JPH11158779A - Fiber processing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fiber processing agent capable of imparting softness, water- and moisture-absorbing property, antifouling property, smoothness, compression-recovering property and antistatic property, all of which are rich in durability, to a fiber material by compounding a specific polyorganosiloxane with a specific urethane prepolymer. SOLUTION: This aqueous emulsion-type processing agent is obtained by compounding a polyorganosiloxane expressed by the formula R<1> is a 1-20C monovalent hydrocarbon; A is R<2> (NR<3> CH2 CH2 )a NR<4> R<5> [R<2> is a 1-8C divalent hydrocarbon; R<3> , R<4> and R<5> are each H, a 1-8C monovalent hydrocarbon or an acyl; (a)=0-10]; G is a (poly)oxyalkylene chain expressed by (R<6> )b O(C2 H4 O)m (C3 H6 O)n R<7> [R<6> is a 1-8C divalent hydrocarbon; R<7> is H, a 1-8C monovalent hydrocarbon or an acyl; (b) is 0 or 1; (m) and (n) are each 0-100]; Z is R<1> , A, G or OR<8> (R<8> is H or a 1-20C monovalent hydrocarbon); (p)=0-1,000, (q) and (r) are each 0-100, (p)+(q)+(r)=2-1,000} with a urethane prepolymer having at least two or more isocyanate groups blocked with removable groups in a molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a fiber material with various properties such as durable flexibility, water and moisture absorption, stain resistance, smoothness, wrinkle resistance, compression recovery, and antistatic properties. And a fiber treatment agent which does not cause yellowing of the treated fiber material.

[0002]

2. Description of the Related Art Conventionally, various types of polyorganosiloxanes and fibers comprising compositions containing the same have been used to impart flexibility, water absorption / moisture absorption, smoothness, wrinkle resistance, compression recovery, and the like to fibers. Treatment agents have been proposed.

For example, in order to impart flexibility, polydimethylsiloxane or an emulsion thereof is used.
In order to provide durable flexibility, wrinkle resistance and compression recovery, a fiber treatment agent containing polymethyl hydrogen siloxane, polydimethyl siloxane whose both ends are capped with a hydroxyl group, and a condensation reaction catalyst; and polymethyl hydrogen siloxane And a fiber treatment agent containing an alkenyl group-containing polyorganosiloxane and an addition reaction catalyst.
Also, for example, a fiber treating agent comprising a polyorganosiloxane having at least two epoxy groups in one molecule and a polyorganosiloxane having at least two amino groups in one molecule; both ends of which are blocked with hydroxyl groups. Fiber treatment agent comprising polyorganosiloxane, organoalkoxysilane having amino group and alkoxyl group in one molecule and / or partially hydrolyzed condensate thereof; fiber treatment agent comprising aminoalkyl trialkoxysilane and epoxy group-containing polyorganosiloxane A polyorganosiloxane having two or more amino groups in one molecule and having both ends blocked with a triorganosiloxy group has been proposed.

[0004] However, all of these conventionally known fiber treatment agents have some disadvantages. For example, a fiber treatment agent containing polydimethylsiloxane as a main component has insufficient wrinkle resistance and compression recovery, and lacks durability in terms of flexibility and smoothness. In addition, when a treating agent containing an alkoxysilane as an essential component is used after being emulsified, the alkoxy group is easily hydrolyzed, the life of the treating bath is short, and the texture of the treated fiber becomes hard. Fiber treatment agents containing polymethyl hydrogen siloxane as an essential component do not sufficiently cure unless a catalyst is used, and have the problem that the use of a catalyst shortens the life of the treatment bath and generates hydrogen gas. .

[0005] Fiber treatment agents which use amino group-containing polyorganosiloxanes alone or in combination with epoxy group-containing polyorganosiloxanes impart good flexibility to the fibers, but generate a large amount of static electricity due to friction, and are inherently However, there is a problem that even if the fibers have moisture absorption and water absorption, they show hydrophobicity after the treatment, and when they are made into clothes, they have almost no moisture absorption and sweat absorption action. In addition, the amino group is oxidized by heat or ultraviolet rays to cause yellowing. In order to improve these problems, a treatment bath contains a funnel oil, a polyorganosiloxane / polyoxyalkylene copolymer,
Improvements have been made by adding hydrophilic surfactants such as polyoxyethylene adducts of higher alcohols, but such surfactants are easily soluble in water and organic solvents used for dry cleaning, Since it is easily dropped off by repeated washing, it has poor durability.

Further, a polysiloxane having an amino group and a polyoxyalkylene group obtained by reacting an amino group-containing polyorganosiloxane with a polyoxyalkylene glycidyl ether or a polyoxyalkylene-containing carboxylic acid is used as a fiber treatment agent. By
Although the durability of the fiber treatment is improved, if the polyoxyalkylene group is large, the moisture absorbing property of the fiber becomes good but the flexibility becomes insufficient, and if it is small, the flexibility is good but the moisture absorbing property becomes poor. Due to lack, both properties have not been satisfied.

For example, Japanese Patent Application Laid-Open No. 7-54275 discloses the use of a polyorganosiloxane having an N, N-bis (polyoxyalkylene) aminoalkyl group as a fabric softening agent. This fabric softener can be stored as a solubilized material, emulsified by adding water, does not yellow the fiber, and can impart excellent flexibility. It is not suitable for applications that require performance.

Japanese Patent Application Laid-Open No. 9-143885 discloses a fiber treatment composition containing an aminoalkyl group-containing polyorganosiloxane and an amide group-containing ether carboxylic acid. In the composition, the amino group present in the polyorganosiloxane reacts with the carboxylic acid to prevent yellowing, but has a hard texture and poor durability in treatment.

JP-A-52-103498 discloses a double-modified polyorganosiloxane having an aminoalkyl group and a polyoxyalkylene chain in the molecule. When such a polyorganosiloxane is used alone as a fiber treatment agent, the yellowing is less than that of a simple aminoalkyl group-containing polyorganosiloxane, but the durability is poor, and the aminoalkyl group is used to increase the durability. Increasing the content lowers the hygroscopicity and causes yellowing.

JP-A-7-54275 discloses a double-modified polyorganosiloxane similar to the above or a double-modified polyorganosiloxane having an epoxy group-containing group and a polyoxyalkylene chain, and a carboxyl group in the side chain. Alternatively, a fiber treating agent used in combination with a polyorganosiloxane having an ester bond is disclosed. Of these, the combination using the carboxylic acid group or the ester bond has insufficient reactivity with the amino group, so that yellowing cannot be completely prevented and the durability is not sufficient. In the combination using, the stability after mixing with and the carboxyl-containing polyorganosiloxane is poor, and uniform treatment cannot be performed.

JP-A-59-157381 discloses that after a polyorganosiloxane having an active hydrogen atom in a molecule is reacted with an organic polyisocyanate, a free isocyanate group is blocked with a heat-labile group. Thus, a fiber treatment agent containing a water-soluble and heat-reactive urethane compound as a main component is disclosed. Such a fiber treating agent easily forms a crosslinked structure on the surface of the fiber by heating, and can form a coating layer having excellent durability. However, as a polyorganosiloxane having an active hydrogen atom, an amino group-containing polyorganosiloxane and a polyoxyalkylene chain-containing polyorganosiloxane are not compatible with each other, so that they cannot be mixed and cross-linked by an isocyanato group. Even if one of them is crosslinked, the former is inferior in hygroscopicity, and the latter cannot provide sufficient flexibility.

[0012]

As described above, a fiber treating agent which imparts flexibility, water absorption and hygroscopicity to a fiber material, and shows the durability of these effects has not been obtained. The object of the present invention is to eliminate the drawbacks of conventionally known fiber treatment agents, to provide excellent flexibility, water absorption and hygroscopicity,
Provides various properties such as antifouling properties, smoothness, anti-wrinkle properties, compression recovery properties, antistatic properties, and rich in durability of those properties,
Specifically, it is an object of the present invention to provide a fiber treating agent which is excellent in washing resistance and does not cause yellowing of fibers.

[0013]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have shown in the molecule represented by the following general formula (I) an amino group and a (poly) oxyalkylene. The inventors have found that the object can be achieved by combining and combining a polyorganosiloxane having a chain and a urethane prepolymer having an isocyanato group blocked with a blocking agent, thereby completing the present invention.

That is, the present invention provides (A) a compound represented by the general formula (I):

Embedded image (Wherein, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms which may be the same or different; A represents a general formula: —R ² (NR ³ CH ₂ CH ₂ ) _a NR
⁴ R ⁵ (wherein, R ² represents a divalent hydrocarbon group having 1 to 8 carbon atoms, and R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent C 1-8 hydrocarbon group. Represents a hydrocarbon group or an acyl group, provided that at least one of R ³ , R ⁴ and R ⁵ is a hydrogen atom, and a is a number from 0 to 10.)
Represents a hydrocarbon group substituted with an amino group,
G has the general formula _{^{:-( R 6) b O (C}} 2 H 4 O) m (C 3 H 6
O) _n R ⁷ (wherein, R ⁶ represents a divalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁷ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms or an acyl group. , B is 0 or 1, m and n are each 0 to 100, provided that m + n is 1 to 200), and Z is the aforementioned R ¹ , A , G or OR ⁸ , wherein R ⁸ is a hydrogen atom or a group having 1 to 20 carbon atoms.
P is 0 to 1,000, q and r are each independently 0 to 100,
p + q + r is from 2 to 1,000), and a polyorganosiloxane containing at least 2 A and at least 1 G in the molecule; and (B) an isocyanato group blocked with a removable group. At least 2 in the molecule
Aqueous urethane prepolymer having an amount of 0.1 to 10 urethane prepolymers per 1 primary and / or secondary amino group in (A) About.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) used in the present invention is a polyorganosiloxane represented by the aforementioned general formula (I) and having an amino group and a (poly) oxyalkylene chain in the molecule. However, (I) indicates the number of intermediate siloxane units and does not necessarily mean a block copolymer, and the component (A) may be a random copolymer with respect to siloxane units.

R ¹ is a substituted or unsubstituted carbon atom having 1 to 2 carbon atoms.
0 is a monovalent hydrocarbon group. R ¹ is methyl,
Linear or branched alkyl groups such as ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, octadecyl;
Cycloalkyl groups such as cyclopentyl and cyclohexyl; aralkyl groups such as 2-phenylethyl and 2-phenylpropyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl and tolyl; and hydrogen atoms of these groups A part or the whole of which is substituted with an arbitrary organic group such as a halogen atom, for example, chloromethyl, 3,3,3-trifluoropropyl, 3-methoxypropyl, chlorophenyl and the like. It may be different. Here, as the substituted hydrocarbon group, a hydrocarbon group substituted by an amino group corresponding to A described later and a hydrocarbon group substituted by a polyoxyalkylene chain corresponding to b = 1 in G are excluded. Is done.
Among them, those having a carbon number of 1 to 6 are preferable because they are easy to synthesize and have excellent flexibility and other properties exhibited by polyorganosiloxane, and among them, an alkyl group in the range is preferable, and a partial alkenyl group is preferable. And / or aryl groups may be present, with methyl groups being most preferred.

A is a general formula: -R ² (NR ³ CH ₂ CH ₂ )
_a is a hydrocarbon group represented by NR ⁴ R ⁵ substituted with an amino group. R ² is a divalent hydrocarbon group having 1 to 8 carbon atoms, examples of which include methylene, trimethylene, tetramethylene, pentamethylene, and 1,4-phenylene, which are easy to synthesize and handle, and are chemically stable. Therefore, a trimethylene group is preferable. R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent hydrocarbon group or an acyl group having 1 to 8 carbon atoms, and in addition to a hydrogen atom; methyl, ethyl, propyl, butyl, hexyl , straight-chain or branched alkyl groups such as octyl, alkenyl groups such as vinyl; cycloalkyl groups such as cyclohexyl and acetyl, although an acyl group such as benzoyl is illustrated, R ^3, R ⁴ And at least one of R ⁵ is a hydrogen atom, in other words, said A has at least one primary and / or secondary amino group. R ³ , R ⁴ and R ⁵ other than a hydrogen atom (if
(If present) are preferably methyl and acetyl groups. a is a number from 0 to 10, and 0 and 1 are preferable because of easy synthesis. As such A, it is easy to synthesize and gives excellent flexibility to the fiber.
-Aminopropyl group and N- (2-aminoethyl)-
A 3-aminopropyl group is particularly preferred.

G is a general formula:-(R ⁶ ) _b O (C ₂ H ₄
O) _m (C ₃ H ₆ O) _n R ⁷ is a (poly) oxyalkylene chain, and b is a number of 0 or 1. The (poly) oxyalkylene chain is a hydrocarbon group which is directly bonded to a silicon atom via b oxygen when b = 0, and substituted with a (poly) oxyalkylene chain when b = 1. And b is preferably 1 from the viewpoint of stability to hydrolysis bonded to a silicon atom via a carbon atom.

R ⁶ is a divalent hydrocarbon group having 1 to 8 carbon atoms, examples of which are the same as those of R ^2, and a trimethylene group is preferable for the same reason. R ⁷ is a terminal group of the (poly) oxyalkylene chain, and is a hydrogen atom or a group having 1 to 1 carbon atoms.
8 is a monovalent hydrocarbon group or an acyl group, R ^3,
The same groups as R ⁴ and R ⁵ are exemplified, and methyl, ethyl, propyl, butyl and acetyl are preferred. m and n are each 0 to 100, and m + n is 1 to 2
00, preferably 5 to 100. If m + n is small, solubility in water or self-emulsification is poor, and antistatic properties
There is a tendency for moisture absorption / perspiration and antifouling properties to be poor.
If it exceeds 00, there is a risk of branching during manufacturing.

Z is a terminal group of the polyorganosiloxane, which may be the same or different, and even if R ¹ , A or G is a hydroxyl group or a hydrocarbyloxy group represented by OR ⁸ It may be. Here, R ⁸ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and in addition to a hydrogen atom; a straight-chain such as methyl, ethyl, propyl, butyl, hexyl and octyl. Linear or branched alkyl groups; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl; and substituted hydrocarbon groups such as 2-methoxyethyl, 2-ethoxyethyl, and 2-butoxyethyl.

In the polyorganosiloxane of the general formula (I), the number q of the intermediate siloxane units containing A is from 0 to 10
0, preferably 2 to 10. If q exceeds 100, the treated fibers will turn yellow. The number r of the intermediate siloxane units containing G is 0 to 100, and 1 to 10
Is preferred. If r exceeds 100, the flexibility becomes poor. p is 0 to 1,000, and p + q + r is 5 to
The number is 1,000, preferably 10-500.
When p is small, the effect of imparting flexibility and smoothness is insufficient, and when it exceeds 1,000, emulsification is difficult, and the effect of imparting water absorption and hygroscopicity is insufficient.

In the present invention, the primary and / or secondary amino groups present in component A of component (A) undergo a crosslinking reaction with the isocyanate groups regenerated from the blocked isocyanate groups of component (B). Thereby, the fiber material is provided with durable antistatic properties, moisture and sweat absorption properties, antifouling properties, flexibility, smoothness, anti-wrinkling properties and compression recovery properties. Therefore, it is necessary that at least two A's exist in one molecule of the component (A), and it is preferable that two to 10 A's exist. Therefore, when q is 0 or 1, A exists as part or all of Z of the terminal siloxane unit.

The (poly) oxyalkylene chain, which is G in the component (A), imparts water-absorbing, moisture-absorbing and sweat-absorbing properties to the fiber material.
Provides antifouling properties and antistatic properties. Therefore, it is necessary that at least one G exists in one molecule of the component (A) containing A, and it is preferable that one to ten Gs exist. Therefore, when r is 0, G exists as part or all of Z of the terminal siloxane unit.

The amount of G in the component (A) is determined based on the amount of G relative to the nitrogen atom in the A contained in the same component (A) in order to simultaneously impart good flexibility and water absorption to the fiber. 1.0-100,000 is preferable as a ratio of 10-10,
A range of 000 is more preferred.

Such a component (A) is obtained, for example, by subjecting a corresponding polyorganohydrosiloxane to hydrosilylation of allyl chloride and one-terminal allylated (poly) oxyalkylene in the presence of a platinum-based catalyst, and then converting a chlorine atom to It can be synthesized by a known production method such as amination.

The component (B) used in the present invention is a urethane prepolymer having at least two isocyanato groups blocked by a removable group in a molecule. In the urethane prepolymer, the group blocking the isocyanate group is eliminated by heating, and the regenerated free isocyanate group reacts with the amino group of the component (A) to form a coating layer having a crosslinked structure on the fiber surface. By doing so, it is a component that contributes to durable fiber treatment, and is preferably water-soluble or emulsifiable in water in order to constitute an aqueous fiber treatment agent together with the component (A).

Such a component (B) is preferably a polyether polyol and / or a polyester polyol, and if necessary, other polyols used in combination with an organic polyisocyanate. It is a block type urethane prepolymer in which a urethane prepolymer having at least two isocyanato groups is blocked by a group capable of being eliminated by heating.

Examples of the polyether polyol include those obtained by adding an alkylene oxide to a compound having two or more active hydrogens. Compounds containing two or more active hydrogens include polyhydric alcohols, ammonia and amines. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, neopentyl glycol, butanediol, hexanediol, octanediol, Diols such as decanediol; glycerin, 1,2,6-hexanetriol,
Triols such as trimethylolethane and trimethylolpropane; and polyols such as erythritol, pentaerythritol and sorbitol are exemplified. As amines,
Alkanolamines such as ethanolamine, triethanolamine, triisopropanolamine, tributanolamine; monoamines such as methylamine; and ethylenediamine, diethylenetriamine,
Triethylenetetramine, diaminodiphenylmethane,
Examples thereof include polyamines such as 4,4'-methylenebis (2-chloroaniline), phenylenediamine, xylylenediamine, and piperazine.

Examples of the alkylene oxide used for the addition polymerization include ethylene oxide, propylene oxide, butylene oxide and the like. One kind or two or more kinds may be used. It is preferable to use ethylene oxide and propylene oxide in combination.

As the polyester polyol, the same polyhydric alcohol as described above or the polyether polyol obtained as described above is condensed or polycondensed with a polybasic fatty acid or an acid anhydride or acid chloride thereof. Things. Examples of the polybasic fatty acid include adipic acid, sebacic acid, isophthalic acid, terephthalic acid and the like.

Further, another polyol compound such as polyvinyl alcohol may be used in combination.

By using such a polyol, a urethane prepolymer having strong hydrophilicity and suitable as the component (B) of the fiber treating agent for imparting water absorbency and flexibility to the fiber can be obtained. Furthermore, since the content of the blocked isocyanato group in one molecule can be increased, the component (A) can be sufficiently cross-linked by using a small amount of the component (B), and the component (A) Has good compatibility and reactivity.

As the organic polyisocyanate, 1,4
Phenylene diisocyanate, 2,4- or 2,6
An isocyanato group bonded to an aromatic carbon atom, such as tolylene diisocyanate, naphthalene diisocyanate, 2,2-bis (4-isocyanatophenyl) methane, diphenylether-4,4'-diisocyanate; Aromatic isocyanates having 1,6-hexamethylene diisocyanate, 1,8-octamethylene diisocyanate, 2,2,4-trimethyl-1,6
Aliphatics such as hexamethylene diisocyanate, 4- (isocyanatomethyl) octamethylene-1,8-diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, xylylene diisocyanate Aliphatic isocyanates having an isocyanato group attached to an isotropic carbon atom are exemplified,
Aliphatic isocyanates are preferred because they do not yellow the treated fibers.

The urethane prepolymer can be synthesized by reacting the above-mentioned active hydrogen of a polyol with an isocyanate group of an organic polyisocyanate.
The ratio of the organic isocyanate to be reacted with the polyols gives an appropriate amount of isocyanate groups to the prepolymer after the reaction and gives good reactivity and crosslink density, so that the amount of isocyanate groups is present in the polyols. The molar ratio to active hydrogen is preferably in the range of 1.1 to 2.0. If this ratio is less than 1.1, the amount of isocyanato groups that crosslink the component (A) is small, and if it exceeds 2.0, the crosslinking density increases and the flexibility of the fiber decreases.

The urethane prepolymer thus obtained has at least two isocyanato groups in the molecule. Due to the stable presence of the isocyanate groups in the presence of water, they are blocked by groups which can be removed by heating or the like. Such a removable group may be a substituted or unsubstituted aryloxy group, a secondary or tertiary alkoxy group, an organooximato group, a substituted or unsubstituted group, in view of suitability for fiber processing, safety and reactivity. Unsubstituted imidazolyl groups, active methylene groups and acidic sulfite groups are preferred, and one type may be used on its own or two or more types may be used in combination. In order to make the blocked urethane prepolymer water-soluble, a group such as a secondary or tertiary lower alkoxy group and an acidic sulfite group is particularly preferable, but it is used by emulsifying in the presence of a surfactant. In such a case, it is not necessary to make it particularly water-soluble.

Preferred blocking agents having the above groups include phenol, cresol, n-butylphenol, tert-butylphenol, phenylphenol,
Substituted or unsubstituted phenols such as chlorophenol; secondary alcohols such as isopropyl alcohol; tertiary alcohols such as tert-butyl alcohol; organooximes such as acetone oxime, methyl ethyl ketoxime and cyclohexanone oxime; Imidazoles such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-heptadecylimidazole and 2-phenylimidazole; active methylenes such as dimethyl malonate, diethyl malonate, acetylacetone, methyl acetoacetate and ethyl acetoacetate Compound; sodium acid sulfite and the like.

The blocking reaction is carried out in the presence or absence of a catalyst such as a tertiary amine such as triethylamine; a metal alcoholate such as sodium methylate; a metal salt such as dibutyltin diacetate or dibutyltin dilaurate. , Blocking agent, usually 30-100
The reaction can be carried out by reacting the urethane prepolymer at a temperature of 0.5 to 48 hours. In order to lower the viscosity of the reaction system and promote the reaction uniformly, it is preferable to carry out the reaction in an inert organic solvent. Examples of the organic solvent used include hydrocarbon solvents such as toluene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; And ether solvents such as dioxane. The amount of the blocking agent to be used is equimolar or excess with respect to the amount of the isocyanate group present in the urethane prepolymer, and is preferably in the range of 1 to 1.5 mol per 1 mol of the isocyanate group.

The component (B), which is a urethane prepolymer thus blocked, is stably present in water, preferably water-soluble, and is 100 to 100% in the absence of water.
By performing the heat treatment at 200 ° C., the blocking agent is eliminated and a free isocyanate group is regenerated.

The number of blocked isocyanato groups in component (B), that is, the number of isocyanate groups in the urethane prepolymer, is determined by the number of primary and / or secondary amino groups in component (A). And the component (B) functions as a cross-linking agent.
There are at least two in the molecule of component (B).

The amount of component (B) is such that the blocked isocyanato groups can be combined with the primary and / or
Alternatively, the amount is 0.1 to 10 with respect to one secondary amino group, and the amount is preferably 0.2 to 5 with respect to one secondary amino group. When the amount is less than 0.1, crosslinking is insufficient, and water-absorbing, moisture-absorbing and sweat-absorbing properties, antifouling properties, flexibility,
It becomes insufficient to impart smoothness, wrinkle resistance, compression recovery and antistatic properties. Conversely, with 10 or more, the reaction between the isocyanate groups not consumed in the crosslinking reaction and the active hydrogen on the fiber surface becomes insufficient. As a result, the crosslink density as a whole increases, and the treated fiber becomes hard, and impairs its water-absorbing, moisture-absorbing, sweat-absorbing properties, flexibility, smoothness, anti-wrinkling properties, compression recovery properties and the like.

Further, in order to improve the durability of the fiber treatment, the above-mentioned fiber treatment agent may be an organoalkoxysilane, especially an alkoxysilane having a carbon-functional amino or epoxy group in the molecule. You may mix | blend an adhesion auxiliary | assistant. Further, a reinforcing agent such as colloidal silica may be blended in order to provide a reinforcing property.

The fiber treating agent of the present invention is obtained by emulsifying and dispersing the component (A) and the component (B) in water together with other components to be added as required. However, (B)
When the component is water-soluble, the component (B) dissolves in water without being dispersed. For emulsification, it is preferable to use one or more of nonionic, cationic, anionic and / or amphoteric surfactants as an emulsifier.

Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene trimethyl nonyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether. Polyoxyethylene alkyl ether surfactants; polyoxyethylene alkyl aryl ether surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and polyoxyethylene dodecyl phenyl ether; Polyoxyethylene sorbitan fatty acid ester having 8 to 22 fatty acids, polyoxyethylene glycerin fatty acid ester, polyoxyethylene fatty acid ester Ether, 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 are exemplified.

Examples of the cationic surfactant include alkyl or unsaturated carbonic acids such as octyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, tallow trimethylammonium chloride, and coconut oil trimethylammonium chloride. Examples include hydrogentrimethylammonium chloride; alkylbenzylammonium chloride such as octyldimethylbenzylammonium chloride and decyldimethylbenzylammonium chloride; and dialkyldimethylammonium chloride such as didodecyldimethylammonium chloride and dioctadecyldimethylammonium chloride.

Examples of the anionic surfactant include alkyl sulfonic acid, alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl (diphenyl ether) sulfonic acid and sodium salts thereof, and polyoxyethylene alkyl sulfate salts. Examples of the amphoteric surfactant include alkyl dimethyl betaine.

The amount of the emulsifier is 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the polyorganosiloxane (A). When the amount is less than 0.1 part by weight, emulsification is difficult, and a desired aqueous emulsion may not be obtained. On the other hand, when the amount exceeds 50 parts by weight, the texture of the treated fiber becomes poor. In addition,
When it is necessary to increase the viscosity of the fiber treating agent of the present invention, a thickening agent such as polyvinyl alcohol and carboxymethyl cellulose sodium salt may be added.

The amount of water is not particularly limited as long as the fiber treating agent of the present invention can form an aqueous emulsion, and is not particularly limited.
It is 20 to 100,000 parts by weight, preferably 50 to 10,000 parts by weight based on parts by weight.

To prepare the above aqueous emulsion,
After mixing the above-mentioned components (A) and (B) and other components to be blended if necessary, an emulsifier and water are mixed, and the mixture is emulsified using an emulsifier such as a homogenizer or a colloid mill to obtain an aqueous emulsion. And (A)
An emulsifier and water may be mixed with each of the component and the component (B), and the resulting mixture may be emulsified by using an emulsifier such as a homogenizer or a colloid mill to obtain an aqueous emulsion.

The fibers treated with the fiber treating agent of the present invention, or the fabrics made of the fibers, are not particularly limited. The fiber treating agent may be a natural fiber such as cotton, hemp, silk, or wool; a regenerated fiber such as rayon, polynosic, or cupra; a semi-synthetic fiber such as acetate; or a synthetic fiber such as nylon, polyester, or acrylic fiber. And particularly suitable for treating cellulosic fibers such as cotton, hemp, rayon, and acetate. In addition, the amount of adhesion in treating a fiber or a woven fabric composed of fibers is different depending on the fiber and is not particularly limited, but generally, the amount of polyorganosiloxane in the fiber treatment agent relative to the treated fiber is 0%. 0.01 to 20% by weight.

The fibers can be treated with the fiber treating agent of the present invention by a method such as dip coating, spray coating, brush coating, knife coating, calender coating, and roll coating.

In order to cure the fiber treating agent attached to the fibers, water is removed by heating, and then 100 to 200.
It is preferable to heat at several degrees Celsius for several seconds to 20 minutes to regenerate the blocked isocyanato group and complete the crosslinking reaction.

[0052]

The fiber treating agent of the present invention imparts excellent flexibility, water absorption / moisture absorption, stain resistance, smoothness, wrinkle resistance, compression recovery and antistatic properties to fibers. These properties imparted to the fiber are excellent in durability, and specifically, excellent in washing resistance. Further, the fiber treating agent of the present invention has an advantage that the treated fiber is not yellowed.

Therefore, the fiber treating agent of the present invention can be used for various natural fibers, regenerated fibers, semi-synthetic fibers and synthetic fibers.
It can be widely used to impart the above-mentioned excellent properties with durability.

[0054]

The present invention will be described more specifically with reference to Preparation Examples, Examples and Comparative Examples. The present invention is not limited to these examples. The molecular structural formula of the polyorganosiloxane indicates the average number of intermediate siloxane units, and does not mean a block copolymer. These intermediate siloxane units are all randomly arranged. In addition, all parts in each example are parts by weight, and the viscosity is a value at 25 ° C.

Preparation Example 1 100 parts of a polyorganosiloxane represented by the molecular structural formula (II) and having an amino group and a polyoxyalkylene chain and having a viscosity of 2,500 cP and an amino equivalent of 4,500 g / mol, and polyoxyethylene ( 5) 25 parts of lauryl ether was mixed, 500 parts of distilled water was further added, and the mixture was stirred to obtain a preliminary mixture. This was emulsified using a homogenizer to prepare an aqueous emulsion E-1.

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Preparation Example 2 100 parts of an amino group-containing polyorganosiloxane represented by molecular structural formula (III) having a viscosity of 1,000 cP and an amino equivalent of 2,000 g / mol, and 25 parts of polyoxyethylene (5) lauryl ether were used. The mixture was further mixed, and 500 parts of distilled water was added thereto and stirred to obtain a premix. This was emulsified using a homogenizer to obtain an aqueous emulsion E.
-2 was prepared.

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Preparation Example 3 Polyoxyalkylene group-containing polyorganosiloxane 100 having a viscosity of 1,000 cP and having the molecular structural formula (IV)
Part and polyoxyethylene (5) lauryl ether 25
Were mixed, and 500 parts of distilled water was further added and stirred to obtain a preliminary mixture. This was emulsified using a homogenizer to prepare an aqueous emulsion E-3.

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Examples 1 and 2 An aqueous solution of a urethane prepolymer containing an isocyanato group blocked with a methylethylketoximato group was added to 100 parts of the aqueous emulsion E-1 (20% of an active ingredient containing an emulsifier) prepared in Preparation Example 1. 10 parts (Example 1) or 50 parts of Elastron BN-08 emulsion (40% active ingredient, content of free isocyanate group when regenerated about 2.9% by weight, trade name of Daiichi Kogyo Seiyaku Co., Ltd.) (Example 2) was blended. The molar ratio of isocyanato groups / amino groups was about 2.0 (Example 1) and 10.0 (Example 2), respectively. 1.0% active ingredient
, To prepare treatment baths of Examples 1 and 2. After immersing cotton broad, polyester / cotton blended broad or polyester broad woven fabrics in the obtained treatment bath, rolls are drawn so that the drawing ratio is 100% for cotton and polyester / cotton blend and 60% for polyester. Squeezing using
Then, a heat-curing treatment was performed at 150 ° C. for 3 minutes to produce respective evaluation samples.

Examples 3 and 4 Instead of elastron BN-08, Elastron MF-25, an aqueous emulsion of an aqueous urethane prepolymer containing isocyanato groups blocked with methyl ethyl ketoximato groups (25% active ingredient, Example 1 except that 2.5 parts (Example 3) or 25 parts (Example 4) of a free isocyanate group content of about 1.2% by weight and a Daiichi Kogyo Seiyaku Co., Ltd. Processing baths of Examples 3 and 4 were prepared in the same manner as in Examples 1 and 2. The molar ratios of isocyanato groups / amino groups were 0.2 (Example 3) and 2.0 (Example 4), respectively. Using these treatment baths, evaluation samples were prepared in the same manner as in Examples 1 and 2.

Comparative Examples 1 to 3 Example 3 except that the amount of Elastron MF-25 was changed to 0 (no addition, Comparative Example 1), 1.0 part (Comparative Example 2) or 250 parts (Comparative Example 3). Comparative Example 1
~ 3 treatment baths were prepared respectively. The molar ratios of isocyanato group / amino group were 0 (Comparative Example 1) and 0.08, respectively.
(Comparative Example 2) and 20 (Comparative Example 3). Using these treatment baths, evaluation samples were prepared in the same manner as in Examples 1 and 2.

Comparative Example 4 Emulsion E-2 (active ingredient 20) prepared in Preparation Example 2 was used as an aqueous emulsion of polyorganosiloxane.
%), And the treatment bath of Comparative Example 4 was prepared in the same manner as in Examples 3 and 4, except that the blending amount of Elastron MF-25 was 55 parts. The molar ratio of isocyanato groups / amino groups was 2.0. An evaluation sample was prepared in the same manner as in Examples 1 and 2 using this treatment bath.

Comparative Example 5 As an aqueous emulsion of a polyorganosiloxane, emulsion E-3 (active ingredient 20) prepared in Preparation Example 3 was used.
%), And a treatment bath of Comparative Example 5 was prepared in the same manner as in Examples 3 and 4, except that the blending amount of Elastron MF-25 was 25 parts. An evaluation sample was prepared in the same manner as in Examples 1 and 2 using this treatment bath.

Evaluation The evaluation samples prepared in Examples 1 to 4 and Comparative Examples 1 to 5 and the untreated broad fabric were evaluated as follows. (1) Flexibility Using a Kawabata pure bending tester KES-FB2 (trade name of Kato Tech Co., Ltd.), measure the B value (flexural rigidity) and 2HB value (recoverability) of the treated cloth, and determine the average value. Was. The smaller the value, the softer it is. (2) Water absorption Measured according to the dropping method of JIS L1096. The smaller the value, the better the water absorption of the treated cloth. (3) Yellowing For the initial sample and the sample subjected to the heat acceleration test at 180 ° C. for 1 minute, Δb of the treated cloth was measured using a colorimeter.
The value was measured. The smaller the value, the more difficult it is to yellow. (4) Durability (Washing resistance) Based on the household washing machine method specified in 103 of JIS L0217, Ultra Ariel (trade name of P & G) 1 g / L as a detergent, bath ratio 1:30, 40 After the washing was repeated 10 times with warm water at ° C., the same evaluation as in the initial stage was performed on the flexibility and water absorption of the sample.

Table 1 shows the mixing ratios of the main components and the molar ratios of isocyanato groups / amino groups in the fiber treating agents of Examples 1 to 4 and Comparative Examples 1 to 5, and the evaluation samples prepared in the above Examples and Comparative Examples and Table 2 shows the evaluation results of the untreated samples.

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[Table 1]

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[Table 2]

As is clear from Table 2, all of the samples obtained in Examples 1 to 4 exhibited better flexibility than the untreated sample, and the flexibility after the durability test showed an initial value in the case of cotton broad. The values hardly changed, and even in the case of polyester / cotton blend (hereinafter, simply referred to as “blend”) broad and polyester broad, the hardening was less. Further, it was excellent in water absorption, and there was no change in cotton broad and blended broad even after the durability test. In the case of polyester broad, a decrease in water absorption after the durability test is observed,
Not as significant as the comparative example. No remarkable yellowing was observed.

On the other hand, unlike Comparative Examples 1 and 2, no blocked urethane prepolymer was blended.
Alternatively, when the amount was small, the flexibility after the durability test was poor, and the yellowing after the heat acceleration test was remarkable. When the blending amount of the urethane prepolymer is excessive as in Comparative Example 3, and when a polyorganosiloxane having no polyoxyalkylene chain is used as in Comparative Example 4, water absorption is poor, The durability test further reduced it. In Comparative Example 3, the flexibility was slightly inferior.

When a polyorganosiloxane having no amino group was used as in Comparative Example 5, the flexibility was poor, and the water absorption of the polyester broad after the durability test was significantly deteriorated.

Claims (2)

[Claims] (A) A general formula: (Wherein, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms which may be the same or different; A represents a general formula: —R ² (NR ³ CH ₂ CH) ₂ ) _a NR ⁴
R ⁵ (wherein, R ² represents a divalent hydrocarbon group having 1 to 8 carbon atoms, and R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 8 carbon atoms. Represents a hydrogen group or an acyl group, provided that at least one of R ³ , R ⁴ and R ⁵
Number is a hydrogen atom, a is represented by a number of 0), represents a hydrocarbon group substituted with an amino group; G is the formula _{^{:-( R 6) b O (C}} 2 H 4 O) _m (C ₃ H ₆ O) _n R
⁷ (wherein, R ⁶ represents a divalent hydrocarbon group having 1 to 8 carbon atoms, R ⁷ represents a hydrogen atom or a monovalent hydrocarbon group or an acyl group having 1 to 8 carbon atoms, and b represents 0 Or 1;
m and n are each 0 to 100, provided that m +
n is a number from 1 to 200), and Z is R ¹ , A, G or OR ^{8 as} defined above.
R ⁸ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms;
000, and q and r are each independently 0 to 10
0, p + q + r is 2 to 1,000), and a polyorganosiloxane containing at least 2 A and at least 1 G in the molecule; and (B) blocked with a removable group. Urethane prepolymer having at least two isocyanate groups in the molecule, wherein the number of the isocyanate groups is 0.1 to 10 with respect to one primary and / or secondary amino group in (A) Aqueous emulsion type fiber treating agent containing an amount. 2. The method according to claim 1, wherein the leaving group is a substituted or unsubstituted phenoxy group, a secondary or tertiary alkoxy group,
The fiber treating agent according to claim 1, which is at least one group selected from an organooximato group, a substituted or unsubstituted imidazolyl group, an active methylene group, and an acidic sulfite group.