JP2001049582A - Treating agent for wool - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a wool treating agent exhibiting excellent stability to ionic substances and suitable as a shrink-proofing agent by forming an aqueous emulsion of an amino-containing diorganopolysiloxane having both molecular chain terminals blocked with hydroxyl groups, etc., using a specific nonionic emulsifier. SOLUTION: The objective wool treating agent is produced by emulsifying (A) 100 pts.wt. of an amino-containing diorganopolysiloxane having both molecular chain terminals with hydroxyl groups or alkoxy groups in 100-1,000,000 pts.wt. of water using 2-100 pts.wt. of a mixture of (B) a nonionic emulsifier such as polyoxyethylene alkyl ether having an HLB of <15, preferably 9-13 and (C) the above emulsifier having an HLB of >=15 at a B:C weight ratio of 1:99 to 99:1, preferably 50:50 to 99:1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a wool treating agent, and more particularly to a wool treating agent exhibiting excellent stability to ionic substances.

[0002]

2. Description of the Related Art It is known that wool fabric has a drawback that when washed at home, it shrinks greatly and becomes felt.
Conventionally, a method for preventing such shrinkage (shrink-proof processing method)
Known methods include a method of chemically treating wool fibers and a method of treating wool fibers with an organic resin. Further, in order to impart a good feeling, a method of treating with an organosilane or a method of treating with an amino group-containing organopolysiloxane is known (see JP-A-4-119173). Among these, the most widely used shrink-prevention method is the chlorination / Harcosett method (Dyeing Industry,
Vol. 36, pages 260-269). This treatment method is a method in which wool top is chlorinated and then treated with a finishing agent. Normally, chlorine is neutralized using sodium sulfite or the like after chlorination treatment, and unnecessary ions generated at this time are treated. The chemical substances and excess sodium sulfite are removed in a rinsing tank and then treated with a finishing agent. However, a small amount of ionic substance remains even through the rinsing tank,
When an organopolysiloxane emulsion having an ionizable functional group such as an amino group is used as a finishing agent, there is a disadvantage that the emulsion is separated or broken.

[0003]

The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that the HLB is 15
By using a nonionic emulsifier of less than 15 and a nonionic emulsifier having an HLB of 15 or more, it was found that an aqueous emulsion composition stable to ionic substances was obtained, and the present invention was reached. That is, an object of the present invention is to provide a wool treating agent which exhibits excellent stability to ionic substances and is useful as a shrinkproofing agent.

[0004]

The present invention provides (A) an amino group-containing organopolysiloxane, (B) a nonionic emulsifier having an HLB of less than 15, (C) a nonionic emulsifier having an HLB of at least 15 and (D) The present invention relates to a wool treating agent, which is an aqueous emulsion composition comprising water.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The amino group-containing organopolysiloxane of the component (A) is
Any type of organopolysiloxane containing at least one amino group in the molecule may be used, and there are no particular restrictions on the type and the like, but those in which the amino group is bonded to a silicon atom via a carbon atom are preferred. Such an amino group-containing organopolysiloxane may be linear, branched, or cyclic. For example, the average molecular formula:

Embedded image The diorganopolysiloxane represented by these is mentioned. In the above formula, R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
Aliphatic saturated hydrocarbon groups such as heptyl group, octyl group, decyl group and dodecyl group; aliphatic unsaturated hydrocarbon groups such as vinyl group, allyl group and hexenyl group; cyclopentyl group;
Alicyclic saturated hydrocarbon group such as cyclohexyl group; aromatic hydrocarbon group such as phenyl group, tolyl group, naphthyl group and substitution in which hydrogen atoms bonded to carbon atoms of these groups are partially substituted by halogen atoms And hydrocarbon groups.
These groups do not need to be the same in the molecule, and may be a combination of two or more kinds.
Among these, a methyl group or a combination of a methyl group and another organic group is preferable. R ¹ is a hydrogen atom or a monovalent hydrocarbon group, and examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a phenyl group, and a cyclohexyl group. X is a group selected from R, a hydroxyl group and an alkoxy group having 1 to 5 carbon atoms, and examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group. Among these, a hydroxyl group or an alkoxy group is preferable. Y represents a hydrogen atom or 1 to 5 carbon atoms
Is an alkyl group. Q is a divalent hydrocarbon group, specifically, an alkylene group such as a methylene group, an ethylene group, a propylene group, or a butylene group; an arylene group represented by the formula: —C ₆ H ₄ —; An alkylene arylene group represented by (CH ₂ ) ₂ C ₆ H ₄ — is exemplified. Among these, a propylene group is preferred. m and n are integers of 1 or more. 25 ° C of this organopolysiloxane
Is preferably a kinematic viscosity is 10 mm ² / s or more at, and more preferably in the range of 50~10,000mm ² / s. a is an integer of 0 to 5, preferably 0 or 1. The amino group-containing organopolysiloxane of this component has, for example, the formula: H ₂ N (CH ₂ ) ₃ Si (CH ₃ ) (O
CH ₃₎ and hydrolysis-condensation product obtained by hydrolyzing the organoalkoxysilane represented by ₂ with excess water, and dimethylcyclopolysiloxane using a basic catalyst such as sodium hydroxide, 80 Heat to 110 ° C. to allow equilibrium reaction. When the reaction mixture reaches a desired viscosity, it can be produced by neutralizing the basic catalyst with an acid (see JP-A-53-98499). Examples of the amino group-containing organopolysiloxane of this component include diorganopolysiloxanes represented by the following average molecular formula.

Embedded image

The components (B) and (C) used in the present invention are nonionic emulsifiers. The nonionic emulsifier (B) has a HLB of less than 15, whereas the nonionic emulsifier (C) has a nonionic emulsifier. The system emulsifier has an HLB of 15 or more. In particular, the component (B) preferably has an HLB in the range of 9 to 13, more preferably 10 to 12. Examples of the nonionic emulsifier include polyoxyethylene alkyl ethers, polyoxyalkylene alkyl phenol ethers, polyoxyalkylene alkyl esters, sorbitan alkyl esters,
Examples thereof include polyoxyalkylene sorbitan alkyl esters. Among them, HL is used as the component (B).
B is less than 15 one or two or more selected,
As the component (C), one or more components having an HLB of 15 or more are selected and used. The compounding amount is preferably such that the total amount of the components (B) and (C) is in the range of 2 to 100 parts by weight with respect to 100 parts by weight of the component (A).
More preferably, it is in the range of 60 parts by weight. The ratio of the component (B) to the component (C) is usually from (1:99) to weight ratio.
Used within the range of (99: 1), (50:50)-
It is preferable to be within the range of (99: 1). HL
B is an index indicating the balance between both the hydrophilic group and the lipophilic group in the emulsifier molecule, and the following several formulas have been proposed for nonionic emulsifiers. For example,
When the emulsifier is a polyhydric alcohol and a fatty acid ester,
The HLB can be calculated using the formula: HLB = 20 × (1-S / A) (where S is the degree of saponification of the ester and A is the acid value of the fatty acid). When only a polyoxyethylene group is contained as a hydrophilic group, the formula: HL
HLB can be calculated using B = E / 5, where E is the weight fraction of oxyethylene groups. These nonionic emulsifiers (B) and (C) may be used simultaneously when emulsifying the amino group-containing organopolysiloxane (A), or may be emulsified using either one of the emulsifiers. After that, another emulsifier may be added to the obtained aqueous emulsion.

[0007] The emulsifier of the aqueous emulsion composition of the present invention may comprise only the above-mentioned components (B) and (C), but if necessary, such as aliphatic amine salts, quaternary ammonium salts and alkylpyridinium salts. Use of a cationic emulsifier or an amphoteric emulsifier in combination may be acceptable.

[0008] The water of the component (D) is the same as the component (A).
This is for emulsifying the component (C), and the amount thereof is not particularly limited, but is usually used in the range of 1 to 1,000,000 parts by weight based on 100 parts by weight of the component (A).

The aqueous emulsion composition of the present invention comprises the above components (A) to (D). In addition to these components, if necessary, an organopolysiloxane other than the component (A); Methyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane,
Alkoxy such as phenyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane Silanes; and hydrolyzed condensates thereof; organic acids such as colloidal silica, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin dilaurate, dioctyltin diacetate, tin octylate, zinc stearate, zinc octylate, and iron octylate Metal salts; catalysts for condensation reactions of amine compounds such as n-hexylamine and guanidine; anti-wrinkling agents, thickening agents, coloring agents, preservatives, fungicides, rust inhibitors and the like may be used in combination. The average particle size of the aqueous emulsion composition of the present invention is usually 0.1 μm or more.

The wool treating agent of the present invention as described above is stable against ionic substances. In particular, the emulsion is separated from ionic substances and sodium sulfite generated by neutralization after chlorination. It does not break or break. Such a wool treating agent of the present invention has an advantage that it can impart excellent shrink resistance and a good texture to wool of any form such as top, rose hair, knitwear, and cloth.

[0011]

Next, the present invention will be described in detail with reference to examples. In the examples, parts and% mean parts by weight and% by weight, and the viscosity is a value at 25 ° C.

[0012]

Example 1 Average molecular formula:

Embedded image Amino group-containing diorganopolysiloxane 30 represented by the formula:
Parts, 2 parts of polyoxyethylene (ethylene oxide-6 mol) lauryl ether (HLB = 11.8) and 1 part of polyoxyethylene (ethylene oxide-20 mol) lauryl ether (HLB = 16.6) were uniformly mixed. Thereafter, 3 parts of water was added and the mixture was stirred uniformly. Next, this was emulsified using a colloid mill type emulsifier, and further 64 parts of water was added to prepare a uniform aqueous emulsion composition. The average particle size of this aqueous emulsion composition was 0.31 μm. A 45 × 45 cm wool 10 was placed in a treatment bath using the aqueous emulsion composition thus obtained as a treatment liquid.
After immersing three 0% non-dyed surge cloth for clothing for 30 seconds, the squeezing rate was adjusted to 100% with a mangle roller, squeezed, spread on a wire net, and dried at room temperature for 24 hours. Next, heat treatment was performed at 130 ° C. for 5 minutes in a hot-air circulation dryer. After allowing it to cool at room temperature, 3
A mark of 0 cm was made and the laundry was washed under the following washing conditions. The washed wool fabric was spread horizontally and dried, and the washing shrinkage (%) in the longitudinal and transverse directions was measured. ○ Washing conditions After washing once under the following conditions, washing was carried out twice more under the same conditions except that the detergent was removed. Bath ratio 1:50 Temperature 40 ° C Detergent Zab [Kao Corporation; weakly alkaline detergent] Time 15 minutes To further examine the stability of the obtained aqueous emulsion composition to ionic substances, 3 parts of the above emulsion was washed with water. After uniformly dispersing the mixture in 97 parts, 10 parts of a 10% aqueous solution of sodium sulfite was added and uniformly mixed. afterwards,
The emulsion was allowed to stand at room temperature until the next day, and the appearance of the emulsion was visually measured. The results are shown in Table 1 below.

[0013]

Example 2 Average molecular formula:

Embedded image Amino group-containing diorganopolysiloxane 30 represented by the formula:
And 3 parts of polyoxyethylene (ethylene oxide-6 mol) lauryl ether (HLB = 11.8) were uniformly mixed, and then 3 parts of water was added and stirred uniformly. Next, this was emulsified using a colloid mill-type emulsifier, and further 63 parts of water was added and uniformly mixed, and then 1 part of polyoxyethylene (ethylene oxide-20 mol) lauryl ether (HLB = 16.6) was added. To prepare an aqueous emulsion composition. The average particle size of this aqueous emulsion composition was 0.30 μm. Using the aqueous emulsion composition thus obtained, the washing shrinkage ratio and the stability to ionic substances were measured in the same manner as in Example 1. The results are shown in Table 1 below.

[0014]

Comparative Example 1 Average molecular formula:

Embedded image Amino group-containing diorganopolysiloxane 30 represented by the formula:
And 3 parts of polyoxyethylene (ethylene oxide-6 mol) lauryl ether (HLB = 11.8) were uniformly mixed, and then 3 parts of water was added and stirred uniformly. Next, this was emulsified using a colloid mill type emulsifier, and further 64 parts of water was added to prepare a uniform aqueous emulsion composition. The average particle size of this aqueous emulsion composition is 0.3
It was 0 μm. Using the aqueous emulsion composition thus obtained, the washing shrinkage ratio and the stability to ionic substances were measured in the same manner as in Example 1. The results are shown in Table 1 below.

[0015]

Comparative Example 2 Average molecular formula:

Embedded image Amino group-containing diorganopolysiloxane 30 represented by the formula:
And 3 parts of polyoxyethylene (ethylene oxide-20 mol) lauryl ether (HLB = 16.6) were uniformly mixed, and then 3 parts of water was added and uniformly stirred. Next, this was emulsified using a colloid mill-type emulsifier, and further 64 parts of water was added to obtain an aqueous emulsion composition. However, the aqueous emulsion composition separated after several hours.

[0016]

Comparative Example 3 Average molecular formula:

Embedded image Amino group-containing diorganopolysiloxane 30 represented by the formula:
Parts, 2 parts of polyoxyethylene (ethylene oxide-6 mol) lauryl ether (HLB = 11.8) and 1 part of polyoxyethylene (ethylene oxide-10 mol) lauryl ether (HLB = 14.1) were uniformly mixed. Thereafter, 3 parts of water was added and the mixture was stirred uniformly. Next, this was emulsified using a colloid mill type emulsifier, and further 64 parts of water was added to prepare a uniform aqueous emulsion composition. The average particle size of this aqueous emulsion composition was 0.32 μm. Using the aqueous emulsion composition thus obtained, the washing shrinkage ratio and the stability to ionic substances were measured in the same manner as in Example 1. The results are shown in Table 1 below.

[0017]

Comparative Example 4 Washing shrinkage of a non-dyed surge cloth for cloth of 100% wool of 45 × 45 cm without treatment with an aqueous emulsion composition was measured in the same manner as in Example 1. The results are shown in Table 1 below.

[0018]

[Table 1]

[0019]

Example 3 Average molecular formula:

Embedded image Amino group-containing diorganopolysiloxane 30 represented by the formula:
Part, polyoxyethylene (ethylene oxide-6 mol) lauryl ether (HLB = 11.8) 3 parts, formula:
After uniformly mixing 1 part of a cationic emulsifier represented by (CH ₃ ) ₃ (C ₁₂ H ₂₅ ) N ⁺ Cl ⁻ , 4 parts of water was added and stirred uniformly. Next, this was emulsified using a colloid mill type emulsifier, and further 51 parts of water and polyoxyethylene (ethylene oxide-20 mol) lauryl ether (HL)
B = 16.6), and 1 part was added, and the mixture was uniformly dissolved and dispersed. Thereafter, 0.5 parts of methyltrimethoxysilane and 9.5 parts of water were further added to prepare a uniform aqueous emulsion composition. The average particle size of this aqueous emulsion composition is 0.1.
It was 29 μm. Using the aqueous emulsion composition thus obtained, the stability to ionic substances was measured in the same manner as in Example 1. The results are shown in Table 2 below.

[0020]

Comparative Example 5 Average molecular formula:

Embedded image Amino group-containing diorganopolysiloxane 30 represented by the formula:
Part, polyoxyethylene (ethylene oxide-6 mol) lauryl ether (HLB = 11.8) 3 parts, formula:
After uniformly mixing 1 part of a cationic emulsifier represented by (CH ₃ ) ₃ (C ₁₂ H ₂₅ ) N ⁺ Cl ⁻ , 4 parts of water was added and stirred uniformly. Next, this was emulsified using a colloid mill-type emulsifier, and further 52 parts of water was added to uniformly disperse and disperse.
Thereafter, 0.5 parts of methyltrimethoxysilane and 9.5 parts of water were further added to prepare a uniform aqueous emulsion composition. The average particle size of this aqueous emulsion composition was 0.30 μm. Using the aqueous emulsion composition thus obtained, the stability to ionic substances was measured in the same manner as in Example 1. The results are shown in Table 2 below.

[0021]

[Table 2]

[0022]

Example 4 Average molecular formula:

Embedded image Amino group-containing diorganopolysiloxane 2 represented by
9.5 parts, partial hydrolyzate of methyltriethoxysilane (kinematic viscosity 75 mm ^{2 / s)} 0.5 part, polyoxyethylene (6 mol) lauryl ether (HLB = 11.8)
After uniformly mixing 3.5 parts, 3 parts of water was added and stirred. Next, this was emulsified using a colloid mill-type emulsifier, and 65.5 parts of water and 1.0 part of polyoxyethylene (45 mol) nonyl ether (HLB = 18.1) were further added to obtain a uniform aqueous emulsion composition. Was prepared. The average particle size of this aqueous emulsion composition was 0.33 μm. Using the aqueous emulsion composition thus obtained, the stability to ionic substances was measured in the same manner as in Example 1. As a result, no destruction of the emulsion was observed and the stability was good. When the washing shrinkage was measured in the same manner as in Example 1, the total washing shrinkage in the vertical and horizontal directions was 7.5%. On the other hand, the laundry shrinkage of the untreated fabric was 18.9%, and it was found that the laundry shrinkage was reduced to half or less by the treatment with the aqueous emulsion composition of the present invention. This proved that the aqueous emulsion composition of the present invention was extremely good as a shrink-proofing agent.

[0023]

The wool treating agent of the present invention is an aqueous emulsion composition comprising the above components (A) to (D),
Since a nonionic emulsifier having an HLB of component (B) of less than 15 and a nonionic emulsifier having an HLB of component (C) of 15 or more are added and blended, they exhibit excellent stability against ionic substances and exhibit shrinkage resistance. It has the feature of being useful as a processing agent.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Isao Ona, 2-2 Chikusa Beach, Ichihara City, Chiba Prefecture Toray Dow Corning Silicone Co., Ltd. Research and Development Headquarters F-term (reference) 4J002 CH022 CH052 CP091 DE027 EH036 EN026 EN136 EU076 FD150 FD312 FD316 GK02 4L033 AA03 AC15 CA64

Claims (3)

[Claims] (A) an amino group-containing organopolysiloxane; (B) a nonionic emulsifier having an HLB of less than 15;
A wool treating agent, which is an aqueous emulsion composition comprising (C) a nonionic emulsifier having an HLB of 15 or more and (D) water. 2. The wool treating agent according to claim 1, wherein the component (A) is an amino group-containing diorganopolysiloxane in which both ends of the molecular chain are blocked with hydroxyl groups. 3. The wool treating agent according to claim 1, wherein the component (A) is an amino group-containing diorganopolysiloxane in which both ends of the molecular chain are blocked with an alkoxy group.