JPH10110160A - Water repellent and oil repellent agent composition for fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject composition having an improved water repellent and oil repellent property and its durability without damaging feeling of fibers by treating fibers with a specific silane compound having an isocyanate group. SOLUTION: This water repellent and oil repellent agent composition contains (A) a silane compound having at least one water repellent organic group and at least one silicon atom directly bonding to an isocyanate group and (B) a solvent dissolving the component A as essential components. Preferably, the component A is a compound expressed by the formula R1 and R<2> are each an isocyanate group or an alkoxyl; R' and R" are each H or a 1-30C monofunctional organic group; Y is a bifunctional organic group; (a) and (b) are each 0 or 1-3, 0<=(a+b)⊖5} and e.g. trichlorotrifluoroethane can be used as the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water / oil repellent composition for fibers, a method for treating the composition, and a fiber or fibrous body treated with the composition.

[0002]

2. Description of the Related Art In recent years, water- and oil-repellent processing of clothing has been actively performed, and various compositions according to the purpose have been provided. For example, (1) a water- and oil-repellent composition containing a copolymer of a fluoroaliphatic group-containing monomer and an acrylate monomer, and a fluoroaliphatic group-containing ester (Japanese Patent Laid-Open No. 5-26)
2948), (2) a perfluoroalkyl group, and
Water / oil repellent composition containing a silane compound having an alkoxyl group directly bonded to a silicon atom (JP-A-1-9518)
1) has been proposed.

[0003]

However, the cloth treated with the water- and oil-repellent agent containing the copolymer (1) has a drawback of giving a hard texture. In addition, the water / oil repellent composition (2) comprises:
The water and oil repellency was insufficient, and the durability was not satisfactory. That is, an object of the present invention is to have improved water and oil repellency and its durability,
Another object of the present invention is to provide a water / oil repellent composition for fibers that does not impair the texture of the fibers.

[0004]

Means for Solving the Problems The inventors of the present invention treated fibers with a specific silane compound having an isocyanate group to give excellent water and oil repellency and excellent durability against heavy rain, In addition, it was found that the fiber texture was excellent.

That is, the present invention provides a water / oil repellent composition for fibers, comprising the following (I) and (II) as essential components. (I) A silane compound having at least one hydrophobic organic group and at least one silicon atom directly bonded to an isocyanate group. (II) A solvent that dissolves (I).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION "Monovalent organic group" in the present specification
Means a group containing a carbon atom, a monovalent hydrocarbon group, a chloroalkyl group, a halogenated hydrocarbon group such as a polyfluoroalkyl group, a hydroxyl group, an epoxy group, an amino group,
1 to which functional groups such as mercapto group and carboxyl group are bonded
Monovalent hydrocarbon group and monovalent halogenated hydrocarbon group, ester bond, ether bond, thioether bond, imino bond, amide bond, urethane bond, etc. and monovalent hydrocarbon group or monovalent halogenated hydrocarbon group And a group bonded to The “divalent organic group” means a group in which a monovalent atom or one of the monovalent atomic groups in the monovalent organic group is replaced by a bond.

[0007] The "hydrocarbon group" is an aliphatic hydrocarbon group or an aromatic hydrocarbon group, preferably an aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. May be an aromatic hydrocarbon group, and particularly preferably a saturated aliphatic hydrocarbon group. The structure of the aliphatic hydrocarbon group may be any of a straight-chain structure, a branched structure, and a cyclic structure, but is preferably a straight-chain structure or a branched structure.

The monovalent aliphatic hydrocarbon group includes an alkyl group, an alkenyl group, a cycloalkyl group, and the divalent aliphatic hydrocarbon group includes an alkylene group, an alkenylene group, and a cycloalkenylene group. Examples of the monovalent aromatic hydrocarbon group include an aryl group.

Among the essential components of the water / oil repellent composition for fibers of the present invention, (I) (hereinafter referred to as compound I) has one or more hydrophobic organic groups and an isocyanate group directly bonded. It is a silane compound having one or more silicon atoms.

As the hydrophobic organic group, a group containing a long-chain hydrocarbon group or a polyfluoro organic group is preferable, and a polyfluoro organic group is particularly preferable.

The polyfluoro organic group means an organic group containing two or more fluorine atoms. The carbon number of the polyfluoro organic group as the hydrophobic organic group is preferably from 3 to 21. The polyfluoro organic group preferably has a linear structure or a branched structure, and particularly preferably has a linear structure. In the case of a branched structure, it is preferable that the branched portion is a short chain having about 1 to 3 carbon atoms.

The number of fluorine atoms in the polyfluoro organic group is represented by (the number of fluorine atoms in the polyfluoro organic group) / (the maximum number of hydrogen atoms that can be contained in the organic group having the same carbon number corresponding to the polyfluoro organic group). ) × 100 (%), preferably at least 60%, particularly preferably at least 80%.

The polyfluoro organic group is preferably a polyfluoro hydrocarbon group in which two or more hydrogen atoms of a hydrocarbon group have been substituted with fluorine atoms, or a group having a polyfluoro hydrocarbon group as a partial structure. As the polyfluorohydrocarbon group, a polyfluoroalkyl group or a polyfluoroalkylene group is preferable. And the polyfluorohydrocarbon group is a polyfluorohydrocarbon group containing an oxygen atom, or
It may be a polyfluorohydrocarbon group containing a sulfur atom. As the group containing an oxygen atom, a group in which an etheric oxygen atom is inserted between carbon-carbon bonds of a polyfluorohydrocarbon group is preferable, and in particular, a polyfluoroalkyloxy group, a polyfluoroalkyleneoxy group, or Groups having a structure are preferred. Further, as the group containing a sulfur atom, a group in which a thioetheric sulfur atom is inserted between carbon-carbon bonds of a polyfluorohydrocarbon group is preferable, and in particular, a polyfluoroalkylthio group, a polyfluoroalkylenethio group, or a A group having a partial structure is preferred.

The group having a polyfluorohydrocarbon group as a partial structure includes a polyfluorohydrocarbon group to which a chlorine atom is bonded, a hydroxyl group, an epoxy group, an amino group, a mercapto group, and a carboxyl group. Examples include a polyfluorohydrocarbon group, and a group in which a polyfluorohydrocarbon group and a divalent linking group are bonded. Examples of the divalent linking group include an ester bond, an ether bond, a thioether bond, an imino bond,
Examples include a bonding group such as an amide bond and a urethane bond, a group in which these bonding groups are bonded to an alkylene group, and an alkylene group. As the alkylene group in the divalent linking group, a dimethylene group or a trimethylene group is preferable.

Further, in any of the polyfluorohydrocarbon group and the group having the polyfluorohydrocarbon group as a partial structure, the polyfluorohydrocarbon group has all of the hydrogen atoms in the hydrocarbon group replaced with fluorine atoms. A preferred group is a perfluorohydrocarbon group. That is, as the polyfluoro organic group, a perfluoro hydrocarbon group,
Alternatively, a group having a perfluorohydrocarbon group as a partial structure is preferable.

As the perfluorohydrocarbon group, a perfluoroalkyl group, a perfluoroalkylene group, a perfluoroalkyloxy group, a perfluoroalkyleneoxy group, a perfluoroalkylthio group, a perfluoroalkylenethio group, or a compound having a partial structure And a group having a perfluoroalkyl group, a perfluoroalkylene group, a perfluoroalkyl portion, a perfluoroalkylene portion, and a perfluoroalkyleneoxy portion. Particularly, a perfluoroalkyl portion having 3 to 21 carbon atoms is preferable. Or a group having 2 to 2 carbon atoms
Groups having 16 perfluoroalkylene moieties are preferred.

The group having a perfluorohydrocarbon group as a partial structure includes the above-mentioned perfluorohydrocarbon group and 2
A group to which a valent linking group is bonded is preferred.

Specific examples of the polyfluoroalkyl group and the perfluoroalkyl group include the following groups. In addition, specific examples of the polyfluoroalkylene group and the perfluoroalkylene group include the groups shown in the specific examples of the compound.

C ₂ F ₅ —, C ₃ F ₇ — [CF ₃ (CF
_{2) 2} -, and (CF ₃₎ includes both ₂ CF-. _{], C 4 F 9 - [} CF 3 (CF 2) 3 -, (CF
₃ ) ₂ CFCF _2- , (CF ₃ ) ₃ C-, CF ₃ CF ₂
CF (CF ₃₎ - _{including], C 5 F 11 - [} CF 3 (CF
_{2) 4 -, (CF 3} ) 2 CF (CF 2) 2 -, (CF
_{3) 3 CCF 2 -, CF} 3 CF 2 CF (CF 3) CF 2
- including structural isomers groups _{such], C 6 F 13 - [} CF 3
(Including groups having structural isomerism such as (CF ₂ ) ₂ C (CF ₃ ) _2- ], C ₈ F ₁₇ −, C ₁₀ F ₂₁ −, C ₁₂ F ₂₅ − and C ₁₅ F _31.
−, HC _t F _2t − (where t is an integer of 1 to 18), (CF ₃ ) ₂ CFC _v F _2v − (where v is 1
It is an integer of １５15. )Such.

CF ₃ (CF ₂ ) ₄ OCF (CF ₃ ) —,
F [CF (CF ₃ ) CF ₂ O] _s CF (CF ₃ ) CF ₂
CF _2- , F [CF (CF ₃ ) CF ₂ O] _t CF (CF
_{3) -, F [CF (} CF 3) CF 2 O] u CF 2 CF 2
−, F (CF ₂ CF ₂ CF ₂ O) _v CF ₂ CF ₂ −, F
(CF ₂ CF ₂ O) _w CF ₂ CF _2- (however, s, t
Is an integer of 1 to 10, u is an integer of 2 to 6, v is an integer of 1 to 11, and w is an integer of 1 to 11. )Such.

Further, the polyfluoro organic group is preferably a group having a perfluorohydrocarbon group as a partial structure, and in the case of a monovalent group, a group in which an alkylene group is bonded to a terminal of a perfluoroalkyl group is preferable. . When the polyfluoro organic group is a divalent group, a group in which an alkylene group is bonded to both terminals of a perfluoroalkylene group is preferable. In any case, the alkylene group is preferably a dimethylene group or a trimethylene group.

On the other hand, in a group containing a long-chain hydrocarbon group as a hydrophobic organic group, the long-chain hydrocarbon group means a hydrocarbon group having 7 or more carbon atoms, and having 7 to 7 carbon atoms. 3
About 0 is preferable. The long-chain hydrocarbon group preferably has a linear or branched structure, and more preferably has a linear structure. In the case of a branched structure, it is preferable that the branched portion is a short chain having about 1 to 3 carbon atoms.

The long-chain hydrocarbon group is preferably an alkyl group, an alkylene group, an alkenyl group or an alkenylene group, and more preferably an alkyl group or an alkylene group. The long-chain alkyl group preferably has 7 to 30 carbon atoms, and the long-chain alkylene group preferably has 7 to 16 carbon atoms. And as the group containing a long-chain hydrocarbon group, a group consisting of only a long-chain hydrocarbon group,
Alternatively, a group in which a divalent linking group is linked to a terminal of a long-chain hydrocarbon group is preferable, and a group in which a divalent linking group is linked to a terminal of a long-chain hydrocarbon group is particularly preferable. The divalent linking group is preferably a linking group such as an ester bond, an ether bond, a thioether bond, an imino bond, an amide bond, a urethane bond, or a group in which these linking groups are linked to an alkylene group.

Compound I is a compound having one or more of the above-mentioned hydrophobic organic groups. The number of hydrophobic organic groups is preferably one. Preferably, the hydrophobic organic group is directly bonded to the silicon atom. Compound I has an isocyanate group (Si-NCO) directly bonded to a silicon atom.
Is a compound having at least one It is considered that the isocyanate group achieves high adhesion between the compound I and the fiber. The number of isocyanate groups is preferably two or more.

Further, compound I is a compound represented by the following formula (A) (hereinafter, referred to as compound A), a compound represented by the following formula (B) (hereinafter, referred to as compound B), or A compound represented by the following formula (C) (hereinafter, referred to as compound C) is preferable.

[0026]

Embedded image (A): (Z ¹ ) _3-a (R ¹ ) _a Si-Y-Si (R ² ) _b (Z ² ) _3-b

However, in the formula (A), Z ¹ , Z ² ,
R ¹ , R ² , Y, a, and b have the following meanings. Z ¹ , Z ² : independently is an isocyanate group or an alkoxyl group, and at least one of Z ¹ and Z ² is an isocyanate group. R ¹ and R ² independently represent a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. Y: divalent organic group. However, at least ^one of R ¹ , R ² and Y is a hydrophobic organic group. a, b: independently 0, 1, 2, or 3, and 0
≦ a + b ≦ 5.

[0028]

Embedded image (B): (R ³ ) _c Si (Z ³ ) _4-c

However, in the formula (B), R ³ , Z ³ ,
And c have the following meanings. R ³ : a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and at least one is a hydrophobic organic group. Z ^{3 is an} isocyanate group or an alkoxyl group,
And one or more isocyanate groups. c: 1, 2, or 3.

[0030]

(C): (R ⁴ ) _d (Z ⁴ ) _3-d SiO [(R ⁵ ) _e (Z ⁵ ) _2-e SiO] _n S
i (R ⁶ ) _f (Z ⁶ ) _3-f

However, in the formula (C), R ^{4 to} R ⁶ ,
Z ^{4 to} Z ⁶ , d, e, f, and n have the following meanings. R ^{4 to} R ^{6 are} independently a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and at least one is a hydrophobic organic group. Z ^{4 to} Z ⁶ : independently an isocyanate group or an alkoxyl group, and at least one of Z ^{4 to} Z ⁶ is an isocyanate group. d, f: independently 0, 1, 2, or 3. e: 0, 1, or 2. However, 1 ≦ d + e + f ≦ 7. n: an integer of 0 or more.

In the compounds A to C, R ^{1 to} R ⁶ are each independently a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. When two or more are present in the molecule, they may be the same or different. For example,
When a in compound A is 2, two R ^{1 s} may be the same or different. When any of R ^{1 to} R ⁶ is a hydrophobic organic group, a group containing a long-chain hydrocarbon group or a polyfluoro organic group is preferable, and a polyfluoro organic group is particularly preferable.

R ^{1 to} R ⁶ which are hydrophobic organic groups are preferably a polyfluorohydrocarbon group or a group having a polyfluorohydrocarbon group as a partial structure.
A polyfluoroalkyloxy group, a polyfluoroalkylthio group, or a group in which these groups are bonded to a divalent linking group are preferable. Further, R ^{1 to} R ⁶ are preferably a perfluoroalkyl group, a perfluoroalkyloxy group, a perfluoroalkylthio group, or a group in which these groups are bonded to a divalent linking group. The number of carbon atoms of the perfluoroalkyl group is preferably from 3 to 16.

[0034] In particular, R ¹ to R ⁶ is perfluoroalkyl group and a divalent linking group bonded structure are preferred, groups perfluoroalkyl group and a divalent linking group bonded linear are preferred, CF ₃ A group represented by (CF ₂ ) _v -Q- (v is an integer of 3 to 15, and Q is a divalent linking group) is preferable. Q is preferably a divalent hydrocarbon group such as an alkylene group, a divalent hydrocarbon group containing an ester bond, and the like, and particularly preferably a polymethylene group having 1 to 3 carbon atoms, for example, a group such as methylene, dimethylene, and triethylene. . On the other hand, R ^{1 to} R
^{When 6} is a group containing a long-chain hydrocarbon group, a group in which a long-chain alkyl group and a divalent linking group are bonded is preferable.

When R ^{1 to} R ⁶ are groups other than a hydrophobic organic group, a lower alkyl group, a halogen atom, a phenyl group and the like are preferable, a lower alkyl group is particularly preferable, and a methyl group or Ethyl groups are preferred.

In addition, Z ^{1 to} Z ⁶ in the compounds A to C
Represents an isocyanate group (-NCO group) or an alkoxyl group. When two or more groups are present in the molecule, they may be the same or different. For example, when two Z ¹ are present in a molecule, they may be the same or different. Further, Z ¹ to Z ⁶ 1 or more in the molecule, an isocyanate group, Z ¹ to Z
⁶ is preferably all isocyanate groups.
Since Z ^{1 to} Z ⁶ are important structures for increasing the adhesion between the compound and the fiber, it is preferable that the number in the compound is large, and two or more silicon atoms are bonded to one silicon atom. Is preferred. When it is an alkoxyl group, a methoxyl group is preferred. Compounds A to C may be used alone or in combination of two or more.

Next, the compound A will be described in detail. In the compound A, when one or both of R ^{1 and} R ² are a hydrophobic organic group, Y is a hydrophobic divalent organic group or a group other than the hydrophobic divalent organic group. There may be. On the other hand, when both R ¹ and R ² are groups other than the hydrophobic organic group, Y is a hydrophobic divalent organic group. Further, all of R ¹ , R ² and Y may be a hydrophobic organic group. In the compound A, it is preferable that Y is a hydrophobic divalent organic group, particularly when Y is a hydrophobic organic group and R ¹ and R ² are groups other than the hydrophobic organic group. Is particularly preferred. When Y is a hydrophobic organic group, a divalent polyfluoro organic group or a divalent long-chain hydrocarbon group is preferred, and a divalent polyfluoro organic group is particularly preferred.

When Y is a divalent polyfluoro organic group, the number of carbon atoms is preferably from 6 to 30, particularly preferably from 6 to 16. As the divalent polyfluoro organic group, a divalent polyfluoro hydrocarbon group is preferable, and in particular, a polyfluoroalkylene group, a polyfluoroalkyleneoxy group, a polyfluoroalkylenethio group, or a partial structure of any of these groups is used. A group is preferable, and a group having a perfluoroalkylene group or a perfluoroalkyleneoxy group as a partial structure is particularly preferable. The perfluoroalkylene group or the group having a perfluoroalkyleneoxy group as a partial structure is preferably a group in which an alkylene group is bonded to a portion of a perfluoroalkylene group or a perfluoroalkyleneoxy group that is bonded to both terminal silicon atoms. The alkylene group is particularly preferably an ethylene group.

On the other hand, when Y is a group other than a divalent polyfluoro organic group, an alkylene group, an alkyleneoxy group, and an alkylenethio group, or a group in which these groups are linked to a divalent linking group are preferable. . These carbon numbers are 2 to
30, particularly preferably 2 to 12.

When R ¹ or R ² is a group other than a hydrophobic organic group, a methyl group is particularly preferred. On the other hand, when R ¹ or R ² is a hydrophobic organic group, a polyfluoro organic group is preferred.

In addition, Z ¹ and Z ² may contain both isocyanate groups and alkoxyl groups, but it is preferable that all of them are isocyanate groups. It is preferable that two or more isocyanate groups are present in compound A, and it is particularly preferable that at least one silicon atom has two or more isocyanate groups bonded thereto, and in particular, both silicon atoms have two or more isocyanate groups. It is preferable that the isocyanate group is bonded. That is, a and b are each preferably 0 or 1.

Specific examples of the compound A include the following compounds. In the following specific examples of compound A, n and m each represent an integer of 1 or more. R
Represents an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms, and particularly preferably a methyl group. R _f is shown a polyfluoroalkyl _{group, C r F 2r + 1 (} CH 2) s - ( where, r is 3 to 12 integer, s is an integer of 2-4.)
A polyfluoroalkyl group having a perfluoroalkyl group portion represented by is preferable, and the perfluoroalkyl group portion is preferably linear. Also, s is 2 or 3
Is particularly preferable, and 2 is particularly preferable. R _F is shown a perfluoroalkyl _{group, C t F 2t + 1 -} ( however, t is 3-16
Indicates an integer. ) Is preferable, and the perfluoroalkyl group portion is particularly preferably linear.

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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Next, the compound B will be described. At least one R ^{3 of the} compound B is a hydrophobic organic group. As the hydrophobic organic group, a polyfluoro organic group is preferable,
Particularly, a group in which a polyfluoroalkyl group and a divalent linking group are linked is preferable. Compound B preferably has one hydrophobic organic group. Further, R ³ may include a group other than the hydrophobic organic group, and the group other than the hydrophobic organic group is preferably a methyl group.

When the number of Z ^{3 in the} compound B is two or more, an isocyanate group and an alkoxyl group may be mixed.
It is preferable that the number of isocyanate groups bonded to one silicon atom is two or more. c is preferably 1 or 2.

Specific examples of compound B include the following compounds. N, m, R, R _f in the specific examples of the compound B,
And R _F have the same meanings as in the specific examples of compound A.

[0055]

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[0056]

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Next, the compound C will be described. R ⁴ to R ⁶ of the compound C, or one is a hydrophobic organic group, but all may be hydrophobic organic groups, R ⁴ to R
^It is preferred that one or two of ⁶ is a hydrophobic organic group. As the hydrophobic organic group, a polyfluoro organic group is preferable, and a group in which a polyfluoroalkyl group and a divalent linking group are bonded is particularly preferable. On the other hand, when R ^{4 to} R ⁶ include a group other than the monovalent polyfluoro organic group, the group other than the polyfluoro organic group is preferably a methyl group.

The compound C can increase the density and crosslinkability to fibers by increasing n, that is, the number of repeating structural units. However, if n is too large, workability during processing will be poor, and practicality will be reduced. Therefore, n can be appropriately changed depending on the purpose, and usually 0 to 5 is preferable, and 1 to 3 is preferable.
Is particularly preferred.

In addition, although Z ^{4 to} Z ⁶ may contain both isocyanate groups and alkoxyl groups, it is preferable that all of them are isocyanate groups. Since increasing the number of silicon atoms directly bonded to the isocyanate groups present in the compound C also increases the adhesion to the fiber, the number of isocyanate groups is preferably two or more, especially The number of isocyanate groups attached to the atom is 2
More than one is desirable. The isocyanate group is preferably present at the terminal of the molecule. When n is large, it is preferable that the isocyanate group is further present near the center of the molecule. D and f of the compound C are preferably from 0 to 2, particularly preferably 0 or 1, and particularly preferably 0. e is preferably 0 or 1, and d + e + f is preferably 1 to 4, particularly preferably 1 to 3.

Specific examples of the compound C of the present invention include the following compounds. In addition, n in specific examples of the compound C,
m, R, R _f , R _F and Z have the same meanings as in the specific examples of compound A.

[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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Since the isocyanate group is a reactive group, if there is a group reactive with the isocyanate group on the fiber surface, the isocyanate group in the silane compound and the reactive group on the fiber surface chemically react. Thus, the silane compound is considered to chemically bond to the fiber surface. For example, if there are hydroxyl groups or amino groups on the fiber surface,
It is considered that these groups react with isocyanate groups to chemically bond to the fiber surface. And, due to the interaction between the silicon atom directly bonded to the isocyanate group and the hydrophobic organic group, the fiber surface has excellent water and oil repellency, texture,
It is considered that these materials can impart durability.

When there is no reactive group with the isocyanate group on the fiber surface or when the reactive group is small, it is considered that the isocyanate group reacts between the silane compound molecules to form a network structure. . Further, it is considered that the isocyanate group in the silane compound also has adhesion to the fiber. And it is considered that excellent water / oil repellency, texture, and durability thereof can be imparted to the fiber surface by the network structure and the adhesion to the fiber.

The water / oil repellent treating agent composition for fibers of the present invention comprises:
Along with compound I, a solvent that dissolves compound (II) (hereinafter simply referred to as “solvent”) is an essential component.

The solvent is a solvent for dissolving Compound I. The solvent can be selected from known or well-known solvents. However, a solvent having a hydrogen atom reactive with an isocyanate group is not desirable. Examples of the solvent include halogenated hydrocarbon solvents, hydrocarbon solvents (preferably aliphatic hydrocarbon solvents), ketone solvents, ester solvents, ether solvents, alcohol solvents, alcohol ester solvents, and ketone ester solvents. Organic solvents such as solvents, ketone alcohol solvents, ether alcohol solvents, ketone ether solvents, ester ether solvents, and glycol solvents are exemplified.

Among these, examples of the solvent include, for example,
Halogenated hydrocarbon solvents such as trichlorotrifluoroethane (R-113 and the like), dichloropentafluoropropane (R-225 and the like), trichlorotrifluoroethane and perfluoroalkanes, and acetates such as methyl acetate and ethyl acetate Solvents, hydrocarbon solvents such as hexane and mineral spirit, and perfluorotributylamine are preferred. One or more of these solvents can be used as needed.

The concentration of Compound I in the composition is 100
The content is preferably 0.1 to 30% by weight based on part by weight. The concentration is the same whether or not other components are contained. Further, the concentration may be appropriately changed depending on the solubility, workability, stability, economy and the like of compound I.

The composition of the present invention may be composed of only the compound I and the solvent, and may further contain other components. Other components include other silane compounds,
Water repellents, oil repellents, crosslinking agents, insect repellents, flame retardants, antistatic agents, anti-wrinkle agents and the like can be mentioned.

As another silane compound, the following formula (D)
[Hereinafter, it is described as compound D. The compound represented by this is preferable.

[0081]

Embedded image (D): (R ⁷ ) _g Si (Z ⁷ ) _4-g

In the formula (D), R ⁷ , Z ⁷ and g have the following meanings. R ^7: a hydrocarbon group other than a hydrogen atom or a hydrophobic organic group (having 1 to 30 carbon atoms). Z ⁷ : isocyanate group or alkoxyl group. g: 0, 1, 2, or 3.

Z ⁷ may be either an isocyanate group or an alkoxyl group, or may be only an alkoxyl group. When it is an alkoxyl group, a methoxyl group or an ethoxyl group is preferred. G is 0
Or 1 is preferred.

Specific examples of the compound D include the following compounds. However, Z ⁷ in the following formula has the same meaning as described above. Si (Z ⁷ ) ₄ [for example, Si (NCO) ₄ , Si (OCH ₃ ) ₄ , Si (NCO) ₄
Such. ^{_{], CH 3 Si (Z 7}} ) 3, C 2 H 5 Si (Z 7) 3, C 3 H 7 Si (Z 7) 3,
C ₄ H ₉ Si (Z ⁷ ) ₃ , C ₆ H ₁₃ Si (Z ⁷ ) ₃ , C ₆ H ₅ Si (Z ⁷ ) ₃ , CH ₂ = CHSi
_{^{(Z 7) 3, H 2}} NC 3 H 6 Si (Z 7) 3, HSC 3 H 6 Si (Z 7) 3, HC (O) (CH 2)
₅ Si (Z ⁷ ) ₃ , H ₂ NC ₂ H ₄ NHC ₃ H ₆ Si (Z ⁷ ) ₃ , CH ₂ = C (CH ₃ ) COOC ₃ H ₆ S
i (Z ⁷ ) ₃ , ClC ₃ H ₆ Si (Z ⁷ ) ₃ , (CH ₃ ) ₂ Si (Z ⁷ ) ₂ , (C ₂ H ₅ ) (C
^{_{H 3) Si (Z 7)}} 2, (C 3 H 7) (CH 3) Si (Z 7) 2, (C 4 H 9) (CH 3) Si
_{^{(Z 7) 2, (C}} 6 H 13) (CH 3) Si (Z 7) 2, (C 6 H 5) (CH 3) Si (Z 7) 2,
(CH ₂ = CH) (CH ₃ ) Si (Z ⁷ ) ₂ , (H ₂ NC ₃ H ₆ ) (CH ₃ ) Si (Z ⁷ ) ₂ , (HSC
_{3 H 6) (CH 3)} Si (Z 7) 2, [HC (O) (CH 2) 5] (CH 3) Si (Z 7) 2, (H 2 N
_{C 2 H 4 NHC 3 H 6} ) (CH 3) Si (Z 7) 2.

When the composition of the present invention contains the compound D, the amount is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the solvent. When compound D is included, antifouling performance can be expected as well as improved durability of water and oil repellency.

The composition of the present invention can be processed into fibers by any method, depending on the type of the article to be treated and the form of adjustment. For example, a method of applying the coating to the fiber surface and drying it by a known method of coating such as dip coating is employed. Further, since the composition contains the compound I having an isocyanate group reactive at room temperature, there is an advantage that the fiber treatment can be performed at room temperature. Here, the normal temperature is 10 to 3
It means a temperature of about 0 ° C. Further, curing may be performed as necessary.

The composition of the present invention may be filled into a container under pressure, and may be of a so-called aerosol type. The aerosol-type water- and oil-repellent agent can be dried immediately by spraying on the object to be processed and exhibit sufficient performance.

The object to be treated which can be treated with the composition of the present invention includes a fiber or a fibrous body. The fibers include animal and plant natural fibers such as cotton, hemp, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; or blends of these. Fibers made of fiber are exemplified, and fibers containing animal and plant natural materials such as cotton, hemp, wool, and silk are particularly preferable. Further, as the fibrous body, a woven fabric of the fiber,
Knitted fabrics, non-woven fabrics and the like can be mentioned.

These fibers or fibrous bodies may be previously treated with another fiber treating agent or surface-modified. Other fiber treating agents include other water and oil repellents, antifouling agents, insect repellents, flame retardants, antistatic agents, anti-wrinkle agents, dyes, and the like. Examples of a method for modifying the surface include a plasma treatment.

[0090]

The reason why the water / oil repellent composition for fibers of the present invention exhibits excellent durability and texture is not necessarily clear, but is considered as follows. That is, since the isocyanate group in the compound I is a reactive group, it is considered that the presence of the isocyanate group on the fiber surface forms a chemical bond. For example, an isocyanate group is considered to react with a hydroxyl group or an amino group on the fiber surface, and a silanol group generated by elimination of an isocyanate group bonded to a silicon atom is considered to react.

Since the reaction of the isocyanate group is considered to occur between the molecules of compound I, the film formed by treating compound I can be a network-like film. Further, it is considered that the isocyanate group also has adhesion to the fiber. Therefore, the water / oil repellency exhibited by the treatment of Compound I shows excellent durability even when physical force due to heavy rain or the like is applied. This effect is also exhibited when the composition is treated at room temperature, which is expected to be based on the fact that the isocyanate group is a reactive group at room temperature. Even if a network-like coating is formed, a skeleton based on siloxane bonds has higher mobility and is more flexible than a skeleton based on carbon-carbon bonds. Therefore, it is considered that the obtained coating film becomes soft and the texture of the fiber becomes soft.

[0092]

【Example】

[Examples 1 to 6] Trichlorotrifluoroethane (R-11) was added to each compound shown in Table 1 or a mixture of the compounds.
Treatment baths 1 to 6 were prepared by adding 3) and adjusting the concentration of the compound to 0.5% by weight. Cotton cloth and nylon cloth were prepared as treatment cloths, and each treatment cloth was immersed in each treatment bath, squeezed with a mangle, and the pickup was adjusted to 80%. Next, a thermo-hygrostat (25 ° C., humidity 60
%), The following evaluation test was conducted on the dried cloth for 3 hours. Table 4 shows the evaluation results.

[0093]

[Table 1]

[Method of evaluating water repellency] JIS L-109
The water repellency number by the spray method of No. 2 (see Table 1) was used. Those with a + (-) mark on the water-repellent number indicate those with slightly better (poor) performance. In addition, those with a cross mark attached to the water repellent number indicate a case where wetness was recognized on the back surface of the treated cloth.

[Evaluation Method of Oil Repellency] A few drops (approximately 4 mm in diameter) of the test solution shown in Table 2 were placed at two places on a test cloth,
(AATCC-TM11)
8-1966). When the oil repellency number is marked with a + (-) mark, the performance is slightly better (poor).

[0096]

[Table 2]

[0097]

[Table 3]

[Evaluation Method for Heavy Rain Durability] The Bundesmann rain test method (heavy rain test according to JIS L-1092) was performed on a test nylon cloth for 15 minutes, air-dried for 15 hours, and then water and oil repellency was measured.

[Evaluation Method of Hand] The tester touched the treated cloth treated with the water- and oil-repellent agent with the cloth before the treatment, and evaluated the change in the tactile sensation according to the following criteria. Hard: ×, slightly hard: △, flexible: 〇.

[Comparative Example 1] Instead of the compound of Example 1,
A treatment bath was prepared using CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ (treatment bath 7), and treated and dried under the same conditions. An evaluation test was similarly performed on the obtained treated cloth. Table 4 shows the results
Shown in

[0101]

[Table 4]

Comparative Example 2 Instead of the treatment bath of Example 1, a water- and oil-repellent (trade name: AG-5650, manufactured by Asahi Glass Co., Ltd.) containing a copolymer containing a perfluoroalkyl group was added with R-
113 was added thereto, and a treatment bath 8 adjusted so that the concentration of the treatment agent was 0.5% by weight was prepared, and treated similarly to obtain a treated cloth. When the texture was evaluated for this, it was stiff and hard touch, that is, x.

[0103]

The water / oil repellent composition for fibers of the present invention can impart excellent water / oil repellency to the fiber surface. Since the binding and adhesion of the compound I to the object to be treated are high density and high strength, the performance derived from the compound I shows excellent durability against physical force due to heavy rain or the like. . The fiber treated with compound I also has the advantage that the texture is not impaired. Further, the composition of the present invention can impart excellent performance to fibers of a natural material, for which it has been difficult to impart water repellency with a conventional water / oil repellent agent. Further, such an effect can be sufficiently exhibited even when the treatment is performed at room temperature.

Therefore, the water / oil repellent composition for fibers of the present invention can be easily treated and has excellent performance.
Furthermore, since the fiber material of the object to be treated is not limited, the composition is excellent in practicality.

Claims (8)

[Claims] A water / oil repellent composition for fibers comprising the following components (I) and (II) as essential components. (I) A silane compound having at least one hydrophobic organic group and at least one silicon atom directly bonded to an isocyanate group. (II) A solvent that dissolves (I). 2. The method according to claim 1, wherein (I) is a silane compound represented by the following formula (A), a silane compound represented by the following formula (B), or a silane compound represented by the following formula (C). Item 1. A water / oil repellent composition for fibers according to Item 1. Embedded image (A): (Z ¹ ) _3-a (R ¹ ) _a Si-Y-Si (R ² ) _b (Z ² ) _{3-b In} the formula (A), Z ¹ , Z ² , R ¹ , R ² ,
Y, a, and b have the following meanings. Z ¹ , Z ² : independently is an isocyanate group or an alkoxyl group, and at least one of Z ¹ and Z ² is an isocyanate group. R ¹ and R ² independently represent a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. Y: divalent organic group. However, at least ^one of R ¹ , R ² and Y is a hydrophobic organic group. a, b: independently 0, 1, 2, or 3, and 0
≦ a + b ≦ 5. Embedded image (B): (R ³ ) _c Si (Z ³ ) _{4-c In} the formula (B), R ³ , Z ³ and c are
Indicates the following meaning. R ³ : a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and at least one is a hydrophobic organic group. Z ^{3 is an} isocyanate group or an alkoxyl group,
And one or more isocyanate groups. c: 1, 2, or 3. Embedded image (C): (R ⁴ ) _d (Z ⁴ ) _3-d SiO [(R ⁵ ) _e (Z ⁵ ) _2-e SiO] _n S
i (R ⁶ ) _f (Z ⁶ ) _{3-f In} the formula (C), R ^{4 to} R ⁶ , Z ^{4 to} Z ⁶ ,
d, e, f, and n have the following meanings. R ^{4 to} R ^{6 are} independently a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and at least one is a hydrophobic organic group. Z ^{4 to} Z ⁶ : independently an isocyanate group or an alkoxyl group, and at least one of Z ^{4 to} Z ⁶ is an isocyanate group. d, f: independently 0, 1, 2, or 3. e: 0, 1, or 2. However, 1 ≦ d + e + f ≦ 7. n: an integer of 0 or more. 3. The water / oil repellent composition for fibers according to claim 1, further comprising a silane compound represented by the following formula (D). Embedded image (D): (R ⁷ ) _g Si (Z ⁷ ) _{4-g In} the formula (D), R ⁷ , Z ⁷ and g have the following meanings. R ^7: a hydrocarbon group other than a hydrogen atom or a hydrophobic organic group (having 1 to 30 carbon atoms). Z ⁷ : isocyanate group or alkoxyl group. g: 0, 1, 2, or 3. 4. The water / oil repellent treating agent for fibers according to claim 1, wherein the hydrophobic organic group is a polyfluoro organic group. 5. The polyfluoro organic group is a perfluoroalkyl group having 3 to 21 carbon atoms, a perfluoroalkylene group having 2 to 16 carbon atoms, a group containing a perfluoroalkyl portion having 3 to 21 carbon atoms, The water / oil repellent treating agent for fibers according to claim 4, which is a group containing a perfluoroalkylene moiety represented by Formulas 2 to 16. 6. A treatment of a water / oil repellent composition for fibers, wherein the water / oil repellent composition for fibers according to any one of claims 1 to 5 is adhered to a fiber surface or a fibrous body surface and dried. Method. 7. The processing method according to claim 6, wherein the drying is performed at room temperature. 8. A fiber or fibrous body treated with the water / oil repellent composition for fibers according to any one of claims 1 to 5.