JP2000282016A - Water-repelling and oil-repelling agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-repelling and oil-repelling agent composition which can exhibit excellent washing durability without deteriorating the touches of fibers or the like and is especially useful for imparting an excellent water- repelling and oil-repelling property to polyamide fibers having a pale color such as white color, by formulating a specific polymer, a surfactant and a specified aqueous medium. SOLUTION: This water-repelling and oil-repelling composition comprises (A) a polymer, (B) a surfactant preferably containing 60-100 wt.% of a nonionic surfactant, and (C) an aqueous solvent comprising water alone or a medium comprising water and a water-soluble organic solvent. The polymer in the component A comprises (i) the polymer units of a (meth)acrylate having a polyfluoroalkyl group, (ii) the polymer units of a polymerizable monomer for example, a compound of the formula: CH2=CHCOOCH2CH2O[O(CH2)5O]4H} which has a polymerizable unsaturated group and a hydroxyl group, wherein the polymerizable unsaturated group is bound to the hydroxyl group through seven or more covalent bonds, and (iii) the polymer units of a (meth)acrylate having a blocked isocyanate group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a water / oil repellent composition and a method for producing the same. ADVANTAGE OF THE INVENTION According to this invention, the water-repellent and oil-repellent composition which gives excellent water-repellent and oil-repellent property to a to-be-processed object is obtained, and especially the light-repellent which provides excellent water-repellent and oil-repellent property to the light-colored polyamide fiber of white etc. A water and oil repellent composition is obtained.

[0002]

2. Description of the Related Art Conventionally, in order to impart water and oil repellency to a fiber or a textile fabric, a polymer containing a (meth) acrylate polymer unit containing a polyfluoroalkyl group (hereinafter referred to as an ^Rf group) has been used. A fluorine-based water / oil repellent containing a fluoropolymer as a main component is used. However, the durability of the water or oil repellency of fibers or fiber fabrics treated with the conventional fluorine-based water and oil repellents is insufficient, and there is a problem that the water and oil repellency is reduced by washing or the like.

In order to solve this problem, (1) a fluorine-based water / oil repellent to which trimethylolmelamine or an organic amine is added (JP-A-54-133486, JP-A-56-1)
65072, JP-A-5-272060), (2) a fluorine-based water- and oil-repellent to which a polyfunctional blocked isocyanate urethane compound is added (JP-A-58-208473, JP-A-2-92985), (3) an aminoplast resin and Fluorinated water / oil repellents to which a polyfunctional blocked isocyanate urethane compound has been added have been proposed.

The fluorine-containing polymer in the above-mentioned water- and oil-repellent agents (1) to (3) contains polymerized units of a polymerizable monomer having an active hydrogen atom, and specifically, N-methylol It contains polymerized units such as acrylamide, 2-hydroxyethyl (meth) acrylate, and 3-chloro-2-hydroxypropyl (meth) acrylate. However, (1) ~
The durability of the conventional water / oil repellent shown in (3) is insufficient, and there is a problem that the washing durability is particularly poor. In addition, this problem was remarkably observed when the fibers were treated with polyamide fibers or woven fabrics.

Also, (4) a method of pretreating with a polyhydric phenol compound and then treating with a fluorine-based water / oil repellent (JP-A-58-46176), and (5) a pretreatment with a sulfonated phenol formaldehyde low-condensate. Later, a method of treating with a fluorine-based water / oil repellent and an amiplast resin (JP-A-1-221576) has been proposed. But,
Even with the object treated by the method (4) or (5), the durability of washing is insufficient, and there is also a problem that the texture of the object becomes coarse and hard. Further, when the treatment is performed by the method (4) or (5), there is a problem that the object to be treated is colored, and there is a problem that the light-colored fiber cannot be treated.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems. The present inventors have studied the cause of the fact that the conventional fluorine-based water- and oil-repellent could not exhibit sufficient performance, the fluorine-containing polymer as an active ingredient in the water- and oil-repellent has an active hydrogen atom Even if it contains a polymerized unit of a polymerizable monomer, since the active hydrogen atom is present at a position close to the polymerization main chain, the ^Rf group is sterically hindered and cannot sufficiently participate in the crosslinking reaction, As a result, it was considered that the quality of the film formed from the water / oil repellent was insufficient, and the durability of the water / oil repellency was insufficient.

In order to effectively promote the crosslinking reaction, a polymer having a reactive group at a position sufficiently away from the polymerization main chain so as not to be sterically hindered by the R ^f group is considered. Was. Furthermore, as a reactive group, a hydroxyl group is selected,
By including a polymer in which this and a blocked isocyanate group are combined in the water / oil repellent composition,
It has been found that a water / oil repellent composition capable of exhibiting excellent washing durability without impairing the texture is provided. Furthermore, it has been found that the object to be treated treated with the water / oil repellent composition has no inconvenience such as coloring.

That is, the present invention provides a water / oil repellent composition comprising the following polymer (X), surfactant (B) and aqueous medium (C). Polymer (X): a polymerized unit of the following polymerizable monomer (a ¹ ),
A polymer essentially comprising a polymerized unit of the following polymerizable monomer (a ² ) and a polymerized unit of the following polymerizable monomer (a ³ ). Polymerizable monomer (a ¹ ): (meth) acrylate having a polyfluoroalkyl group. Polymerizable monomer (a ² ): a polymerizable monomer having a polymerizable unsaturated group and a hydroxyl group, and wherein the polymerizable unsaturated group and the hydroxyl group are linked via 7 or more covalent bonds. Mers. Polymerizable monomer (a ³ ): (meth) acrylate having a blocked isocyanate group. Aqueous medium (C): Water or a medium comprising water and a water-soluble organic solvent.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, acrylate and methacrylate are collectively referred to as (meth) acrylate. The same applies to notations such as (meth) acrylamide. The R ^f group refers to a group in which two or more hydrogen atoms of an alkyl group have been substituted with fluorine atoms. The ^Rf group preferably has 2 to 20 carbon atoms, particularly preferably 6 to 16 carbon atoms. The R ^f group may have a linear structure or a branched structure, and preferably has a linear structure. In the case of a branched structure, the branched portion is preferably present at the terminal of the R ^f group, and is preferably a short chain having about 1 to 4 carbon atoms.

The R ^f group may have a halogen atom other than a fluorine atom. Other halogen atoms include
A chlorine atom is preferred. An etheric oxygen atom or a thioetheric sulfur atom may be inserted between carbon-carbon bonds in the R ^f group. The structure of the terminal portion of the R ^f group includes -CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF ₂
H, -CFH _2, -CF ₂ Cl and the like preferably, particularly -CF ₂ CF ₃ preferred.

[0011] The number of fluorine atoms in the R ^f groups, [(R ^f number of fluorine atoms in the group) / (R ^f number of hydrogen atoms contained in the alkyl group corresponding same carbon number and group)] × 100 When expressed in (%), it is preferably at least 60%, particularly preferably at least 80%. Further, the R ^f group is preferably a group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms (that is, a perfluoroalkyl group), or a group having a perfluoroalkyl group at a terminal portion.

The carbon number of the perfluoroalkyl group is from 2 to
20 is preferable, and especially 4-16 is preferable. If the number of carbon atoms in the perfluoroalkyl group is small, the water repellency and oil repellency tend to decrease, and if the number of carbon atoms in the perfluoroalkyl group is large, it may be difficult to handle (meth) acrylate having an ^Rf group. .

Specific examples of the R ^f group include the following groups. _{C 4 F 9 - [F (} CF 2) 4 -, (CF 3) 2 CFC
F ₂ —, (CF ₃ ) ₃ C—, or CF ₃ CF ₂ (CF ₃ ) C
One] structural isomers groups such F-, C ₅ F ₁₁ - [e.g. _{F (CF 2) 5 -]} , C 6 F 13 - [ e.g. F (C
_{F 2) 6 -], C} 7 F 15 - [ e.g. _{F (CF 2) 7 -]} ,
C ₈ F ₁₇ - [e.g. _{F (CF 2) 8 -]} , C 9 F 19 - [ e.g. _{F (CF 2) 9 -]} , C 10 F 21 - [ e.g. F (C
_{F 2) 10 -], C} 12 F 2 5 - [ e.g. F (CF _{2)
12 -], C 14 F 29} - [ e.g. _{F (CF 2) 14 -]} , C
₁₆ F ₃₃ - [e.g. _{F (CF 2) 16 -]} , Cl (CF 2)
_t −, H (CF ₂ ) _t − (where t is an integer of 4 to 16), (CF ₃ ) ₂ CF (CF ₂ ) _k − (where k is 1 to
13 integers).

When the R ^f group is a group in which an etheric oxygen atom or a thioetheric sulfur atom is inserted between carbon-carbon bonds, the following groups may be mentioned. _{F (CF 2) 5 OCF (} CF 3) -, F [CF (C
_{F 3) CF 2 O] r} CF (CF 3) CF 2 CF 2 -, F [CF
(CF ₃ ) CF ₂ O] _r 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 -, F
_{(CF 2) 5 SCF (CF} 3) -, F [CF (CF 3) CF
_{2 S] r CF (CF 3} ) CF 2 CF 2 -, F [CF (CF 3)
CF ₂ S] _r CF (CF ₃ ) —, F [CF (CF ₃ ) CF _{2
S] u CF 2 CF 2 -} , F (CF 2 CF 2 CF 2 S) v CF 2 C
F _2- , F (CF ₂ CF ₂ S) _w CF ₂ CF _2- (r is 1 to 5
U is an integer of 2 to 6, v is an integer of 1 to 6, w is 1
-9) and the like.

The water and oil repellent composition of the present invention comprises a polymer (X), a surfactant (B) and an aqueous medium (C) as essential components. The polymer (X) is a polymerizable monomer (a ¹ )
A polymerized unit of ((meth) acrylate having an R ^f group),
A polymerizable monomer (a ² ) (a polymerizable monomer having a polymerizable unsaturated group and a hydroxyl group, and wherein the polymerizable unsaturated group and the hydroxyl group are linked via 7 or more covalent bonds); Monomer) and a polymerizable monomer (a ³ ) ((meth) acrylate having a blocked isocyanate group).

The polymerizable monomer (a ¹ ) in the polymer (X) refers to a compound in which the R ^f group is present at the alcohol residue of (meth) acrylate. Polymerizable monomer (a
The ^1), a compound represented by the following formula a ¹¹ is preferred.
However, R ^f and R ^f group in the formula a ^11, Q is a divalent organic radical,
R represents a hydrogen atom or a methyl group. As R ^f is in the _{^{R f -Q-OCOCR = CH 2}} ··· formula a ¹¹ formula a ^11, R ^f group is preferably free of ether oxygen atoms or thioether sulfur atoms, particularly a perfluoroalkyl group is preferred, especially A perfluoroalkyl group having a linear structure is preferred. Examples of the linear perfluoroalkyl group include-(CF ₂ ) _n F
(However, n is an integer of 2 to 20, preferably an integer of 4 to 16, and particularly preferably an integer of 6 to 12.)

[0017] As Q in the formula a ¹¹ is, - (CH _{2)
p + q -, - (CH} 2) p CONR a (CH 2) q -, - (CH
_{^{2) p OCONR a (CH 2}} ) q -, - (CH 2) p SO 2 NR
^a (CH ₂ ) _q -,-(CH ₂ ) _p NHCONH (CH ₂ ) _{q
-, - (CH 2) p} CH (OH) (CH 2) q -, - (CH
^{_{2) p CH (OCOR a)}} (CH 2) q - and the like are preferable. Here, Ra represents ^a hydrogen atom or an alkyl group. Also,
p and q each independently represent an integer of 0 or more;
It is an integer of 22.

Further, the equation a¹¹Is-(C
H_Two)_{p + q}-,-(CH_Two)_pCONR ^a(CH_Two)_q−
Or-(CH_Two)_pSO_TwoNR^a(CH_Two)_q-
And q is an integer of 2 or more, and p + q is 2 to 6.
Is preferable, and-(C) when p + q is 2 to 6
H_Two)_{p + q}-(Ie, ethylene group to hexamethylene
A compound of the formula (a)¹¹Is particularly preferred. Ma
Equation a¹¹R which binds to Q in^fThe carbon atoms of
Preferably, a fluorine atom is bonded.

Examples of the polymerizable monomer (a ¹ ) include the following compounds. However, R in the following compounds represents a hydrogen atom or a methyl group. F (CF ₂ ) ₅ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₆ CH ₂ CH ₂ OCOCR = CH ₂ , H (C
F ₂ ) ₆ CH ₂ OCOCR = CH ₂ , H (CF ₂ ) ₈ CH ₂ OCOCR = CH ₂ , H (CF ₂ ) ₁₀ CH ₂
OCOCR = CH ₂ , H (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₈ CH ₂ CH ₂ CH
₂ OCOCR = CH ₂ , F (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₁₀ CH ₂ CH ₂
OCOCR = CH ₂ , F (CF ₂ ) ₁₂ CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₁₄ CH ₂ CH ₂
OCOCR = CH ₂ , F (CF ₂ ) ₁₆ CH ₂ CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₄
CH ₂ CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ OCOCR = CH ₂ , (C
F ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₈ SO ₂ N (C ₃ H ₇ ) CH ₂ C
H ₂ OCOCR = CH ₂ , F (CF ₂ ) ₈ (CH ₂ ) ₄ OCOCR = CH ₂ , F (CF ₂ ) ₈ SO ₂ N (C
H ₃ ) CH ₂ CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₈ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂ OCOCR = C
H ₂ , F (CF ₂ ) ₈ CONHCH ₂ CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ (C
H ₂ ) ₃ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH (OCOCH ₃ ) OCOCR = CH
₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH (OH) CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (C
F ₂ ) ₇ CH ₂ CH (OH) CH ₂ OCOCR = CH ₂ , F (CF ₂ ) ₉ CH ₂ CH ₂ OCOCR = C
H ₂ , F (CF ₂ ) ₉ CONHCH ₂ CH ₂ OCOCR = CH ₂ .

The polymer (X) of the present invention contains at least one polymerized unit of the polymerizable monomer (a ¹ ). When two or more polymerizable units of the polymerizable monomer (a ¹ ) are included, the polymerizable units are preferably (meth) acrylate polymer units having an R ^f group having a different number of carbon atoms. The polymer (X) in the present invention is:
The polymerization unit of the polymerizable monomer (a ² ) is essential together with the polymerization unit of the polymerizable monomer (a ¹ ).

The polymerizable monomer (a ² ) is preferably selected from known or well-known polymerizable monomers. Further, the polymerizable monomer (a ² ) is preferably a polymerizable monomer having one or two polymerizable unsaturated groups, particularly preferably a polymerizable monomer having one polymerizable unsaturated group. . As the polymerizable unsaturated group in the polymerizable monomer (a ² ), a vinyl group or an isopropenyl group is preferable. The number of hydroxyl groups in the polymerizable monomer (a ² ) is preferably one. The hydroxyl group in the polymerizable monomer (a ² ) is preferably a hydroxyl group bonded to a carbon atom.

Further, as the polymerizable monomer (a ² ),
Polymerization having a vinyl group, a (meth) acryloyl group or a residue obtained by removing one or two hydroxyl groups from two carboxyl groups of maleic acid, and having a hydroxyalkyl group or a hydroxyhalogenated alkyl group It is preferably an acidic compound.

The polymerizable unsaturated group and the hydroxyl group in the polymerizable monomer (a ² ) are linked via seven or more covalent bonds. That is, between the polymerizable unsaturated group and the hydroxyl group,
There is a divalent linking group, and in the divalent linking group, a series of divalent or higher valent atoms capable of forming a covalent bond has 6 or more linear atoms. When two or more polymerizable unsaturated groups and two or more hydroxyl groups are present in the polymerizable monomer (a ² ), a covalent bond existing between each hydroxyl group and each polymerizable unsaturated group is present. All the numbers are 7 or more.

The polymerizable monomer (a ² ) is a polymerizable monomer having one polymerizable unsaturated group and one hydroxyl group,
The number of covalent bonds between the polymerizable unsaturated group and the hydroxyl group is 7
The number is preferably at least 11, more preferably at least 11, and especially preferably at least 13. The number of the covalent bonds is preferably 70 or less. Further, the lower limit of the number of the covalent bonds is preferably not less than the number of chain lengths of the R ^f group in the polymerizable monomer (a ¹ ),
In particular, it is preferably (the chain number + 3) or more.

[0025] As the polymerizable monomer in the present invention (a ²⁾ is a compound represented by the following formula a ^21, a compound represented by a compound or the formula a ²³ represented by the following formula a ²² is preferred.

[0026]

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However, the symbols in the formulas a ²¹ to a ²³ have the following meanings. ^{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R 8, R 9: each independently, a hydrogen atom or a methyl group. n: an integer of 2 to 6. m: an integer from 1 to 20. x, y, z: each independently an integer of 0 to 30. However,
x + y + z is an integer of 2 or more. a, b, c: each independently an integer of 0 to 30. However,
a + b + c is an integer of 2 or more. p: an integer of 3 to 6.

[0028] In formula a ^21, m is preferably 2 to 10, n is preferably 3 to 5. Specific examples of the compound represented by the formula a ^21, the following compounds may be mentioned.

[0029]

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The oxyalkylene moieties in formula a ^22, means that it is linked to form blocks. In the formula a ²² is preferably one or both of x and z is 0. Also, x in the formula a ²² is preferably 0 to 10,
y is preferably 2 to 20, and z is preferably 0 to 10. Also, (x + y + z) is preferably 3 to 20. Specific examples of the compound represented by the formula a ^22, the following compounds may be mentioned.

[0031]

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The oxyalkylene moieties in formula a ^23, means that it is linked to form blocks. In the formula a ^23, it is preferable that at least one of a or c is 0. Further, a is preferably 0 to 10 in the formula a ^23, b is preferably from 2 to 20, c is preferably 0 to 10 is. Further, (a + b + c) is preferably 3 to 20. Specific examples of the compound represented by the formula a ^23, the following compounds may be mentioned.

[0033]

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Further, as the polymerizable monomer (a ² ),
The following compounds are particularly preferred.

[0035]

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The polymer (X) of the present invention comprises a polymerizable unit of the polymerizable monomer (a ³ ) together with a polymerizable unit of the polymerizable monomer (a ¹ ) and a polymerizable unit of the polymerizable monomer (a ² ). A polymerization unit is required. Having a blocked isocyanate group (meth)
The acrylate refers to a (meth) acrylate having at least one blocked isocyanate group, and is preferably a compound having a structure in which an isocyanate group of an isocyanate group-containing (meth) acrylate is blocked with a blocking agent.

Here, as the isocyanate group-containing (meth) acrylate, 2-isocyanateethyl (meth) acrylate or (meth) acrylate having a functional group capable of bonding to an isocyanate group and one or more polyisocyanates are used. A reaction product obtained by allowing the isocyanate groups to react at a remaining ratio is preferable. As the (meth) acrylate having a functional group capable of binding to an isocyanate group, a (meth) acrylate having a hydroxyl group is preferable, and a mono- or diester of (meth) acrylic acid and a polyhydric alcohol is particularly preferable.

Examples of the polyhydric alcohol include ethylene glycol, polyoxyethylene glycol, propylene glycol, polyoxypropylene glycol, glycerin, trimethylolpropane-alkylene oxide adduct, and pentaerythritol.

As the polyisocyanate, an aliphatic polyisocyanate is preferable, and hexamethylene diisocyanate, isophorone diisocyanate, 4,4 ′
-Aliphatic isocyanates such as dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, norbornene diisocyanate, nullate-modified aliphatic isocyanates, prepolymer-modified or burette-modified derivatives, or 2-3 of the aliphatic isocyanates The monomer is preferably an aliphatic isocyanate, or a nullate-modified, prepolymer-modified or buret-modified derivative thereof.

As the blocking agent, alkyl ketoximes, phenols, alcohols, β-diketones, lactams, amines and the like are preferable. Methyl ethyl ketoxime, ε-caprolactam, phenol, cresol, acetylacetone, diethyl malonate Isopropyl alcohol, t-butyl alcohol, maleimide and the like, particularly preferred are alkyl ketoximes such as methyl ethyl ketoxime, lactams such as ε-caprolactam and the like.
A blocking agent consisting of a compound at 80 ° C. is preferred.

Specific examples of the polymerizable monomer (a ³ ) include:
The following compounds are mentioned. Compounds in which isocyanate groups of 2-isocyanatoethyl (meth) acrylate are blocked with methyl ethyl ketoxime, compounds in which isocyanate groups of 2-isocyanateethyl (meth) acrylate are blocked with ε-caprolactam, isophorone diisocyanate and 2-hydroxyethyl (meth) acrylate A compound in which isocyanate groups of a 1: 1 (molar ratio) reaction product with methyl ethyl ketoxime are blocked,
A compound in which the isocyanate group of a reaction product of isophorone diisocyanate and 2-hydroxypropyl (meth) acrylate in a ratio of 1: 1 (molar ratio) is blocked with methyl ethyl ketoxime, and a 1: 1 mixture of norbornene diisocyanate and 2-hydroxyethyl (meth) acrylate ( (Mole ratio) Compound in which the reaction product is blocked with methyl ethyl ketoxime.

In the present invention, the polymerizable monomer (a ³ )
Has a blocked isocyanate group,
It may have another group other than the R ^f group. Further, the polymerizable monomer (a ² ) may have another group except for the R ^f group and the blocked isocyanate group as long as it has a polymerizable unsaturated group and a hydroxyl group.

The polymer (X) in the present invention may contain a polymerizable unit of the following polymerizable monomer (a ⁴ ) together with a polymerizable unit of the polymerizable monomers (a ¹ ) to (a ³ ). Good. Polymerizable monomer (a ⁴ ): an alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms and / or a cycloalkyl (meth) acrylate having a cycloalkyl group having 5 to 8 carbon atoms.

Examples of the alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and dodecyl (meth) acrylate. A) acrylate, octadecyl (meth) acrylate, behenyl (meth) acrylate; As the cycloalkyl (meth) acrylate having a cycloalkyl group having 5 to 8 carbon atoms, cyclohexyl (meth) acrylate is preferable.

[0045] Further, the polymer of the present invention (X) is the polymerizable monomer (a ¹⁾ with polymerized units of ~ (a ^4), the polymerizable monomer (a ¹⁾ non ~ (a ⁴⁾ Polymerizable monomer (a ⁵ )
May be included. Polymerizable monomer (a ⁵ )
As, known or well-known polymerizable monomers,
A polymerizable monomer having one or two polymerizable unsaturated groups is preferred, and a polymerizable monomer having one polymerizable unsaturated group is particularly preferred.

As the polymerizable monomer (a ⁵ ), olefins such as ethylene, propylene, butadiene, isoprene, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride and chloroprene, styrene, α-methylstyrene, Styrenes such as 4-methylstyrene, (meth) acrylamides such as diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, ethyl vinyl ether, cyclohexyl vinyl ether, allyl glycidyl ether, etc. Ethers, vinyl carboxylate such as vinyl acetate, vinyl alkyl ketone such as ethyl vinyl ketone, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-chloro -2-hydroxypropyl (meth) acrylate, polyoxyalkylene mono (meth) acrylate monomethyl ether, polyoxyalkylene di (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, (meth) acrylate having a polydimethylsiloxane group , Triallyl cyanurate, N-vinylcarbazole, N-alkylmaleimide, maleic anhydride, monoalkyl maleate, dialkyl maleate and the like are preferred.

The polymer (X) in the present invention comprises a polymerizable unit of the polymerizable monomer (a ¹ ), a polymerizable unit of the polymerizable monomer (a ² ), and a polymerizable unit of the polymerizable monomer (a ³ ). It is preferable that the polymer be a polymer composed of only polymerized units or a polymer containing polymerized units of the polymerizable monomer (a ⁴ ) together with the polymerized units of the polymerizable monomers (a ¹ ) to (a ³ ). .

The proportion of each polymer unit in the polymer (X) is such that the polymer unit of the polymerizable monomer (a ¹ ) is 60 to 96% by mass and the polymer unit of the polymerizable monomer (a ² ) is ² %. It is preferable that the polymerization unit of the polymerizable monomer (a ³ ) is 2 to 30% by mass. The polymerizable monomer (a ³ ) is 2 to 20% by mass.
It is particularly preferred that Further, the polymerizable monomer (a ⁴ )
When a polymerized unit of 0.1 is contained, the polymer (X) has a molecular weight of 0.1.
The content is preferably 1 to 20% by mass, and the polymerizable monomer (a
^When the polymerized unit of ⁵ ) is included, the content is preferably 0.1 to 20% by mass in the polymer (X).

The water / oil repellent composition of the present invention contains a surfactant (B). Even if the surfactant (B) is one kind,
There may be more than one species. The surfactant (B) preferably includes a nonionic surfactant as an essential component, and may be composed of only a nonionic surfactant. The surfactant (B) may include a nonionic surfactant and a surfactant other than the nonionic surfactant. It may consist of The surfactant (B) is preferably a surfactant containing a nonionic surfactant in a proportion of 60 to 100% by mass.

When the surfactant (B) contains another surfactant in addition to the nonionic surfactant, the other surfactant is preferably a cationic surfactant or an amphoteric surfactant. . Further, the surfactant (B) is preferably a surfactant containing no fluorine atom in terms of stability of the liquid after emulsification under pressure and water / oil repellency.

The nonionic surfactant in the surfactant (B) is preferably at least one nonionic surfactant selected from the following surfactants (b ¹ ) to (b ⁶ ). In particular, surfactants (b ¹ ), (b ² ),
At least one selected from (b ³ ), (b ⁴ ) and (b ⁶ ) is preferable from the viewpoint of less effect on the environment and water / oil repellency.

The surfactant (b ¹ ) is a nonionic surfactant comprising a polyoxyalkylene monoalkyl ether, a polyoxyalkylene monoalkenyl ether, or a polyoxyalkylene monoalkapolyenyl ether.

An alkyl group in the surfactant (b ¹ ),
The alkenyl group or alkapolyenyl group preferably has 4 to 26 carbon atoms. Also, an alkyl group,
The alkenyl group or the alkapolyenyl group may have a linear structure or a branched structure, respectively. In the case of a branched structure, a secondary alkyl group, a secondary alkenyl group, or a secondary alkapolyenyl group is preferred. Specific examples of the alkyl group, alkenyl group or alkapolyenyl group include octyl group, dodecyl group, tetradecyl group,
Examples include a hexadecyl group, an octadecyl group, a behenyl group (a docosyl group), and an oleyl group (a 9-octadecenyl group).

The surfactant (b ¹ ) is preferably a polyoxyalkylene monoalkyl ether or a polyoxyalkylene monoalkenyl ether. The polyoxyalkylene portion of the surfactant (b ¹ ) is preferably composed of one or two oxyalkylene groups, and when composed of two types, it is preferred that their connection is block-like. The polyoxyalkylene portion preferably comprises a portion in which two or more oxyethylene groups and / or oxypropylene groups are linked.

[0055] The surfactant (b ^1), a compound represented by the following formula b ¹¹ are preferred. However, R ¹⁰ in the following formula b ¹¹ represents an alkyl group having 8 or more carbon atoms or an alkenyl group having 8 or more carbon atoms, s represents an integer of 5 to 50, and g represents 0 to 2
Indicates an integer of 0. When g and s are 2 or more,
Is connected becomes blocky The oxyethylene group and oxypropylene group in the formula b ^11.

[0056]

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R ¹⁰ in the formula b ¹¹ may have either a straight-chain structure or a branched structure. s is preferably an integer of 10 to 30, and g is preferably an integer of 0 to 10. When s is 4 or less or g is 21 or more, it becomes poorly soluble in water and does not dissolve uniformly in the aqueous medium (C), so that the effect of improving permeability may decrease. When s is 51 or more, hydrophilicity is increased, and there is a possibility that water repellency is reduced.

Specific examples of the compound (formula b ¹¹ ) include the following compounds. Where s and g are
Has the same meaning as described above, and the preferred embodiment is also the same. Further, the oxyethylene group and the oxypropylene group are connected in a block shape.

[0059]

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The surfactant (b ² ) has at least one carbon-carbon triple bond and at least one hydroxyl group in the molecule,
And a nonionic surfactant comprising a compound exhibiting surface activity.

The surfactant (b ² ) is preferably a nonionic surfactant comprising a compound having one carbon-carbon triple bond and one or two hydroxyl groups in the molecule. Further, the nonionic surfactant may have a polyoxyalkylene moiety as a partial structure. As the polyoxyalkylene portion, a polyoxyethylene portion, a polyoxypropylene portion, a portion in which oxyethylene groups and oxypropylene groups are connected in a random shape, or a portion in which polyoxyethylene and polyoxypropylene are connected in a block shape, Is mentioned. Surfactant (b
² ) As specific examples of the following formulas b ²¹ , b ²² and b ²³
Or a compound represented by the following formula b ²⁴ are preferred.

[0062]

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However, A ¹ , A ² and A ³ in the formulas b ²¹ to b ²⁴ each independently represent an alkylene group, m and n each represent an integer of 0 or more, and (m + n) represents 1
Represents an integer of 1 or more, and k represents an integer of 1 or more. When m, n or k is 2 or more, A ¹ , A ² and A ³ may each consist of only one kind of alkylene group or may consist of two or more kinds of alkylene groups. .

R ^{11 to} R ¹⁶ each independently represent a hydrogen atom or an alkyl group. When it is an alkyl group, it is preferably an alkyl group having 1 to 12 carbon atoms, particularly preferably 6 to 1 carbon atoms.
Two alkyl groups are preferred. Specific examples of these groups include a methyl group, an ethyl group, a propyl group, a butyl group and an isobutyl group.

The oxyalkylene portion preferably comprises an oxyethylene portion, an oxypropylene portion, or both an oxyethylene portion and an oxypropylene portion. The number of oxyalkylene groups of the surfactant (b ²⁾ in the 1-50 is preferred.

Further, as the surfactant (b ² ), a nonionic surfactant represented by the following formula b ²⁵ is preferable. However, x and y in formula b ²⁵ represents 0 or respective integers. The nonionic surfactant (formula b ²⁵ ) may be used alone or in combination of two or more.

[0067]

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The nonionic surfactant (formula b ²⁵ ) includes a nonionic surfactant in which the average of the sum of x and y is 10, and a nonionic surfactant in which x is 0 and y is 0 Or a nonionic surfactant in which the average of the sum of x and y is 1.3.

The surfactant (b ³ ) comprises a polyoxyethylene portion in which two or more oxyethylenes are continuously connected,
A nonionic surfactant comprising a compound in which two or more oxyalkylenes having 3 or more carbon atoms are continuously connected to a polyoxyalkylene moiety and both terminals are hydroxyl groups. The oxyalkylene having 3 or more carbon atoms in the surfactant (b ³ ) is preferably oxytetramethylene and / or oxypropylene.

[0070] As the surfactant (b ^3), a nonionic surfactant made of a compound represented by the following formula b ³¹ or the formula b ³² are preferred. Note the h in the formula b ³¹ and the formula b ³² 0
An integer of ~ 200, r is an integer of 2 ~ 100, t is 0 ~ 20
It represents an integer of 0. When h is 0, t is an integer of 2 or more. When t is 0, h is an integer of 2 or more. Further, -C ₃ H ₆ in the formula b ³¹ - moiety, -CH (CH ₃₎ C
Regardless of H ₂ — or —CH ₂ CH (CH ₃ ) —, —CH (CH ₃ ) CH ₂ — and —CH ₂ CH (CH ₃ ) —
And may be mixed. Further, each polyoxyalkylene moiety in the following formula is connected in a block shape.

[0071]

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Further, as the surfactant (b ³ ), a nonionic surfactant comprising any of the following compounds is preferable.

[0073]

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[0074] Surfactant (b ⁴⁾ is a nonionic surfactant having an amine oxide moiety in its molecule, a nonionic surfactant made of a compound represented by the following formula b ⁴¹ are preferred.

[0075]

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[0076] wherein b ⁴¹ of R ^17, R ¹⁸ and R ¹⁹ each independently represent a monovalent hydrocarbon radical. Surfactants having an amine oxide moiety (N → O) in the molecule are sometimes classified as cationic surfactants, but are treated as nonionic surfactants in the present invention. The surfactant may be one kind or two or more kinds. The surfactant (b ^4), a nonionic surfactant is particularly represented by the following formula b ^42, preferable because of improving the dispersion stability of the polymer (X).

[0077]

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[0078] Formula b ⁴² in R ²⁰ is an alkyl group having 6 to 22 carbon atoms, a phenyl group an alkenyl group having 6 to 22 carbon atoms, an alkyl group (6 to 22 carbon atoms) bonded or alkenyl group (carbon, (6 to 22) represents a bonded phenyl group, and is an alkyl group having 8 to 22 carbon atoms or 8 to 22 carbon atoms.
The alkenyl group of is preferred.

Specific examples of the nonionic surfactant (formula b ⁴² ) include the following compounds. [H (CH ₂ ) ₁₂ ] (CH ₃ ) ₂ N (→ O), [H (C
H ₂ ) ₁₄ ] (CH ₃ ) ₂ N (→ O), [H (CH ₂ ) ₁₆ ]
(CH ₃ ) ₂ N (→ O), [H (CH ₂ ) ₁₈ ] (CH ₃ ) ₂
N (→ O).

The surfactant (b ⁵ ) is a condensate of polyoxyethylene mono (substituted phenyl) ether or a nonionic surfactant composed of polyoxyethylene mono (substituted phenyl) ether. As the substituted phenyl group in the surfactant (b ⁵ ), a phenyl group substituted with a monovalent hydrocarbon group is preferable, and a phenyl group substituted with an alkyl group, an alkenyl group or a styryl group is more preferable.

As the surfactant (b ⁵ ), a condensate of polyoxyethylene mono (alkylphenyl) ether,
Preference is given to condensates of polyoxyethylene mono (alkenylphenyl) ether, polyoxyethylene mono (alkylphenyl) ether, polyoxyethylene mono (alkenylphenyl) ether or polyoxyethylene mono [(alkyl) (styryl) phenyl] ether.

Polyoxyethylene mono (substituted phenyl)
Specific examples of the condensate of ether or polyoxyethylene mono (substituted phenyl) ether include formaldehyde condensate of polyoxyethylene mono (nonylphenyl) ether and polyoxyethylene mono (nonylphenyl)
Ether, polyoxyethylene mono (octylphenyl) ether, polyoxyethylene mono (oleylphenyl) ether, polyoxyethylene mono [(nonyl)
(Styryl) phenyl] ether, polyoxyethylene mono [(oleyl) (styryl) phenyl] ether and the like.

The surfactant (b ⁶ ) is a nonionic surfactant composed of a fatty acid ester of a polyol. Examples of the polyol in the surfactant (b ⁶ ) include polyethylene glycol, decaglycerin, and ethers of polyethylene glycol and a polyol (other than polyethylene glycol).

As the surfactant (b ⁶ ), 1: 1 (molar ratio) ester of octadecanoic acid and polyethylene glycol, 1: 4 (molar ratio) ester of ether of sorbite and polyethylene glycol, and oleic acid A 1: 1 (molar ratio) ester of polyoxyethylene glycol and sorbitan with octadecanoic acid, a 1: 1 (molar ratio) ester of polyethylene glycol and sorbitan with oleic acid, and dodecanoic acid 1: 1 (molar ratio) ester with sorbitan, (1 or 2): 1 (molar ratio) ester of oleic acid and decaglycerin, (1 or 2): 1 (molar ratio) of octadecanoic acid and decaglycerin Esters are mentioned.

When the surfactant (B) contains a cationic surfactant, it is preferable to use a cationic surfactant comprising a substituted ammonium salt. As the cationic surfactant comprising a substituted ammonium salt, one or more of the hydrogen atoms bonded to the nitrogen atom of the ammonium salt is substituted with an alkyl group, an alkenyl group, or a polyoxyalkylene group having a hydroxyl group at the end. cationic surfactants are preferred comprising a compound, cationic surfactants are preferred in particular consisting of a compound represented by the following formula b ^7.

[0086] _{^{[(R 21) 4 N +}} ] · X - ··· formula b ⁷ provided that the symbols in the formula b ⁷ have the following meanings. R ²¹ : 4
R ²¹ each independently represent a hydrogen atom, a carbon number of 1 to 2
An alkyl group having 2 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or a polyoxyalkylene group having a terminal hydroxyl group. However, four R ²¹ are not simultaneously hydrogen atoms. X ^-: counter ion.

When R ²¹ is an alkyl group, a long-chain alkyl group having 6 to 22 carbon atoms is preferred. When R ²¹ is an alkyl group other than a long-chain alkyl group, a methyl group or an ethyl group is preferred. When R ²¹ is an alkenyl group, a long-chain alkenyl group having 6 to 22 carbon atoms is preferred.
When R ²¹ is a polyoxyalkylene group,
Polyoxyethylene groups are preferred. X ⁻ is preferably a chloride ion, an ethyl sulfate ion or an acetate ion.

The compound (formula b ⁷ ) includes mono (long-chain alkyl) amine hydrochloride, mono (long-chain alkyl) dimethylamine hydrochloride, mono (long-chain alkyl) dimethylamine acetate, mono (long-chain alkenyl) Dimethylamine hydrochloride,
Mono (long chain alkyl) dimethylamine / ethyl sulfate,
Mono (long-chain alkyl) trimethylammonium chloride, di (long-chain alkyl) monomethylamine hydrochloride, di (long-chain alkyl) dimethylammonium chloride, mono (long-chain alkyl) monomethyldi (polyoxyethylene)
Ammonium chloride, di (long-chain alkyl) monomethylmono (polyoxyethylene) ammonium chloride and the like.

Further, as the compound (formula b ⁷ ), monooctadecyltrimethylammonium chloride, monooctadecyldimethylmonoethylammonium ethyl sulfate, mono (long-chain alkyl) monomethyldi (polyethylene glycol) ammonium chloride, di (tallowalkyl) dimethylammonium Chloride, dimethylcoconutamine acetate and the like are preferred.

When the surfactant (B) contains an amphoteric surfactant, alanines, imidazolinium betaines,
Ampholytic surfactants comprising amidobetaines or betaine acetate are preferred. Specific examples of the amphoteric surfactant include dodecyl betaine, octadecyl betaine, dodecyl carboxymethyl hydroxyethyl imidazolinium betaine, dodecyl dimethyl amino acetate betaine, and fatty acid amidopropyl dimethyl amino acetate betaine.

The amount of the surfactant (B) is preferably from 1 to 10% by mass, more preferably from 3 to 10% by mass, based on the polymer (X). If the amount of the surfactant (B) is too small, the stability of the emulsion may be reduced. If the amount is too large, the wet friction durability of the water / oil repellency of the aqueous dispersion may be reduced. However, when the polymer (X) contains polymerized units of a polymerizable monomer having self-emulsifiability, the amount of the surfactant (B) may be reduced.

The aqueous medium (C) is a medium composed of only water or water and a water-soluble organic solvent. The water-soluble organic solvent in the aqueous medium (C) is selected from acetone, isopropyl alcohol, saturated polyhydric alcohol, (mono or poly) alkyl ether of saturated polyhydric alcohol, and alkylene oxide adduct of saturated polyhydric alcohol. One or more types are preferred, and a saturated polyhydric alcohol and a (mono or poly) alkyl ether of a saturated polyhydric alcohol are particularly preferred. As the saturated polyhydric alcohol, a compound having 2 to 4 hydroxyl groups is preferable, and particularly, ethylene glycol, propylene glycol, glycerin, trimethylolethane or trimethylolpropane is preferable.

Saturated polyhydric alcohol (mono or poly)
As the alkyl ether, a monoalkyl ether of a diol or a dialkyl ether of a diol is preferable, and in particular, diethylene glycol monomethyl ether,
Dipropylene glycol monomethyl ether and dipropylene glycol dimethyl ether are preferred, and diethylene glycol monomethyl ether or dipropylene glycol monomethyl ether is particularly preferred.

The reactants of the saturated polyhydric alcohol with ethylene oxide and / or propylene oxide include:
Dipropylene glycol, tripropylene glycol,
Tetrapropylene glycol or polypropylene glycol in which five or more oxypropylene groups are connected are preferred.

Further, as the water-soluble organic solvent in the aqueous medium (C), ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol,
One or more solvents selected from tetraethylene glycol, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, glycerin, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and polypropylene glycol are also preferable.

The amount of the water-soluble organic solvent in the aqueous medium (C) is preferably from 2 to 50% by mass, more preferably from 5 to 40% by mass, based on the polymer (X). If the amount is too small, the stability of the water / oil repellent composition may be low, and the washing durability may be too large. The amount of the aqueous medium (C) is preferably 1 to 5 times the mass of the total amount of the polymer (X).

The method for producing the water / oil repellent composition of the present invention is as follows.
A raw material composition containing a polymerizable monomer (a ¹ ), a polymerizable monomer (a ² ), a polymerizable monomer (a ³ ), a surfactant (B) and an aqueous medium is emulsified under pressure. After that, a method of polymerizing is preferable. It is preferable to use the above-mentioned aqueous medium (C) as the aqueous medium.

When the polymer (X) in the present invention contains polymerized units of a polymerizable monomer other than the polymerizable monomers (a ¹ ) to (a ³ ), the polymerizable monomer It is preferable to include a polymerizable monomer which is liquid or solid under the emulsification conditions under pressure in the raw material composition in the raw material composition. On the other hand, among the polymerizable monomers other than the polymerizable monomers (a ¹ ) to (a ³ ), the polymerizable monomer which is a gas under the emulsification conditions under pressure emulsifies the raw material composition under pressure. It is preferable to introduce it into the emulsion after the emulsion is formed.

Among the polymerizable monomers other than the polymerizable monomers (a ¹ ) to (a ³ ), the polymerizable monomers which are liquid or solid under the usual emulsification conditions under pressure include: Monomer (a ⁴ ). Further, the polymerizable monomer (a ⁵ )
Contains a polymerizable monomer which is liquid or solid and a polymerizable monomer which is gas under the above-mentioned conditions, and therefore, it is preferable to appropriately use them.

Further, components other than the polymerizable monomer, the aqueous medium, and the surfactant (B) (hereinafter, referred to as other components) may be added to the raw material composition. Other components include a chain transfer agent and a pH adjuster.
Since The chain transfer agent capable of improving various properties of the water and oil repellent composition of the present invention, a compound represented by R ²⁵ SH (However, R ²⁵ in the formula represents an alkyl group having 12 to 18 carbon atoms Is preferably added. The amount of chain transfer agent is
It can be appropriately changed depending on the molecular weight of the polymer (X).

The raw material composition is emulsified under pressure, but usually, it is preferable to pre-emulsify by a method such as stirring. However, in the production method of the present invention, pre-emulsification does not necessarily have to be performed.

The emulsification under pressure is preferably carried out using a high-pressure emulsifier. Examples of the high-pressure emulsifying device include Manton-Gaulin, hydroshear, and microfluidizer. By emulsifying the raw material composition under pressure, an emulsion of a polymerizable monomer is generated. The pressure during emulsification is preferably 1 MPa to 50 MPa (gauge pressure). The temperature of the raw material composition during pressurization is 40 to 80 ° C.
It is preferred that The emulsification under pressure can be carried out only by keeping the raw material composition under pressurized conditions. However, if necessary, stirring or the like may be carried out.

The emulsion formed by emulsification under pressure has a small average particle size of the polymerizable monomer particles contained in the emulsion, is thermodynamically stable, and has a low molecular weight during polymerization. Most have the advantage of reacting efficiently. The average particle size in the emulsion after the pressure emulsification is 0.1.
1-300 nm is preferred. Here, when the polymer (X) in the present invention contains polymerized units of a polymerizable monomer which is gas under the conditions of pressure emulsification, the polymerizable monomer is added to the raw material composition after pressure emulsification. It is preferred to carry out the polymerization after the introduction.

The polymerizable monomer which is gaseous under ordinary pressure emulsification conditions is preferably selected from those listed as the polymerizable monomer (a ⁵ ), and in particular, the following polymerizable monomer (a ⁵⁰ ) is preferred. Polymerizable monomer (a ⁵⁰ ): vinyl halide or vinylidene halide.

The halogen atom in vinyl halide or vinylidene halide is preferably a fluorine atom or a chlorine atom. As the vinyl halide, vinyl chloride, vinyl fluoride, and chlorotrifluoroethylene are preferable, and vinyl chloride is particularly preferable. As the vinylidene halide, vinylidene chloride, vinylidene fluoride and the like are preferable. Further, as the polymerizable monomer (a ⁵⁰ ),
Vinyl chloride or vinyl fluoride is preferred, and vinyl chloride is particularly preferred.

In the present invention, it is preferable that the raw material composition after pressure emulsification is polymerized by an emulsion polymerization reaction. As a method for the emulsion polymerization reaction, a general emulsion polymerization reaction technique can be employed. For example, it is preferable to perform polymerization by adding a polymerization initiator to the raw material composition after pressure emulsification. The polymerization initiator is not particularly limited, and a usual polymerization initiator such as an organic peroxide, an azo compound, a persulfate, or the like, or an ionizing radiation such as γ-ray can be used. The reaction temperature of the polymerization reaction can be appropriately changed depending on the radical initiator used, and is preferably from 30 to 80C. The reaction time is preferably 4 to 70 hours.

According to the production method of the present invention, the polymer (X)
Is dispersed in an aqueous medium (C).
Also called an aqueous dispersion. ) Is obtained. The polymer (X) dispersed in the aqueous medium (C) is preferably dispersed in the form of particles. The average particle size of the particles of the polymer (X) is 0.03
〜0.25 μm is preferred.

The aqueous dispersion obtained by the polymerization reaction may be used as it is as the water / oil repellent composition of the present invention, and may be diluted with water and / or an organic solvent as needed. When diluting, it is preferable to dilute only with water. When an organic solvent is used at the time of dilution, it is preferable to use the water-soluble organic solvent exemplified in the aqueous medium (C). The aqueous dispersion obtained by the method of the present invention has a high stability, and has the advantage that the stability can be maintained even if impurities are present.

The water / repellent composition of the present invention may further contain other components according to the purpose. Other components include additives such as a cross-linking agent, another polymer, another water repellent, another oil repellent, an insect repellent, a flame retardant, an antistatic agent, a dye stabilizer, an anti-wrinkle agent, and the like. As another component, a crosslinking agent is preferable.

As the cross-linking agent, a blocked isocyanate compound, a melamine resin compound, a glyoxal resin compound, a urea resin compound, and a cross-linkable monomer (eg, a blocked product such as N-methylol acrylamide and 2-isocyanatoethyl methacrylate) are essential. Examples include a polymer having a polymerization unit, and a blocked isocyanate compound or a melamine resin compound is preferable.

Here, the blocked isocyanate compound is a compound having no polymerizable unsaturated group, and is preferably a compound obtained by reacting the isocyanate group of the polyisocyanate with the blocking agent. Emulsified blocked isocyanate compounds are commercially available and can be easily obtained. As the melamine resin compound, trimethylol melamine, hexamethylol melamine and the like are preferable.

The water / oil repellent composition of the present invention is preferably used for treating fibers or textile fabrics. As the fiber or fiber woven fabric, 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; Examples include inorganic fibers such as glass fibers and carbon fibers, mixed fibers thereof, and fiber fabrics made of the fibers.

The water- and oil-repellent composition of the present invention exhibits excellent water- and oil-repellency to a light-colored polyamide fiber without any problem such as coloring, and therefore, it is preferable to treat the light-colored polyamide fiber with light-colored polyamide fiber. Particularly preferred. An arbitrary method can be used for the treatment depending on the material of the object to be treated, the preparation form of the water / oil repellent composition, and the like. For example, a method is employed in which the material is adhered to the surface of the object to be processed by a coating method such as dip coating and dried. When applied together with a crosslinking agent, curing may be performed.

The water / oil repellent composition of the present invention exhibits excellent stability even when other compounds are used in combination.
In addition, it exhibits excellent water and oil repellency for washing, dry cleaning, and the like, and imparts excellent water and oil repellency to light-colored polyamide fibers without coloring. Further, by selecting the composition, a water / oil repellent composition is provided which is more advantageous than before in terms of working environment and the like.

[0115]

The mechanism by which the water- and oil-repellent composition of the present invention exhibits excellent performance is not necessarily clear, but includes a polymerized unit of a specific polymerizable monomer (a ² ) in the polymer. By interacting with the polymerized units of (meth) acrylate having a blocked isocyanate group, the quality of the film formed on the surface of the object to be treated is remarkably improved, and the water and water repellency has excellent durability. It is presumed to exhibit oil performance.

[0116]

EXAMPLES The present invention will be specifically described below, but the present invention is not limited thereto. In the following, Reference Examples 1-2
Has a blocked isocyanate group (meth)
Synthesis examples of acrylates, Examples 1 to 6 are Examples, and Examples 7 to 9 are Comparative Examples.

REFERENCE EXAMPLE 1 A four-necked glass flask was equipped with a reflux condenser, a thermocouple thermometer, and a stirrer, and 155 g (1 mol) of 2-isocyanatoethyl methacrylate was added.
Methyl isobutyl ketone (MIBK) was charged as a solvent, and the temperature was raised to 80 ° C. under dry nitrogen. 87 g (1 mol) of methyl ethyl ketoxime was added dropwise and reacted for 2 hours.
242 g of a methyl ethyl ketoxime adduct of 2-isocyanate ethyl methacrylate (MIE) was obtained. From the infrared absorption spectrum (IR) of the product, it was confirmed that the absorption of the isocyanate group had completely disappeared.

Reference Example 2 A four-necked glass flask was equipped with a reflux condenser, a thermocouple thermometer, and a stirrer, charged with 130 g (1 mol) of 2-hydroxyethyl methacrylate, and further charged with 222 g of isophorone diisocyanate (1 mol). 1
Mol), heated to 80 ° C. under dry nitrogen and kept for 3 hours. After stirring for 1 hour, titration confirmed that 50% of the isocyanate groups had been blocked. Further, 87 g (1 mol) of methyl ethyl ketoxime was added dropwise and reacted for 2 hours to obtain 439 g of a methyl ethyl ketoxime adduct (MIP) of a reaction product of 2-hydroxyethyl methacrylate and isophorone diisocyanate. It was confirmed by IR that the absorption of the isocyanate group had completely disappeared.

Example 1 (Example) Perfluoroalkylethyl acrylate [F (CF ₂ ) _n CH ₂ CH ₂ OCOC
H = CH ₂ , where n is a mixture of 6 to 16; Hereinafter, it is referred to as FA. _{] (153g), CH 2 =} CH
COOCH ₂ CH ₂ O ｛CO (CH ₂ ) ₅ O｝ ₄ H (TCE
A, 46 g), MIE (56 g), n-dodecyl mercaptan (DoSH, 4.6 g), polyoxyethylene (1-methylundecyl ether) (PEOLE, 1
2.8 g), dimethyl coconutamine acetate (FDM
C, 1.3 g), dipropylene glycol monomethyl ether (DPGMME, 25.6 g), and ion-exchanged water (380 g) were stirred at 50 ° C. for 30 minutes. Next 40
High-pressure emulsifier while maintaining at ~ 50 ° C (Mantong Gorin)
And emulsified at 40 MPa. The average particle size of the emulsion after emulsification was 0.23 μm.

Next, this was transferred to a 1 L glass autoclave, and azobisisobutyronitrile (3.6 g) was used.
Was added. The inside of the autoclave was purged with nitrogen, and the temperature was raised to 60 ° C. while stirring to carry out a polymerization reaction for 6 hours to obtain a milky white emulsion. The average molecular weight of the polymer in the emulsion was 14,500, the concentration of solids contained in the emulsion was 38.2% by mass, and the average particle size of the polymer was 0.1.
It was 11 μm. Emulsion diluted with ion-exchanged water so as to have a solid concentration of 20% by mass was used as stock solution 1.
And

Example 2 (Example) FA (231 g), T
CEA (7.7 g), MIE (16.6 g), DoSH
(4.6 g), PEOLE (12.8 g), FDMC
(1.3 g), DPGMME (25.6 g), and ion-exchanged water (380 g) were stirred at 50 ° C. for 30 minutes. Next, the mixture was emulsified at 40 MPa using a high-pressure emulsifier (Manton Gorin) while maintaining the temperature at 40 to 50 ° C. The average particle size of the emulsion after emulsification was 0.18 μm.

Next, a polymerization reaction was carried out in the same manner as in Example 1 to obtain a milky white emulsion. The average molecular weight of the polymer in the emulsion was 17000, the concentration of solids contained in the emulsion was 37.8% by mass, and the average particle size of the polymer was 0.08 μm. A solution obtained by diluting the emulsion with ion-exchanged water so that the solid content concentration was 20% by mass was used as a stock solution 2.

Example 3 (Example) FA (239 g), C
H ₂ ＣC (CH ₃ ) COO (CH ₂ CH ₂ O) ₄ H (TEG
MA, 11.5 g), MIE (5.1 g), DoSH
(4.6 g), PEOLE (12.8 g), FDMC
(1.3 g), DPGMME (25.6 g), and ion-exchanged water (380 g) were stirred at 50 ° C. for 30 minutes. Next, the mixture was emulsified at 20 MPa using a high-pressure emulsifier (Manton Gorin) while maintaining the temperature at 40 to 50 ° C. The average particle size of the emulsion after emulsification was 0.19 μm.

Next, a polymerization reaction was carried out in the same manner as in Example 1 to obtain a milky white emulsion. The average molecular weight of the polymer in the emulsion was 15,500, the concentration of solids contained in the emulsion was 38.9% by mass, and the average particle size of the polymer was 0.08 μm. A solution obtained by diluting the emulsion with ion-exchanged water so as to have a solid content concentration of 20% by mass was used as a stock solution 3.

Examples 4 to 6 (Examples) and Examples 7 to 9 (Comparative Examples) A polymerization reaction was carried out in the same manner as in Example 1 using the polymerizable monomers, organic solvents and surfactants shown in Table 1. , Got an emulsion. The emulsion was diluted to obtain stock solutions 4 to 9.

[0126]

[Table 1]

However, the abbreviations in Table 1 are as follows. CHMA: cyclohexyl methacrylate, PCEA: CH ₂ CHCHCOOCH ₂ CH ₂ O {CO (CH ₂ ) ₅ O} ₅ H, PET: CH ₂ CC (CH ₃ ) COO (CH ₂ CH ₂ O) ₁₀ (CH ₂ (CH ₂ CH ₂ CH ₂ O)
_{5 H, M90G: CH 2 =} C (CH 3) COO (CH 2 CH 2 O) 9 CH 3, HEA: 2- hydroxyethyl acrylate, DPG: dipropylene glycol, TPG: tripropylene glycol, B1: wherein b ²⁵ Wherein PEOOE: polyoxyethylene monooleyl ether; StTMAC: trimethyl monooctadecyl ammonium chloride.

[Method for treating cloth] Stock solutions 1 to 9 obtained above
With a solid content of 1.6% by mass, a melamine-based crosslinking agent (trade name: Sumitex Resin M-3) 0.3% by mass, and a catalyst (trade name: Sumitex Accelerator AC)
X) What was diluted with ion-exchanged water so that it might become 0.3 mass% was used as the processing liquid. A nylon taffeta cloth was immersed in the treatment liquid, and the cloth was squeezed between two rubber rollers to adjust the wet pickup to 60% by mass. Then 9 at 110 ° C
It was dried for 0 second and further heat-treated at 170 ° C. for 60 seconds.
The treated cloth after the treatment was evaluated for Bundesmann water repellency, oil repellency, Bundesmann water repellency after washing, oil repellency after washing, and texture by the following methods. The results are shown in Table 4.

[Bundesman water repellency] Evaluation method JIS-
Based on the L1092 rain test (shower method), the water repellency was measured using a Bundesmann rain test device, and the water repellency number shown in Table 2 was used.

[0130]

[Table 2]

[Oil repellency] AATCC-TM118-19
66, and represented by the oil-repellent numbers shown in Table 3.

[0132]

[Table 3]

[Hand] The hand was visually observed.

[Washing treatment method] An automatic reversing spiral electric washing machine (manufactured by Toshiba Corporation; same performance as VH-1150) was used.
800g of test cloth (fabric after processing) of 5cm and 40 ± 2
0.2 mass% weak alkaline detergent at ℃ (JIS-K3
371 (weakly alkaline, Class 1) solution (25 L) and washed under strong conditions for 25 minutes. Next, after dehydration for about 30 seconds by a centrifugal dehydrator, rinsing was performed for 10 minutes while overflowing room temperature water. Thereafter, the sample was again dehydrated for about 30 seconds, rinsed under the same conditions for 10 minutes, and then dehydrated for about 30 seconds. This operation was performed five times to form one set, and the set was repeated 20 times to obtain a test cloth after washing 100 times.

[0135]

[Table 4]

[0136]

The water / oil repellent composition of the present invention exhibits practically excellent performance in terms of water / oil repellency and washing durability.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toyotsu Shimada 1150 Hazawa-cho, Kanagawa-ku, Yokohama, Kanagawa Prefecture Inside Asahi Glass Co., Ltd.

Claims (10)

[Claims] 1. A water / oil repellent composition comprising the following polymer (X), surfactant (B) and aqueous medium (C). Polymer (X): a polymerized unit of the following polymerizable monomer (a ¹ ),
A polymer essentially comprising a polymerized unit of the following polymerizable monomer (a ² ) and a polymerized unit of the following polymerizable monomer (a ³ ). Polymerizable monomer (a ¹ ): (meth) acrylate having a polyfluoroalkyl group. Polymerizable monomer (a ² ): a polymerizable monomer having a polymerizable unsaturated group and a hydroxyl group, and wherein the polymerizable unsaturated group and the hydroxyl group are linked via 7 or more covalent bonds. Mers. Polymerizable monomer (a ³ ): (meth) acrylate having a blocked isocyanate group. Aqueous medium (C): Water or a medium comprising water and a water-soluble organic solvent. 2. The water / oil repellent composition according to claim 1, wherein the surfactant (B) is a surfactant containing a nonionic surfactant in a proportion of 60 to 100% by mass. 3. The polymerizable monomer according to claim 1, wherein the polymerizable monomer (a ² ) is a polymerizable monomer in which a polymerizable unsaturated group and a hydroxyl group are linked via at least 11 covalent bonds. The water / oil repellent composition according to the above. 4. The polymerizable monomer according to claim 1, 2 or 3, wherein the polymerizable monomer (a ² ) is a polymerizable monomer represented by the following formula a ²¹ , a ²² or a ^23. The water / oil repellent composition according to the above. However, the symbols in the formula a ²¹ ~a ²³ have the following meanings. ^{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R 8, R 9: each independently, a hydrogen atom or a methyl group. n: an integer of 2 to 6. m: an integer from 1 to 20. x, y, z: each independently an integer of 0 to 30. However,
x + y + z is an integer of 2 or more. a, b, c: each independently an integer of 0 to 30. However,
a + b + c is an integer of 2 or more. p: an integer of 3 to 6. Embedded image 5. The polymerizable monomer (a ¹ ) in the polymer (X) has a proportion of polymerized units of from 60 to 96% by mass and the polymerizable monomer (a)
5. The water repellent according to claim 1, wherein the proportion of the polymerized unit of ² ) is 2 to 30% by mass and the proportion of the polymerized unit of the polymerizable monomer (a ³ ) is 2 to 20% by mass. Oil repellent composition. 6. The surfactant (B) comprises the following surfactant (b)
¹⁾ ~ (b ⁶⁾ water and oil repellent composition according to claim 1 is a surfactant comprising one or more nonionic surfactant selected from. Surfactant (b ¹ ): a nonionic surfactant composed of polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether, or polyoxyalkylene monoalkapolyenyl ether. Surfactant (b ^2): 1 or more carbon in the molecule - carbon triple bond and at least one hydroxy group, and a nonionic surfactant made of a compound showing the surfactant. Surfactant (b ³ ): a polyoxyethylene portion in which two or more oxyethylenes are continuously connected, and a polyoxyalkylene portion in which two or more oxyalkylenes having 3 or more carbon atoms are continuously connected, And a nonionic surfactant comprising a compound having hydroxyl groups at both ends. Surfactant (b ⁴ ): a nonionic surfactant having an amine oxide moiety in the molecule. Surfactant (b ⁵ ): a nonionic surfactant composed of a condensate of polyoxyethylene mono (substituted phenyl) ether or polyoxyethylene mono (substituted phenyl) ether. Surfactant (b ⁶ ): a nonionic surfactant composed of a fatty acid ester of a polyol. 7. The water / oil repellent composition according to claim 1, further comprising a crosslinking agent. 8. A fiber or fiber woven fabric treated with the water / oil repellent composition according to any one of claims 1 to 7. 9. A polymerizable monomer (a)¹), The following polymerizable monomer
Monomer (a^Two), The following polymerizable monomer (a ^Three), Surfactant
The raw material composition containing (B) and the aqueous medium is mixed with milk under pressure.
A method for producing a water / oil repellent composition which is polymerized and then polymerized. Polymerizable monomer (a¹): Having a polyfluoroalkyl group
(Meth) acrylate. Polymerizable monomer (a^Two): Having a polymerizable unsaturated group and a hydroxyl group
And the polymerizable unsaturated group and the hydroxyl group are 7 or more
A polymerizable monomer linked via a covalent bond. Polymerizable monomer (a^Three): Blocked isocyanate
(Meth) acrylates having groups. 10. The method for producing a water / oil repellent composition according to claim 9, wherein the raw material composition further contains a compound represented by R ²⁵ SH. Here, R ²⁵ in the formula represents an alkyl group having 12 to 18 carbon atoms.