsion type synthetic fiber treating agent obtained by emulsifying the treating agent with a specific surfactant. .

That is, the present invention provides (A) the following general formula:

Embedded image [Where R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ² is a divalent hydrocarbon group having 1 to 6 carbon atoms, R ³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms] Wherein R ⁴ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, a is an integer of 0 to 3, and m and n are 0.0001 <n / (m + n) <0.1, 10
<(M + n) <10,000. The amino group-containing organopolysiloxane represented by the formula 1
00 parts by weight, (B) alkyl polysilicate
0.01 to 10 parts by weight and (C) the following general formula

Embedded image (Where R ⁶ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, 10 <L
<2,000. Organopolysiloxane represented by)
It is a synthetic fiber treating agent containing 0 to 50 parts by weight.

Hereinafter, the present invention will be described in detail.
In the amino group-containing organopolysiloxane (A), R ¹ is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, dodecyl, tetradecyl, hexadecyl. An alkyl group such as octadecyl group, vinyl group,
An alkenyl group such as an allyl group; an aryl group such as a phenyl group or a tolyl group; a cycloalkyl group such as a cyclohexyl group, or part or all of the hydrogen atoms bonded to these carbon atoms substituted with a halogen atom, a cyano group, or the like; They are monovalent hydrocarbon groups having the same or different types and selected from chloromethyl group, trifluoropropyl group, cyanoethyl group and the like, and having 1 to 20 carbon atoms. However, it is preferable that 90 mol% or more of R ¹ is a methyl group from the viewpoint of hand.

R ² has 1 to 6 carbon atoms such as a methylene group, a dimethylene group, a trimethylene group and a tetramethylene group.
Is a divalent hydrocarbon group. Among these, a trimethylene group is preferable. R ³ is a hydrogen atom or a monovalent alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group. R ³ is preferably a hydrogen atom or a methyl group or an ethyl group from the viewpoint of reactivity, and more preferably a hydrogen atom. R ⁴ is a hydrogen atom or an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group;
An aryl group such as a phenyl group; a cycloalkyl group such as a cyclohexyl group, or a group in which part of the carbon atoms of these groups has been substituted with an oxygen atom, a nitrogen atom, a sulfur atom, or the like, and a hydrogen atom bonded to a carbon atom of any of these groups Selected from chloromethyl group, trifluoropropyl group, cyanoethyl group, 2,3-dihydroxypropyl group and the like, in which a part or all of is substituted by halogen atom, cyano group, hydroxyl group, etc., and having 1 to 10 carbon atoms. And a hydrogen atom is preferable among them. A is an integer of 0 to 3.

The relationship between m and n is 0.0001 <n /
(M + n) <0.1. When n / (m + n) is 0.1 or more, the yellowing effect of the treated cloth deteriorates due to yellowing, and when n / (m + n) is 0.0001 or less, the flexibility becomes poor. This range is necessary because it becomes insufficient, and more preferably 0.001 <n / (m + n) <0.03. Further, the sum of m and n is 10 <(m + n) <10,000, and when it is 10 or less, the softening effect is insufficient, and
If it is more than 00, it is difficult to emulsify and it is difficult to handle, so this range is necessary, preferably 50 <(m + n) <3,000, more preferably 100 <.
(M + n) <2,000.

Specific examples of the amino group-containing organopolysiloxane include the following compounds of the following (Formula 5).
(Or, these amino groups are blocked with glycidyl alcohol or the like.) In addition, a branch unit can be introduced into the amino group-containing organosiloxane as long as the properties of the synthetic fiber treating agent of the present invention are not changed. It is.

[0010]

Embedded image

In the alkyl polysilicate of the component (B), examples of the alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group. The alkyl group is preferably selected from a methyl group, an ethyl group, and a propyl group from the viewpoint of reactivity. The compounding amount of the alkyl polysilicate is 0.01 to 10 parts by weight based on 100 parts by weight of the amino group-containing organopolysiloxane (A). 0.01
If the amount is less than part by weight, the crosslinking effect is weak and the durability (stability) is low.
Run out. If the amount exceeds 10 parts by weight, the crosslinking reaction proceeds too much and the flexibility is reduced. Therefore, this range is necessary, and preferably 0.1 to 5 parts by weight.

In the organopolysiloxane of the component (C), R ⁶ is a monovalent hydrocarbon group having 1 to 20 carbon atoms similar to R ¹ described above, and 90 mol% or more is a methyl group from the viewpoint of texture. Is preferred. L is less than 10 and
In the case of 2,000 or more, the compatibility with the amino group-containing organopolysiloxane becomes poor, and it becomes impossible to enhance the dark color effect, so it is necessary to be within this range,
More preferably, 20 <L <500. Component (C) is used in an amount of 0 to 50 parts by weight with respect to 100 parts by weight of component (A).
When an organosiloxane as a component is blended, a more excellent dark color effect can be provided. However, if the amount is more than 50 parts by weight, the flexibility is lowered, so that the amount is preferably 50 parts by weight or less, more preferably 30 parts by weight or less.

When various synthetic fibers are treated with the synthetic fiber treating agent of the present invention, they can be diluted with an appropriate solvent and adjusted to a desired concentration, but can be dissolved in water with a surfactant. After emulsifying and dispersing to form an emulsion, it is preferable to dilute with water to adjust to a desired concentration, adhere to the fiber by means of dipping, spraying or the like, heat-treat and dry. In the case of emulsification, the surfactants used include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, sorbitan fatty acid ester, and glycerin fatty acid ester; Cationic surfactants such as quaternary ammonium salts are preferred. Above all, to enhance the darkening effect of the treated cloth, use HL
A polyoxyethylene alkyl ether or a polyoxyethylene alkyl phenyl ether in which B is 12 to 16 is preferred. Those with an HLB of less than 12 have insufficient emulsifying power and cannot produce a stable emulsion. If the HLB is more than 16, the compatibility with the amino group-containing organopolysiloxane is poor, and the dark color effect is reduced. For this reason, the HLB is preferably in the range of 12 to 16, and more preferably 13 to 15.

The amount of these surfactants is preferably 1 to 50 parts by weight based on 100 parts by weight of the synthetic fiber treating agent of the present invention. If the amount is less than 1 part by weight, the stability of the emulsion is insufficient, and if it exceeds 50 parts by weight, the characteristics are not changed and it is uneconomical. Is 5 to 30 parts by weight.

Further, specific examples of the surfactant are listed by chemical formulas. C ₁₂ H ₂₅ O (C ₂ H ₄ O) _× H, C ₁₃ H ₂₇ O (C ₂ H ₄ O) _× H, C ₁₆ H
₃₃ O (C ₂ H ₄ O) _x H, C ₁₈ H ₃₇ O (C ₂ H ₄ O) _x H, C ₈ H ₁₇ C ₆ H ₄ O (C ₂ H ₄ O) _x
H, C ₉ H ₁₉ C ₆ H ₄ O (C ₂ H ₄ O) _× H and the like. (Where C ₆
H ₄ represents a phenylene group, and x represents a positive integer. Incidentally, the amount of adhesion to the fiber when the synthetic fiber treating agent of the present invention is treated on the fiber is not particularly limited.
About 0.1 to 5% by weight of the fiber is sufficient.

[0016]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples. The viscosities described in the examples are values at 25 ° C.

[Preparation of emulsion] Amino group-containing organopolysiloxane (a) to (e) represented by the following formula (6):
And an organopolysiloxane (f) to (g) to prepare an emulsion. The other raw materials (h) to (L) will be described later.

Embedded image

(Emulsion Preparation Example 1) An amino group-containing organopolysiloxane (a) 240 g, an organopolysiloxane (f) 60 g, an alkyl polysilicate (h) 1 g, and polyoxyethylene tridecyl ether (j) 30 g were blended. , Homomixer / TK Auto Homomixer Model M (trade name, manufactured by Tokushu Kika Co., Ltd.)
After 0 g was added, phase inversion was performed by high-speed stirring with a homomixer. After the phase inversion, the mixture was further stirred for 10 minutes, and then 639 g of water was added to obtain a cloudy emulsion 1.

(Emulsion Preparation Examples 2 to 11 ) The respective components were blended in the amounts shown in (Table 1), and cloudy emulsions 2 to 11 were obtained in the same manner as in Preparation Example 1. (Table 1)
Among the raw materials used in Preparation Examples 1 to 11 described above, those other than those described above are shown below. The unit of the number for each ingredient is g. Alkyl polysilicate (h): Ethyl polysilicate (SiO ₂ minutes: 40% by weight) Alkyl polysilicate (i): Ethyl polysilicate (SiO ₂ minutes: 20% by weight) Emulsifier (j): Polyoxyethylene tridecyl ether ( H
LB: 14.5), emulsifier (k): polyoxyethylene tridecyl ether mixture [mixing ratio: (HLB 7.9) / (HLB 18.3) = 1 /
3], emulsifier (L): polyoxyethylene nonylphenyl ether (HLB: 14.1).

[0020]

[Table 1]

(Examples 1 to 7 and Comparative Examples 1 to 4 ) A black polyester georgette cloth was immersed in a 6% aqueous solution of the emulsions 1 to 13 obtained above, and the squeezing rate was 100% with a mangle roll. After drying at 120 ° C. for 2 minutes, curing was further performed at 170 ° C. for 1 minute. After evaluating the darkness and flexibility of the cloth according to the method described below, the cloth was washed five times with a washing machine [the washing machine used was one manufactured in accordance with JIS L-217-105], and after washing. Was measured for darkness. Next, the durability (stability) thereof was evaluated from the difference in the value of the darkness L before and after washing, and the results are summarized in Table 2 below.

[0022]

[Table 2]

(Criteria for Evaluation of Flexibility by Touch) 〇: Soft feeling, Δ: Slightly hard, Kissim feeling, ×: Rough feeling. (Evaluation of dark color) Color difference meter ZE-2000 (manufactured by Nippon Denshoku Industries)
The L value was measured using. L value: 12 to 13 (good dark color effect), L value: 13 to 14 (with some dark color effect), L value: 14 to (no dark color effect). From the results of (Table 1) and (Table 2), it was confirmed that the synthetic fiber treated with the synthetic fiber treating agent of the present invention provided a stable dark color effect and flexibility.

[0024]

The synthetic fiber treated with the synthetic fiber treating agent of the present invention can provide a stable dark color effect and flexibility.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-269174 (JP, A) JP-A-2-191773 (JP, A) JP-A-4-214482 (JP, A) 31477 (JP, B1) Hiroshi Horiguchi "new surfactant" February 5, 1993, Sankyo Shuppan Co., Ltd., the first 66-70 rows and the 587-588 line (58) investigated the field (Int.Cl. ⁷ , DB name) D06P 5/00-5/22 D06P 1/52-1/58 D06M 15/643-15/657 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] (A) The following general formula: [Where R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ² is a divalent hydrocarbon group having 1 to 6 carbon atoms, R ³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms] , R ⁴ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, a is an integer of 0 to 3, m and n are 0.0001 <n / (m + n) <0.1, 10 <(m
+ N) <10,000. The amino group-containing organopolysiloxane represented by the formula 1
00 parts by weight, (B) alkyl polysilicate
0.01 to 10 parts by weight and (C) the following general formula: (Where R ⁶ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, L is 10
<L <2,000. A synthetic fiber treating agent comprising 0 to 50 parts by weight of an organopolysiloxane represented by the formula (1). 2. An aqueous emulsion type synthetic fiber treating agent obtained by emulsifying 100 parts by weight of the synthetic fiber treating agent according to claim 1 with 1 to 50 parts by weight of a nonionic surfactant and / or a cationic surfactant. 3. The aqueous emulsion type synthetic fiber treating agent according to claim 2, wherein the surfactant is a nonionic surfactant having an HLB of 12 to 16.