JP2003003378A - Fiber treatment agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an emulsion type fiber treatment agent having excellent dilution stability, compounding stability and mechanical stability, and also having excellent stability during high-temperature storage and low-temperature storage. . (A) 100 parts by weight of an amino-functional polyorganosiloxane, (B) 10 to 200 parts by weight of a mixture of a nonionic surfactant and a carboxylic acid type amphoteric surfactant,
(C) 20 to 400 parts by weight of water, and the mixture of (B) has a nonionic surfactant / sulfonic acid type amphoteric surfactant ratio (weight ratio) of 1 / 0.1 to 1/20. An oil-in-water type amino-functional silicone emulsion is used as a main component of a fiber treatment agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an emulsion type fiber treating agent, and particularly to excellent dilution stability, compounding stability and mechanical stability during fiber treatment, and stability during high temperature storage and low temperature storage. The present invention relates to a fiber treatment agent containing an amino-functional silicone emulsion having excellent properties as a main component.

[0002]

2. Description of the Related Art Conventionally, cotton, hemp, silk, wool, angora,
Natural fibers such as mohair; Regenerated fibers such as rayon and bemberg; Semi-synthetic fibers such as acetate; Syntheses such as polyester, polyamide, polyacrylonitrile, polyvinyl chloride, vinylon, polyethylene, polypropylene, nylon, polyurethane elastic fibers. Fibers; and fibrous materials such as glass fibers, carbon fibers, inorganic fibers such as silicon carbide fibers, flexibility, smoothness, wrinkle resistance,
In order to impart various properties such as elongation-recoverability and water repellency, a surfactant is added to polyorganosiloxane and the silicone oil emulsion obtained by using an emulsifying machine or the emulsification of low-molecular cyclic dimethylsiloxane is emulsified. Similar silicone emulsions obtained by polymerization have been used.

However, the silicone emulsions obtained by these methods have an average particle size of the oil phase of 0.3 μm or more, and 20 to 20% of water is used for fiber treatment.
The dilution stability when diluting 100 times, the compounding stability when various additives are used together, and the stability against mechanical shearing force in steps such as stirring, circulation, and squeezing of the treatment liquid are insufficient. As a result, the emulsion is destroyed and polyorganosiloxane floats on the surface of the treatment bath.
This has the drawback of forming oil droplets (referred to as oil spots) on the fiber material and causing stains on the fiber. Further, when such a silicone emulsion is used for fiber treatment, the oil phase does not sufficiently permeate the fine structure of the fiber and forms a silicone layer on the surface of the fiber, so that an amino-functional polyorganosiloxane is used as the base oil. The used one had a problem of producing a slimy feeling.

Further, a microemulsion having an average particle size of less than 0.3 μm, which is obtained by emulsifying a polyorganosiloxane having a polar group or a silanol group under specific conditions, is used for care of textile products. It has been proposed (Japanese Patent Application Laid-Open No. 60-127327). Such a microemulsion is inadequate although the above-mentioned stability is improved to some extent, and the drawback that oil spots occur remains.

Proposed is a fiber treating agent containing a microemulsion having an average particle size of 0.15 μm or less, which is obtained by dropping a crude emulsion of a cyclic polyorganosiloxane low molecular weight product into water containing an emulsion polymerization catalyst. (Japanese Patent Laid-Open No. 2
-35071). Further, it has been proposed that a cyclic polyorganosiloxane monomer is used in combination with a nonionic surfactant and an ionic surfactant to obtain a microemulsion of less than 0.14 μm (JP-A-4-227932). ). However, the microemulsion obtained by such emulsion polymerization has a drawback that stability is significantly impaired by various additives.

Therefore, the applicant of the present application has filed Japanese Patent Application Laid-Open No. 9-530.
In Japanese Patent No. 16, a fiber treatment agent containing a microemulsion produced by a specific method as a main component was proposed. Such a fiber treating agent eliminates the drawbacks of the prior art and is excellent in dilution stability, compounding stability, and mechanical stability during fiber treatment. In addition, there are cases in which the stability is poor during high temperature storage, and wastewater separation and oil separation occur, and during low temperature storage, emulsifier coagulation occurs and whitening occurs.

[0007]

SUMMARY OF THE INVENTION The present invention is intended to eliminate the above-mentioned drawbacks of the existing fiber treating agents, and has excellent dilution stability, compounding stability and mechanical stability. In addition, it is an object of the present invention to provide an emulsion-type fiber treatment agent which is excellent in stability during high temperature storage and low temperature storage.

[0008]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has identified a nonionic surfactant and a carboxylic acid type amphoteric surfactant as a surfactant used for producing an emulsion. It was found that the combined use in a ratio is extremely effective, and the present invention has been completed.

That is, the present invention relates to a mixture of 100 parts by weight of (A) amino-functional polyorganosiloxane, (B) a mixture of a nonionic surfactant and a carboxylic acid type amphoteric surfactant, 10-2.
00 parts by weight, (C) 20 to 400 parts by weight of water, and the mixture (B) has a nonionic surfactant / sulfonic acid type amphoteric surfactant ratio (weight ratio) of 1 / 0.1 to 1: 1. / 20
Is a fiber treatment agent containing an oil-in-water amino-functional silicone emulsion as a main component.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The (A) amino-functional polyorganosiloxane used in the present invention typically comprises the following siloxane units (a) and (b): (a) R _a Q _b SiO _{(4-ab) / 2} units;
(B) R _c SiO _{(4-c) / 2} unit [in the formula, R may be the same as or different from each other, and is a monovalent substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms ( However, some of them may be a silicon functional group; and Q is a general formula —R ¹ NZ ₂ (wherein R ¹ is an ether bond, a thioether bond, an ester in the chain). Represents a divalent hydrocarbon group in which a bond or a carbonylthioether bond may be present; Z may be the same or different with each other, and is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or 2- Represents an amino functional group); a is a number from 0 to 2; b is a number from 1 to 3, where a + b is a number from 1 to 3; Three
Of the amino acid number], which is an amino-functional polyorganosiloxane in which a silicon functional group may be present.

R of the above-mentioned (a) unit and (b) unit is methyl, ethyl, propyl, butyl, amyl,
Alkyl groups such as hexyl; alkenyl groups such as vinyl and allyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; phenyl groups; 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl , Halogenated hydrocarbon groups such as chlorophenyl and bromophenyl; and mercaptohydrocarbon groups such as 3-mercaptopropyl, 6-mercaptohexyl and mercaptophenyl. Further, a part of R is a hydroxyl group; or methoxy,
It may be an alkoxy group such as ethoxy and propoxy. As R, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is most preferable. In addition, since a fine microemulsion can be obtained, R
It is preferable that a part of the above is a silicon functional group.

In the amino functional group Q of the unit (a),
R bonded to the silicon atom of¹ As methylene, tri
Methylene, 2-methyltrimethylene, tetramethylene,
Alkylene groups such as hexamethylene and decamethylene;
Phenylene, biphenylene, bis (phenylene-4-i)
Ru) methylene, arylene groups such as naphthylene;
(CH₂)₃ OCH2-,-(CH₂)₃ O (CH₂)₂ -,
-(CH₂)₃ S (CH₂) ₂ -Like ether linkages in the chain
Divalent hydrocarbon group having a compound or a thioether bond;
-(CH₂)₃ C (O) OCH₂ -,-(CH₂)₃ C
(O) O (CH₂)₂ -,-(CH₂)₃ C (O) S (CH
₂)₂ -Such as an ester bond or a carbonyl group in the chain
Examples of the divalent hydrocarbon group having an ether bond,
The trimethylene group is the most suitable because it is easy to synthesize and stable.
preferable.

As mentioned above, Z is a hydrogen atom or an alkyl group such as methyl, ethyl, propyl or butyl;
Most preferably, it is a 2-aminoethyl group, and at least one of the two Z is a 2-aminoethyl group.

That is, the amino functional group Q is most preferably an N- (2-aminoethyl) -3-aminopropyl group having two amino groups.

The amino group content of the amino-functional polyorganosiloxane is preferably 0.02 to 3.0 meq / g, more preferably 0.3 to 1.5 meq / g,
Most preferred is 0.6 to 1.0 meq / g.

To obtain such an amino group content,
The molar ratio of the (a) unit to the (b) unit is 1: 2 to 1:13.
The range of 00 is preferable, 1: 5 to 1:65 is more preferable, and 1:15 to 1:20 is the most preferable.

The component (A) is, for example, when R ¹ is a trimethylene group, an amino group represented by the general formula: CH ₂ ═CHCH ₂ NZ ₂ (in the formula, Z is as described above) in the polyorganohydrogensiloxane. Containing unsaturated compounds,
It can be synthesized by reacting in the presence of a hydrosilylation catalyst.

Component (A) is, for example, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-
Obtained by ring-opening polymerization of a low-molecular weight cyclic polydiorganosiloxane such as octamethylcyclotetrasiloxane in the presence of an amino group-containing alkoxysilane such as (2-aminoethyl) -3-aminopropylmethyldimethoxysilane. You can

In this case, an amino-functional polyorganosiloxane having an alkoxy group such as methoxy or ethoxy and a silicon functional group such as a hydroxyl group generated by hydrolysis of the alkoxy group at the molecular end and in some cases in the molecule is obtained. To be In order to form a microemulsion having a fine oily phase, those having such a silicon functional group are preferable. Depending on the purpose, this may be treated with a silylating agent such as hexamethyldisilazane and substituted with a trimethylsilyl group before use.

Preferred amino-functional polyorganosiloxanes have the general formula (I):

[0021]

[Chemical 1]

Wherein Z is as defined above, preferably-(CH ₂ ) ₂ NH ₂ ; R ² is a methyl group, R ³ or

[0023]

[Chemical 2]

Is a side chain represented by the formula;
³ is a methyl group, an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group; x is a number from 1 to 20, y and z are each a number from 0 to 1500, provided that y and z
Has 20 to 1500 dimethylsiloxy groups in the molecule.
Is an oily polyorganosiloxane. x is preferably 5-10, most preferably 8. The above formula (I) represents the number of siloxane units, and does not mean a block copolymer.

The present invention provides the component (B) surfactant as
It is characterized by using a mixture of a nonionic surfactant and a carboxylic acid type amphoteric surfactant.

Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene trimethylnonyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene isocetyl ether, polyoxyethylene stearyl ether and polyoxyethylene stearyl ether. Polyoxyethylene alkyl ether-based surfactants such as oxyethylene oleyl ether and polyoxyethylene behenyl ether; polyoxyethylene alkyl such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether and polyoxyethylene dodecyl phenyl ether Aryl ether type surfactant; polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid Ether, polyoxyethylene fatty acid esters, polyoxyethylene hardened castor oil, glycerin fatty acid esters, polyglycerol fatty acid esters, sorbitan fatty acid esters, and ester-based surfactants such as sucrose fatty acid esters.

Particularly preferred are polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether. These nonionic surfactants may be used alone or in combination of two or more.

On the other hand, examples of the carboxylic acid type amphoteric surfactant include betaine type coconut oil fatty acid amide propyl betaine, lauric acid amide propyl betaine lauryl dimethylaminoacetic acid betaine, coconut oil alkyl betaine, and the like. Amidopropyl betaine is preferred. These betaine-type amphoteric surfactants are 1
The seeds may be used alone or in combination of two or more.

The amount of the surfactant (B) used is preferably 10 to 200 parts by weight, more preferably 30 to 180 parts by weight, based on 100 parts by weight of the component (A). If it is less than 10 parts by weight, a good microemulsion cannot be obtained, and 2
When it is used in an amount of more than 00 parts by weight, an excessive amount of the surfactant may hinder the adhesion of the amino-functional polyorganosiloxane to the fiber, or the viscosity of the resulting composition may be increased to deteriorate the fluidity of the fiber treatment. Because it will be difficult.

Further, in the present invention, in the mixture (B), the ratio (weight ratio) of nonionic surfactant / carboxylic amphoteric surfactant is 1 / 0.1 to 1/20, preferably 1
It is necessary to be in the range of / 1 to 1/10.

Among the components (B), the nonionic surfactant is
It mainly functions to disperse the amino-functional polyorganosiloxane of the component (A) in water. Further, since the carboxylic acid type amphoteric surfactant also has a function as a storage stabilizer of the composition in addition to a function as an emulsifier, if the ratio is too small, the storage stability is deteriorated and is too large. It becomes difficult to obtain a good emulsion because the composition is extremely discolored. The water of the component (C) is 10 parts of the component (A).
20 to 400 parts by weight is used with respect to 0 parts by weight.

The silicone emulsion of the present invention can be produced by a conventionally known method. That is, the step of adding an acid such as acetic acid to convert at least a part of the amino-functional polyorganosiloxane in the system into a salt at the end of the emulsion production step, and adding a water-soluble polyhydric alcohol such as glycerin are included. However, it is well known that it is permissible to add an effective amount of the preservative as necessary.

Examples of the emulsifying machine used include a homomixer, a homogenizer, and a colloid mill.

The silicone emulsion thus obtained can be used as it is or after diluted with water as a fiber treating agent. Further, depending on the purpose, a resin finishing agent such as glyoxal resin, melamine resin, urea resin, polyester resin, acrylic resin; and / or a water repellent agent or fiber such as polyorganohydrogensiloxane or polydimethylsiloxane. You may use together the emulsion of a softening agent.

Examples of the fiber material treated with the fiber treatment agent of the present invention include natural fibers such as wool, silk, hemp, cotton, angora and mohair; regenerated fibers such as rayon and bemberg and acetate. Semi-synthetic fibers such as; synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyvinyl chloride, vinylon, polyethylene, polypropylene, nylon, polyurethane elastic fibers; and inorganic fibers such as glass fibers, carbon fibers, silicon carbide fibers Exemplified, in terms of shape, staples,
Examples include filaments, tows, tops, and threads, and morphological examples include knits, woven fabrics, nonwoven fabrics, and papers.

In order to treat the fiber material with the fiber treatment agent of the present invention, a method such as spray treatment, roll treatment, brush coating or dipping is used. The amount of adhesion varies depending on the material and form of the fiber material and the treatment purpose and is not particularly limited, but is generally in the range of 0.01 to 10.0% by weight as the amino-functional polyorganosiloxane content with respect to the fiber material. Is. Then, the fiber material is allowed to form an amino-functional polyorganosiloxane layer by a method such as standing at room temperature, blowing with hot air, and heat treatment.

[0037]

EFFECTS OF THE INVENTION According to the present invention, it has excellent dilution stability, compounding stability and mechanical stability as compared with the conventional emulsion type silicone fiber treating agents, and it is processed into fibers without generation of oil spots. , An emulsion type fiber treatment agent that permeates the fine structure of the fiber to give the fiber good water repellency with excellent durability and excellent flexibility, and gives a dry texture without a slimy feel on the surface. In addition, this fiber treatment agent does not have inferior stability such as poor stability during high temperature storage, wastewater separation or oil separation, and no whitening phenomenon due to emulsifier coagulation during low temperature storage. It has low temperature stability.

[0038]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. In these examples, parts represent parts by weight and% represent% by weight, unless stated otherwise. The invention is not limited by these examples. Example 1 Polydimethylsiloxane containing 2-aminoethyl-3-aminopropyl group with a terminal trimethylsilyl group blocked (viscosity of 1.00
0 cSt, amino content 0.6 meq / g, silicone (i) 100 parts, polyoxyethylene (7) cetyl ether 16 parts, polyoxyethylene (13) cetyl ether 16 parts,
And 40 parts of glycerin were added, and the mixture was heated with stirring at 50 ° C. for about 10 minutes. Next, 1.6 parts of acetic acid and 50 parts of coconut oil fatty acid amide propyl betaine (30% aqueous solution) were added and stirred to form a viscous gel, and further 270 parts of coconut oil fatty acid amide propyl betaine (30% aqueous solution), and Add 6 parts of purified water and stir uniformly, silicone content 20%, average particle size 25n
m silicone emulsion composition (emulsion-
1) was obtained. Example 2 Polydimethylsiloxane containing 2-aminoethyl-3-aminopropyl group having a terminal trimethylsilyl group blocked (viscosity 70,0
00cSt, amino content 0.02 meq / g, silicone (i
i)) 100 parts by weight of polyoxyethylene (7) cetyl ether 1
0 parts, 10 parts of polyoxyethylene (13) cetyl ether, and 40 parts of glycerin were added, and the mixture was heated with stirring at 50 ° C. for about 10 minutes. Next, 1.6 parts of acetic acid and 50 parts of coconut oil fatty acid amide propyl betaine (30% aqueous solution) were added and stirred to form a viscous gel, and further 350 parts of coconut oil fatty acid amide propyl betaine (30% aqueous solution) was added. Add and stir evenly,
A silicone emulsion composition (emulsion-2) having a silicone content of 17.8% and an average particle size of 275 nm was obtained. Comparative Example 1 2-Aminoethyl-3-aminopropyl Group-Containing Polydimethylsiloxane Blocking Terminal Trimethylsilyl Group
0 cSt, amino content 0.6 meq / g, silicone (i) 100 parts, polyoxyethylene (7) cetyl ether 16 parts, polyoxyethylene (13) cetyl ether 16 parts,
And 40 parts of glycerin were added, and the mixture was heated with stirring at 50 ° C. for about 10 minutes. Then, 1.6 parts of acetic acid and 50 parts of purified water are added and stirred to form a viscous gel, and then 276 parts of purified water is added and uniformly stirred to give a silicone content of 20% and an average particle size.
A 20 nm silicone emulsion composition (Emulsion-3) was obtained.

With respect to these emulsions, high temperature holding (50 ° C., 4 weeks) and low temperature holding (10 ° C., 4 weeks)
The change in state in the case of doing was visually evaluated.

Further, each of the above emulsions was diluted with water so that each active ingredient was 3%, and 100% cotton was prepared.
Dipped in cloth and dried at 100 ° C for 5 minutes, then
It heated at 0 degreeC for 2 minutes, and obtained the hardened film. The treated cloth was observed for the presence of oil spots.

The results are shown in Table 1.

[0042]

[Table 1]

Claims (2)

[Claims] 1. 100 parts by weight of (A) an amino-functional polyorganosiloxane, 10 to 200 parts by weight of a mixture of (B) a nonionic surfactant and a carboxylic acid type amphoteric surfactant,
(C) Contains 20 to 400 parts by weight of water, and the mixture (B) has a nonionic surfactant / carboxylic acid type amphoteric surfactant ratio (weight ratio) of 1 / 0.1 to 1/20. A fiber treatment agent containing an oil-in-water type amino-functional silicone emulsion as a main agent. 2. The fiber treatment agent according to claim 1, wherein the nonionic surfactant of the component (B) is polyoxyethylene alkyl ether, and the carboxylic acid type amphoteric surfactant is a betaine type amphoteric surfactant.