KR20180004750A - Water-repellent oil-repellent composition and method for producing water-repellent and oil-repellent fiber product - Google Patents

Abstract

[식 중, R¹ 및 R²는 각각 독립적으로 수소 원자, 할로겐 원자 또는 메틸기를 나타내고, R³ 및 R⁴는 각각 독립적으로, 옥시기, 카르보닐기 및 하이드록시기로 이루어진 그룹으로부터 선택되는 적어도 1종의 기를 포함하고 있어도 좋은 1가의 함불소 탄화수소기, 또는, 옥시기, 카르보닐기 및 하이드록시기로 이루어진 그룹으로부터 선택되는 적어도 1종의 기를 포함하고 있어도 좋은 불소 원자를 포함하지 않는 탄소수 1 내지 30의 1가의 탄화수소기를 나타내고, R³ 및 R⁴ 중 적어도 한쪽은, 옥시기, 카르보닐기 및 하이드록시기로 이루어진 그룹으로부터 선택되는 적어도 1종의 기를 포함하고 있어도 좋은 1가의 함불소 탄화수소기이고, X¹ 및 X²는 각각 독립적으로 2가의 유기기 또는 단결합을 나타낸다]
화학식 (2)

[식 중, R⁵ 및 R⁶은 각각 독립적으로 수소 원자, 할로겐 원자 또는 메틸기를 나타내고, R⁷은 옥시기, 카르보닐기 및 하이드록시기로 이루어진 그룹으로부터 선택되는 적어도 1종의 기를 포함하고 있어도 좋은, 탄소수 1 내지 30의 1가의 탄화수소기 또는 1가의 함불소 탄화수소기를 나타내고, R⁸은 수소 원자, 할로겐 원자 또는 메틸기를 나타내고, X³은 2가의 유기기 또는 단결합을 나타낸다]
화학식 (3)

[식 중, R⁹ 및 R¹⁰은 각각 독립적으로 수소 원자, 할로겐 원자 또는 메틸기를 나타내고, R¹¹ 및 R¹²는 각각 독립적으로, 옥시기, 카르보닐기 및 하이드록시기로 이루어진 그룹으로부터 선택되는 적어도 1종의 기를 포함하고 있어도 좋은 불소 원자를 포함하지 않는 탄소수 1 내지 30의 1가의 탄화수소기를 나타내고, X⁴ 및 X⁵는 각각 독립적으로 2가의 유기기 또는 단결합을 나타낸다]The water and oil repellent composition of the present invention comprises a monomer (A) represented by the following formula (1), a monomer represented by the following formula (2) and a monomer represented by the following formula (3) And a monomer composition comprising the monomer (B) of the general formula (1).
(1)

Wherein R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or a methyl group, R ³ and R ⁴ each independently represent an alkyl group having at least one kind selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group Or a monovalent hydrocarbon group of 1 to 30 carbon atoms which does not contain a fluorine atom and may contain at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group, a monovalent hydrocarbon group And at least one of R ³ and R ⁴ is a monovalent fluorinated hydrocarbon group which may contain at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group, and X ¹ and X ² are Independently represent a divalent organic group or a single bond]
(2)

Wherein R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom or a methyl group, and R ⁷ is a group having a number of carbon atoms, which may contain at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group, 1 to 30 monovalent hydrocarbon groups or monovalent fluorinated hydrocarbon groups, R ⁸ represents a hydrogen atom, a halogen atom or a methyl group, and X ³ represents a divalent organic group or a single bond]
(3)

Wherein R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom or a methyl group, and R ¹¹ and R ¹² are each independently at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group And X ⁴ and X ⁵ each independently represent a divalent organic group or a single bond, which may be the same or different and each independently represent a hydrogen atom or a monovalent hydrocarbon group of 1 to 30 carbon atoms,

Description

Water-repellent oil-repellent composition and method for producing water-repellent and oil-repellent fiber product

The present invention relates to a water and oil repellent composition capable of imparting water and oil repellency to a textile product, and a method for producing a water and oil repellent textile product.

Conventionally, various water-repellent and oil-soluble components having a perfluoroalkyl group have been proposed for the purpose of imparting water and oil repellency to a fiber product.

In recent years, a water- and oil-repellent component having a perfluoroalkyl group having a carbon number of 8 has been reported to be a perfluorooctanesulfonic acid (C ₈ H ₁₇ SO ₂ F, hereinafter referred to as PFOS (Hereinafter abbreviated as " PFOA ") or perfluorooctanoic acid (C ₇ H ₁₅ COOH, hereinafter abbreviated as PFOA). In addition, as the number of carbon atoms of the perfluoroalkyl group is larger than 8, the influence on the environment is more likely to be concerned. In addition to PFOS and PFOA, perfluoroalkanesulfonic acid or perfluoroalkanoic acid having more than 8 carbon atoms And water-repellent components having a perfluoroalkyl group having not more than 6 carbon atoms are being studied.

As a water and oil-repellent component having a perfluoroalkyl group having 6 or less carbon atoms, for example, Patent Documents 1 and 2 below disclose a water- and oil-repellent component having a perfluoroalkyl group having a perfluoroalkyl group having 6 or less carbon atoms Water-repellent < / RTI >

Patent Document 1: JP-A-2010-001499 Patent Document 2: Japanese Patent Laid-open Publication No. 2012-503028

The water- and oil-repellent component having a perfluoroalkyl group having a carbon number of 6 or less tends to be poor in water and oil repellency and durability as compared with a compound having a carbon number of 8 or more. In Patent Documents 1 and 2, in order to improve the durability of water-repellent and oil-repellent properties and the texture of a workpiece, it is preferable that a specific monomer containing a polyfluoroalkyl group and a specific monomer containing no polyfluoroalkyl group It is disclosed that a monomer is copolymerized.

However, even with the water- and oil-repellent components described in Patent Documents 1 and 2, it is difficult to simultaneously satisfy water and oil repellency, durability thereof, and improvement in touch feeling of workpieces.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a water and oil repellent composition which can impart good water and oil repellency and durability and feel, and a method for producing a water and oil repellent fiber product using the same.

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted intensive studies to solve the above problems and have found that a water- and oil-repellent composition containing a copolymer obtained by copolymerizing a specific monomer composition as a water- The present invention has been accomplished on the basis of this finding based on the discovery that good water and oil repellency and durability and feel can be imparted to the composition.

The water and oil repellent composition of the present invention comprises a monomer (A) represented by the following formula (1), a monomer represented by the following formula (2) and a monomer represented by the following formula (3) And a monomer composition comprising the monomer (B) of the general formula (1).

(1)

Wherein R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or a methyl group, R ³ and R ⁴ each independently represent an alkyl group having at least one kind selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group Or a monovalent hydrocarbon group of 1 to 30 carbon atoms which does not contain a fluorine atom and may contain at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group, a monovalent hydrocarbon group R < ³ > and R < ⁴ > At least one of them is a monovalent fluorinated hydrocarbon group which may contain at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group, X ¹ and X ² each independently represents a divalent organic group or a group Lt; / RTI >

(2)

Wherein R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom or a methyl group, and R ⁷ is a group having a number of carbon atoms, which may contain at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group, 1 to 30 monovalent hydrocarbon groups or monovalent fluorinated hydrocarbon groups, R ⁸ represents a hydrogen atom, a halogen atom or a methyl group, and X ³ represents a divalent organic group or a single bond]

(3)

Wherein R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom or a methyl group, and R ¹¹ and R ¹² are each independently at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group And X ⁴ and X ⁵ each independently represent a divalent organic group or a single bond, which may be the same or different and each independently represent a hydrogen atom or a monovalent hydrocarbon group of 1 to 30 carbon atoms,

According to the water and oil-repellent agent composition of the present invention, good water and oil repellency, durability and texture can be imparted to textile products and the like by containing the copolymer having the above-mentioned constitution.

In the water and oil repellent composition of the present invention, it is preferable that R ³ and R ⁴ in the formula (1) are at least one kind selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group Is preferably a monovalent fluorinated hydrocarbon group which may contain a group of the formula

From the viewpoint of water and oil repellency and durability, it is preferable that R ³ and R ⁴ in the above formula (1) are a perfluoroalkyl group having 2 to 18 carbon atoms, a group represented by the following formula (4) ) Is preferable.

(4)

C _m F _{(2m + 1)} (CH ₂ ) _p O (R ¹³ O) _n -

Wherein m represents 2 to 18, p represents 0 or 1 to 5, R ¹³ represents a perfluoroalkylene group having 2 to 5 carbon atoms, and n represents a perfluoroalkyl group represented by (R ¹³ O) The average addition mole number of the phenoxy group is 1 to 10]

(5)

F (R < ¹⁴ > O) _s-

[, R ¹⁴ in the formula is an alkylene group of a perfluoroalkyl group having 1 to 5, s is (R ¹⁴ O) a perfluoroalkyl represents an average addition mole number of the alkylene group represented by, from 1 to 10;

In the water and oil repellent composition of the present invention, R ⁷ in the formula (2) and R ¹¹ and R ¹² in the formula (3) are preferably a straight chain alkyl group having a carbon number of 8 to 30, a carbon number of 8 to 30 Branched chain alkyl group, or a cyclic alkyl group having 8 to 30 carbon atoms.

Further, in the water and oil-repellent composition of the present invention, the monomer composition may further comprise at least one monomer (C) selected from the group consisting of vinyl chloride and vinylidene chloride.

The present invention also provides a method for producing a water- and oil-repellent fiber product, which comprises the step of treating a fiber product with a treatment liquid comprising the water and oil repellent composition according to the present invention.

According to the present invention, it is possible to provide a water and oil-repellent composition capable of imparting good water and oil repellency, durability and feel, and a method of manufacturing a water and oil repellent fiber product using the same. The water and oil repellent composition of the present invention can impart good water and oil repellency and durability and feel to a textile product as compared with conventional water and oil repellent components having a perfluoroalkyl group having 6 or less carbon atoms. The durability of the water and oil repellency imparted by the water and oil repellent composition of the present invention is excellent in washing resistance and abrasion resistance. That is, the water and oil repellency imparted to the textile product by the water and oil repellent composition of the present invention may be less likely to be deteriorated by washing, friction or the like.

Hereinafter, the present invention will be described in detail. In the present specification, alkyl (meth) acrylate means both of alkyl acrylate and alkyl methacrylate.

The water and oil repellent composition of the present embodiment is a composition comprising a monomer (A) represented by the following formula (1), a monomer represented by the following formula (2) and a monomer represented by the following formula (3) And a monomer composition containing one type of monomer (B).

(1)

Wherein R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or a methyl group, R ³ and R ⁴ each independently represent an alkyl group having at least one kind selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group Or a monovalent hydrocarbon group of 1 to 30 carbon atoms which does not contain a fluorine atom and may contain at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group, a monovalent hydrocarbon group R < ³ > and R < ⁴ > At least one of them is a monovalent fluorinated hydrocarbon group which may contain at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group, X ¹ and X ² each independently represents a divalent organic group or a group Lt; / RTI >

(2)

Wherein R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom or a methyl group, and R ⁷ is a group having a number of carbon atoms, which may contain at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group, 1 to 30 monovalent hydrocarbon groups or monovalent fluorinated hydrocarbon groups, R ⁸ represents a hydrogen atom, a halogen atom or a methyl group, and X ³ represents a divalent organic group or a single bond]

(3)

Wherein R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom or a methyl group, and R ¹¹ and R ¹² are each independently at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group And X ⁴ and X ⁵ each independently represent a divalent organic group or a single bond, which may be the same or different and each independently represent a hydrogen atom or a monovalent hydrocarbon group of 1 to 30 carbon atoms,

The monomer (A) represented by the above formula (1) is preferably a monomer in which R ¹ and R ² are hydrogen atoms from the viewpoint of versatility of the raw material and safety of the product after decomposition.

The monomer (A) represented by the above formula (1) is preferably a monomer (A) represented by the formula (1) in which both R ³ and R ⁴ are an oxy group, a carbonyl group and a hydroxy group (4), or a group represented by the following formula (5): " (5) " R < 1 > Is more preferable.

(4)

C _m F _{(2m + 1)} (CH ₂ ) _p O (R ¹³ O) _n -

Wherein m represents 2 to 18, p represents 0 or 1 to 5, R ¹³ represents a perfluoroalkylene group having 2 to 5 carbon atoms, and n represents a perfluoroalkyl group represented by (R ¹³ O) The average addition mole number of the phenoxy group is 1 to 10]

(5)

F (R < ¹⁴ > O) _s-

[, R ¹⁴ in the formula is an alkylene group of a perfluoroalkyl group having 1 to 5, s is (R ¹⁴ O) a perfluoroalkyl represents an average addition mole number of the alkylene group represented by, from 1 to 10;

The monomer (A) represented by the above formula (1) is preferably a perfluoroalkyl group having 2 to 6 carbon atoms, both of R ³ and R ⁴ , M is 2 to 6, p is 2 to 4 (preferably 2 to 3, more preferably 2), n is 1 to 10, or s in the above formula (5) is 1 More preferably from 10 to 10 carbon atoms. Of these, from the viewpoints of water-repelling and oil repellency and durability (particularly washing resistance and abrasion resistance), both R ³ and R ⁴ are more preferably perfluoroalkyl groups having 2 to 6 carbon atoms, and perfluoro Lt; / RTI > alkyl group. It is preferable that both R ³ and R ⁴ in the formula (4) have 2 to 6, p is 2 to 4 (preferably 2 to 3, more preferably 2), and n Is more preferably a group having 1 to 5 carbon atoms or a group having 1 to 5 carbon atoms in the above formula (5).

When X ¹ and X ² in the above formula (1) are divalent organic groups, examples of divalent organic groups include -OR ¹⁵ -, -NH-R ¹⁶ -, -R ¹⁷ - (provided that R ¹⁵ and R ¹⁶ And R ¹⁷ represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms), -OR ¹⁸ -N (R ¹⁹ ) -SO ₂ -, -OR ²⁰ -SO ₂ -R ²¹ -, -OR ²² -SR ²³ -, and -OR ²⁴ -N (H) C (O) - wherein R ¹⁸ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ represent a single bond or a divalent hydrocarbon group of 1 to 10 carbon atoms , And R ¹⁹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). Among these, X ¹ and X ² are preferably -OR ¹⁵ - from the viewpoints of ease of production and functionality (in particular, water repellency). In ^{addition, R 15, R 16, R} 17, R 18, R 20, R 21, R 22, R 23 and R ²⁴ are, from the point of view of ease of manufacture and function (especially durable water repellent), 2 of 2 to 4 carbon atoms , More preferably a divalent hydrocarbon group having 2 to 3 carbon atoms (still more preferably an ethylene group).

The water and oil repellent composition containing the copolymer obtained by copolymerizing the monomer composition containing the monomer (A) and the monomer (B) according to the present embodiment can be obtained by mixing the monomer (A) and the monomer (B) (Particularly, washability and abrasion resistance) tend to be improved as compared with a water- and oil-repellent composition containing a polymer obtained by polymerizing a monomer composition containing only a monomer (A). A monomer represented by the above formula (2) as a monomer (B), it is preferred in terms of versatility of the raw materials, R ⁵ and R ⁶ is a hydrogen atom. R ⁷ in the formula (2) is preferably a monovalent hydrocarbon group of 1 to 30 carbon atoms which does not contain a fluorine atom and may contain at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group, Or a monovalent fluorinated hydrocarbon group of 1 to 30 carbon atoms which may contain at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group.

A monomer represented by the above formula (2), R ⁷ is an oxy group, a carbonyl group and a hydroxy group may contain a group of at least one member selected from the group consisting good that do not contain fluorine atom having 1 to monovalent hydrocarbon group of 30 It is preferable that R ⁷ is a straight chain alkyl group having 8 to 30 carbon atoms, a branched chain alkyl group having 8 to 30 carbon atoms, or a straight chain alkyl group having 8 to 30 carbon atoms, in view of water and oil repellency and durability (particularly washing resistance and abrasion resistance) To 30 carbon atoms. Of these, from the viewpoints of water-repelling and oil repellency and durability (particularly washing resistance and abrasion resistance) and feeling, it is more preferable to be a straight chain or branched chain alkyl group having from 16 to 22 carbon atoms. In addition, if the monomer represented by the above formula (2), R ⁷ is an oxy group, a carbonyl group and hydroxyl may include groups of at least one member selected from the hydroxy group the group consisting of a good C1 also monovalent to 30 fluorinated hydrocarbon group (4), or a group represented by the formula (5): wherein R ⁷ is a perfluoroalkyl group having 2 to 18 carbon atoms, a group represented by the formula It is preferable that the period is displayed.

Further, the monomers, good reactivity, from the viewpoint of flexibility of the textile product obtained, R ⁸ is preferably a hydrogen atom, and water and oil repellency and its durability (in particular washing resistance and abrasion resistance) of the formula (2) , It is preferable that R ⁸ is a methyl group or a halogen atom (especially a chlorine group). Of the methyl groups and halogen atoms, methyl groups are preferable from the viewpoints of flexibility and cost.

When X ³ in the formula (2) is a divalent organic group, examples of the divalent organic group include -OR ²⁵ -, -SO ₃ N-, -NH-R ²⁶ -, and -R ²⁷ - ²⁵ , R ²⁶ And R ²⁷ represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms), -OR ²⁸ -N (R ²⁹ ) -SO ₂ -, -OR ³⁰ -SO ₂ -R ³¹ -, -OR ³² -SR ³³ -, and -OR ³⁴ -N (H) C (O) - (wherein R ²⁸ , R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ represent a single bond or a divalent hydrocarbon group of 1 to 10 carbon atoms , And R ²⁹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Among these, in view of ease of manufacture and function (especially durable water repellent), X ³ is -OR ²⁵ -, or -NH-R ²⁶ - is more preferable that the-in is desired, and -OR ^25. In ^{addition, R 25, R 26, R} 27, R 28, R 30, R 31, R 32, R 33 and R ³⁴ are, from the point of view of ease of manufacture and function (especially durable water repellent), 2 of 2 to 4 carbon atoms , More preferably a divalent hydrocarbon group having 2 to 3 carbon atoms (still more preferably an ethylene group).

A monomer represented by the chemical formula 3 as the monomer (B) is, in terms of ease of manufacture and function (particularly water repellency durability), it is preferred that R ⁹ and R ¹⁰ is a hydrogen atom.

The monomers represented by the above formula (3) are preferably those in which R ¹¹ and R ¹² are each a straight chain alkyl group having 8 to 30 carbon atoms, a straight chain alkyl group having a carbon number A branched alkyl group having 8 to 30 carbon atoms, or a cyclic alkyl group having 8 to 30 carbon atoms, and more preferably a linear or branched alkyl group having 16 to 22 carbon atoms.

When X ⁴ and X ⁵ in the above formula (3) are divalent organic groups, examples of divalent organic groups include -OR ³⁵ -, -SO ₃ N-, -NH-R ³⁶ -, and -R ³⁷ - However, R ^35, R ³⁶ and R ³⁷ represents a divalent hydrocarbon group of a single bond or a carbon number of 1 to ^{10), -OR 38 -N (R} 39) -SO 2 -, -OR 40 -SO 2 -R 41 - , -OR ⁴² -SR ⁴³ - and -OR ⁴⁴ -N (H) C (O) -, provided that R ³⁸ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are a single bond, 10, and R ³⁹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), and the like. Among these, in view of ease of manufacture and function (especially durable water repellent), X ⁴ and X ⁵ is -OR ³⁵ -, or -NH-R ³⁶ - is preferable, and, -OR ³⁵ - is more preferable that the. In ^{addition, R 35, R 36, R} 37, R 38, R 40, R 41, R 42, R 43 and R ⁴⁴ are, from the point of view of ease of manufacture and function (especially durable water repellent), 2 of 2 to 4 carbon atoms , More preferably a divalent hydrocarbon group having 2 to 3 carbon atoms (still more preferably an ethylene group).

Among the above monomers, monomers (B) are preferably at least one kind of monomers represented by the above formula (2) from the viewpoints of water-repelling and oil repellency and durability (particularly wash resistance and abrasion resistance) and feeling.

In the present embodiment, it is preferable to use a monomer represented by the following formula (B-1) as the monomer (B) from the viewpoint of water and oil repellency and durability (especially washing resistance and abrasion resistance) and feeling.

The formula (B-1)

CH ₂ = C (R ⁸ ) (COOR ⁷ )

Wherein, R ⁷ and R ⁸ are as defined above, to in terms of the caregiver oil and texture, preferably, R ⁸ is a hydrogen atom addition R ⁷ a carbon number of 8 to 30 straight chain alkyl or C2 to the More preferably, R ⁸ is a hydrogen atom and R ⁷ is a perfluoroalkyl group having a carbon number of 12 to 22 (more preferably, from the viewpoint of water-repellent and oil repellency and durability (particularly wash resistance and abrasion resistance) Preferably 16 to 22) straight-chain alkyl groups. In the present embodiment, from the viewpoints of water and oil repellency and durability (especially washing resistance and abrasion resistance) and feeling, it is preferable that R ⁸ is a hydrogen atom and R ⁷ is a hydrocarbon group having 12 to 22 carbon atoms Is a straight chain alkyl group of 16 to 22 carbon atoms and a monomer in which R ⁸ is a hydrogen atom and R ⁷ is a perfluoroalkyl group having 2 to 18 carbon atoms.

The copolymer according to the present embodiment contains the monomer (A) and the monomer (B) as a copolymerization component, which makes it possible to improve water repellency and durability (particularly, washability And a durability (in particular, washing resistance and abrasion resistance) and a feeling of touch are improved as compared with the copolymer of the monomer (A) and the short chain vinyl alkyl ether or the short chain carboxylate. There is a tendency to improve. In addition, the copolymer according to the present embodiment has an advantage that it can be obtained in a shorter reaction time than in the case of reacting the monomer (A) with a vinyl alkyl ether or a vinyl carboxylate.

In the monomer composition of the present embodiment, the mixing ratio (mass ratio) of the monomer (A) to the monomer (B) is preferably from (A): (B) is preferably 10:90 to 90:10, and more preferably 20:80 to 80:20.

The monomer composition according to the present embodiment preferably further comprises at least one monomer (C) selected from the group consisting of vinyl chloride and vinylidene chloride from the viewpoints of durability (in particular, washing resistance and abrasion resistance) .

In this case, the blending amount of the monomer (C) should preferably be such that the total mass of the monomers (A) and (B) and the mass of the monomers (C) are different from the viewpoints of water and oil repellency and durability (especially washing resistance and abrasion resistance) (C) is preferably from 95: 5 to 70:30, and more preferably from 90:10 to 80:20, in terms of mass ratio [(A) + (B)].

The monomer composition according to the present embodiment can be copolymerized with a monomer other than the monomer (A), the monomer (B) and the monomer (C) for the purpose of imparting functionalities such as adhesiveness, adhesion and abrasion resistance to the resulting copolymer. And may contain other monomer (D).

Examples of the other monomer (D) include vinyl acetate, styrene,? -Methylstyrene, p-methylstyrene, glycidyl (meth) acrylate, (meth) acrylamide, N, (Meth) acrylamide, methylol diacetone (meth) acrylamide, N-methylol (meth) acrylamide, 3-chloro-2-hydroxypropyl (meth) acrylate, vinyl alkyl ether, halogenated alkyl vinyl ether (Meth) acrylates such as vinyl alkyl ketone, butadiene, isoprene, chloroprene, aziridinyl ethyl (meth) acrylate, aziridinyl (meth) acrylate, polyoxyalkylene , 2-ethylhexyl polyoxyalkylene (meth) acrylate, polyoxyalkylene di (meth) acrylate, triallyl cyanurate, allyl glycidyl ether, allyl acetate, N-vinylcarbazole, maleimide, N - methylmaleimide, (2-dime (Meth) acrylate having a side chain of silicon such as amino (meth) acrylate, aminoethyl (meth) acrylate, glycerol (meth) acrylate, alkylene di (meth) acrylate, vinylsilane, and trimethoxysilyl (Meth) acrylate having a polysiloxane, (meth) acrylate having a blocked isocyanate group, and (meth) acrylate having a urethane bond. Of these monomers, monomers having a reactive group capable of reacting with a melamine resin, an isocyanate compound, or a glyoxal resin are preferred.

The other monomers (D) may be used singly or in combination of two or more.

When butyl (meth) acrylate is used as the monomer (B), and styrene is used as the monomer (D), an alkyl (meth) acrylate having 8 to 30 carbon atoms is used as the monomer (B) Compared to inferior, but relatively good performance can be obtained. In this case, the mixing ratio (molar ratio) of the monomer (A) to the butyl (meth) acrylate and styrene is preferably 1: 1: 1 to 3: 1, : 1: 1.2 to 2.5, more preferably 1: 1: 2.3.

In the copolymer according to the present embodiment, the arrangement of the monomers (structural units) is not particularly limited, and it may be a random copolymer, a block copolymer or an alternate copolymer.

In the copolymer according to the present embodiment, when the monomer remains after the polymerization reaction described later, it is preferable to remove the monomer by a method such as reduced pressure distillation if necessary.

The copolymer according to the present embodiment preferably has a melt viscosity of 5 to 20,000 Pa · s at 105 ° C, and more preferably 10 to 10000 Pa · s. When the melt viscosity is within the above range, water repellency and durability (particularly, wash resistance and abrasion resistance), feel and processing stability are easily obtained at a high level. When the melt viscosity is less than 5 Pa · s, the water repellency and durability (particularly washing resistance and abrasion resistance) tend to decrease. When the melt viscosity exceeds 20,000 Pa · s, the water repellency and durability (especially wash resistance and abrasion resistance) Tends to lower, toughen (cure) the texture, or lower the processing stability.

The melt viscosity can be measured using a flow tester CFT-500D (manufactured by SHIMADZU) at a measurement temperature of 105 占 폚.

The copolymer according to this embodiment can be obtained by applying a conventionally known copolymerization method. For example, a solution polymerization method using an organic solvent as a solvent, an emulsion polymerization method using water as a solvent, and an organic solvent or various surfactants.

Examples of the organic solvent include aliphatic alcohols having 1 to 8 carbon atoms such as methanol, ethanol, isopropanol, n-butanol, 2-butanol, t-butanol, n-hexanol, 2-ethylhexanol and glycerin; Glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol and tripropylene glycol; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl Glycol ethers such as ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and 3-methoxy-3-methyl-1-butanol; Glycol esters such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate; hydrocarbons such as n-hexane, isohexane, cyclohexane, methylcyclohexane, n-heptane, isooctane, n-decane, mineral taphene, terphenyl oil, isoparaffin, toluene, xylene and solvent naphtha; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone and diacetone alcohol; Esters such as ethyl acetate, methyl acetate, butyl acetate, methyl lactate, and ethyl lactate; Ethers such as diethyl ether, diisopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, dioxane, methyl tertiary butyl ether, butyl carbitol, and tetrahydrofuran; Dimethylformamide, DMSO, propylene carbonate, dimethyl carbonate, halogen compounds, nitrogen compounds, sulfur compounds, inorganic solvents, organic acids, and the like. Among these, at least one selected from the group consisting of glycols and glycol ethers is preferable from the viewpoints of water and oil repellency, product stability, treatment liquid stability, and penetration into the fiber product of the treatment liquid, and dipropylene glycol, tri Propylene glycol, polypropylene glycol (average molecular weight: 200 to 4000) and dipropylene glycol monomethyl ether are more preferable.

These solvents may be used singly or in combination of two or more. When two or more kinds are used in combination, it is preferable to use them in combination with water. The use of a mixed solvent is preferable because it is easy to control the solubility and emulsion and dispersibility of the copolymer and control of permeability into a fiber product is easy at the time of treatment.

As the surfactant, it is preferable to use a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or the like.

Examples of the cationic surfactant include a monoalkyltrimethylammonium salt having 8 to 24 carbon atoms, a dialkyldimethylammonium salt having 8 to 24 carbon atoms, a monoalkylamine acetic acid salt having 8 to 24 carbon atoms, a dialkylamine acetic acid salt having 8 to 24 carbon atoms, 24 alkyl imidazoline quaternary salts, and the like. Of these, monoalkyltrimethylammonium salts having 12 to 18 carbon atoms and dialkyldimethylammonium salts having 12 to 18 carbon atoms are preferred from the viewpoints of emulsification and processing stability.

These cationic surfactants may be used singly or in combination of two or more.

Examples of the nonionic surfactant include alkylene oxide adducts of alcohols, polycyclic phenols, amines, amides, fatty acids, polyhydric alcohol fatty acid esters, fats and polypropylene glycols and the like.

Examples of the alcohols include linear or branched alcohols or alkenols having 8 to 24 carbon atoms, and acetylene alcohols represented by the following formula (6).

(6)

Wherein R ⁴⁵ and R ⁴⁶ each independently represent a linear or branched alkyl group having 1 to 8 carbon atoms or an alkenyl group having a linear or branched chain having 2 to 8 carbon atoms,

Examples of the polycyclic phenols include monovalent phenols such as phenol and naphthol which may have a hydrocarbon group of 1 to 12 carbon atoms or their styrene (styrene,? -Methylstyrene, vinyltoluene) adducts or their benzyl chloride reaction products have. Examples of the amines include linear or branched aliphatic amines having 8 to 44 carbon atoms.

Examples of amides include straight chain or branched chain fatty acid amides having 8 to 44 carbon atoms.

Examples of the fatty acids include straight chain or branched chain fatty acids having 8 to 24 carbon atoms.

Examples of the polyhydric alcohol fatty acid esters include a condensation reaction product of a polyhydric alcohol with a straight chain or branched chain fatty acid having 8 to 24 carbon atoms.

Examples of the fats include vegetable oils, animal fats, vegetable waxes, animal waxes, mineral waxes, and hydrogenated oils.

Of these, from the viewpoint that the effect on the water and oil repellency is small, the effect on the light resistance is small and the emulsifying property of the copolymer is good, an alcohol or an alkene having 8 to 24 carbon atoms in the straight chain or branched chain, Acetylenic alcohol represented by the above formula (6) is more preferable, and acetylenic alcohol represented by the above formula (6) is more preferable.

Examples of the alkylene oxide include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,4-butylene oxide, styrene oxide and epichlorohydrin. have. Ethylene oxide and 1,2-propylene oxide are preferable, and ethylene oxide is more preferable as the alkylene oxide from the viewpoint that the effect on the water-repellent oil-repellent is small and the emulsifying property of the copolymer becomes good.

The number of moles of the alkylene oxide added is preferably from 1 to 200, more preferably from 3 to 100, and still more preferably from 5 to 50. When the number of moles of alkylene oxide added is within the above range, water-oil repellency and product stability can be easily obtained at a high level. When the addition mole number of the alkylene oxide is less than 1 mole, the product stability tends to be lowered and the water / oil repellency tends to decrease. When it exceeds 200 mols, the water / oil repellency tends to decrease.

In the copolymer according to the present embodiment, when a nonionic surfactant having an HLB of 6 to 20 is used as the nonionic surfactant, a better aqueous dispersion can be obtained. Here, HLB is based on HLB of Griffin, and Griffin's equation is changed to the following equation. Here, the hydrophilic group refers to an ethylene oxide group.

HLB = (hydrophilic group x 20) / molecular weight

These nonionic surfactants may be used singly or in combination of two or more kinds. In the case of using a combination of two or more kinds, when a nonionic surfactant is used so that the weighted average HLB is 8 to 16, a better water dispersion can be obtained.

These surfactants may be used singly or in combination of two or more. In view of emulsion dispersibility of the monomers during copolymerization, emulsion dispersibility of the copolymer, stability of the treatment solution, and water repellency and oil repellency, It is preferable to use a cationic surfactant and a nonionic surfactant in combination.

Such a surfactant is preferably contained in an amount of 1 to 20 mass% with respect to the copolymer, and is preferably contained in an amount of 3 to 16 mass% with respect to the copolymer. When the blending amount of the surfactant is within the above range, the processing stability, water-repellent and oil-repellent properties and durability (particularly, washing resistance and abrasion resistance) can be easily obtained at a high level. If it is less than 1% by mass, the processing stability tends to be lowered. When it exceeds 20% by mass, the water and oil repellency and the durability thereof (particularly, washing resistance and abrasion resistance) tend to decrease.

In the present embodiment, it is preferable to prepare a copolymer by emulsion polymerization in a solvent containing water. The solution or emulsion dispersion of the copolymer thus obtained may be used as it is or may be diluted. Further, the copolymer may be separated and dissolved or emulsified and dispersed in a solvent.

In the present embodiment, it is preferable to preliminarily emulsify using a high-pressure emulsifier or the like before the initiation of the polymerization reaction. For example, a mixture composed of a monomer, a surfactant, an organic solvent, water and the like is preferably mixed and dispersed with a homomixer or a high-pressure emulsifier. Mixing and dispersing the raw material mixture before the initiation of the polymerization is preferable because the stability of the water-repellent and oil-repellent component of the finally obtained water / oil repellent composition is improved.

At the start of the polymerization reaction, heat, light, radiation, a radical polymerization initiator, and an ionic polymerization initiator are preferably used. Particularly, a water-soluble or oil-soluble radical polymerization initiator is preferable, and general initiators such as an azo-based polymerization initiator, a peroxide-based polymerization initiator, and a redox-based initiator can be used depending on the polymerization temperature. The polymerization initiator is preferably an azo-based compound, and when polymerization is carried out in a solvent using water, a salt of an azo-based compound is more preferable. The polymerization temperature is not particularly limited, but is preferably 20 to 150 占 폚, more preferably 40 to 90 占 폚.

In the polymerization reaction, a molecular weight regulator may be used. As the molecular weight regulator, aromatic compounds or mercaptans are preferable, and alkylmercaptans are more preferable.

In the water and oil repellent composition of the present embodiment, it is preferable that the copolymer is dispersed as particles in a solvent. The average particle diameter in this case is preferably from 10 to 1,000 nm, more preferably from 50 to 300 nm, and even more preferably from 80 to 200 nm from the viewpoints of water and oil repellency and product stability.

The average particle diameter was measured using a laser diffraction / scattering type particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho Co., Ltd.), and the percentage integrated value of the particle diameter of the ultraviolet absorber for fibers was 50% And measuring the average particle size of the particles.

The water and oil repellent composition of the present embodiment preferably contains a solvent from the viewpoint of ease of handling. As such a solvent, a solvent equivalent to a solvent usable for obtaining the copolymer can be used.

Among them, it is preferable to use the same solvent as the copolymer from the same viewpoint.

The content of the solvent in the water and oil repellent composition is preferably 50 to 90% by mass, more preferably 55 to 75% by mass, based on the total amount of the composition.

When the water and oil repellent composition contains an organic solvent, the content of the organic solvent is preferably 1 to 20% by mass, more preferably 5 to 15% by mass, based on the total amount of the composition.

In the present embodiment, the water-repellent and oil-repellent fiber product can be obtained by treating the fiber product with the treatment liquid containing the water and oil repellent composition of the present embodiment. The water and oil repellent composition of the present embodiment can be used as a treatment liquid as it is, or can be diluted with water or an organic solvent to prepare a treatment liquid.

It is preferable that the treatment liquid according to the present embodiment contains 0.3 to 5% by mass of the water and oil repellent composition of the present embodiment from the viewpoint that the amount of the water and oil repellent composition to the fiber product is easily controlled.

The treatment liquid according to the present embodiment preferably includes an organic solvent. As such an organic solvent, an organic solvent equivalent to an organic solvent usable for obtaining the copolymer can be used. Of these, isopropyl alcohol and diethylene glycol monobutyl ether can be suitably used from the viewpoints of processing stability and permeability into textile products.

Such an organic solvent is preferably contained in the treatment liquid in an amount of 0.3 to 3 mass%, more preferably 0.5 to 1.5 mass%, based on the total amount of the treatment liquid.

The water and oil repellent composition of the present embodiment preferably has a pH of 2.0 to 6.0 from the viewpoints of water and oil repellency, texture, and processing stability. The pH of the treatment liquid according to the present embodiment is preferably 3.0 to 7.0, more preferably 4.0 to 6.0 from the viewpoints of water and oil repellency, texture, and processing stability.

The pH of the water and oil repellent composition according to the present embodiment and the treatment liquid according to the present embodiment can be adjusted to any desired pH by using a pH adjuster. Examples of such a pH adjuster include acids such as formic acid, acetic acid, malic acid, and citric acid; Alkaline substances such as caustic soda, sodium carbonate, and ammonia water can be used. Of these, it is preferable to adjust the pH using acetic acid and malic acid.

When the fiber product is treated with the treatment liquid according to the present embodiment, the treatment liquid may contain a wetting agent, an antifoaming agent, an antistatic agent, a texture adjusting agent, a melamine resin, an isocyanate compound, a glyoxal resin, a catalyst, May be used in combination.

As the melamine resin, a compound having a melamine skeleton can be used. Examples thereof include polymethylol melamine such as trimethylol melamine and hexamethylol melamine; Alkoxymethyl melamine in which a part or all of the methyl group of polymethylol melamine is an alkoxymethyl group having an alkyl group having 1 to 6 carbon atoms; And acyloxymethyl melamine in which some or all of the methylol groups of polymethylolmelamine are acyloxymethyl groups having acyl groups having 2 to 6 carbon atoms. These melamine resins may be any of monomers or dimers of dimers or higher, or a mixture thereof. Also, a co-condensation of an element or the like with a part of melamine can be used. Examples of such melamine resins include betamycin M-3, betamycin M-3 (60), betamycin MA-S, betamycin J-101, and betamycin J-60 manufactured by DIC Kabushiki Kaisha -101 LF, UNIKA RESIN 380K manufactured by Union Kagakuko Kogyo Co., Ltd., Riken Resin MM series manufactured by MIKI RIKEN KOGYO CO., LTD., And the like.

The isocyanate compound is not particularly limited as long as it has at least two isocyanate groups in the molecule, and known polyisocyanate compounds can be used. Examples thereof include diisocyanate compounds such as alkylene (preferably having 1 to 12 carbon atoms) diisocyanate, aryldiisocyanate and cycloalkyldiisocyanate, and modified polyisocyanate compounds such as dimers or trimers of these diisocyanate compounds .

The modified polyisocyanate compound derived from the diisocyanate compound is not particularly limited as long as it has two or more isocyanate groups and includes, for example, a buret structure, an isocyanurate structure, a urethane structure, a uretdione structure, Structure, trimer structure and the like, and adducts of aliphatic isocyanate of trimethylol propane. Polymeric MDI (MDI = diphenylmethane diisocyanate) can also be used as the polyisocyanate compound. These isocyanate compounds may or may not be blocked with an isocyanate group as a block.

Commercially available polyisocyanate compounds can be used. Examples of commercially available polyisocyanate compounds include BASONATO series manufactured by BASF Corporation, BYHIDULUM series, SBU isocyanate series, DEG MODULAR series, and SUMIDUL series , &Quot; Dyuranate " series manufactured by Asahi Kasei Chemicals Co., Ltd., and " Coronate series " manufactured by Tosoh Corporation, and the "Aquanate" series manufactured by Nippon Polyurethane Industry Co., NK assistant IS-100, NK assist IS-80, NK assist V, and NK assistant series manufactured by Nikkaki Kagaku Co., Ltd., such as "BUNOK" series manufactured by DIC Corporation, NY, NK assist NY-27, NK assist NY-30, and NK assist NY-50.

As the glyoxal resin, conventionally known ones can be used, and examples thereof include 1,3-dimethylglyoxal urea resin, dimethyloldihydroxyethylene urea resin, dimethylol dihydroxypropylene urea resin and the like. The functional groups of these resins may be substituted with other functional groups. Examples of such glyoxal resins include betamycin N-80, betamycin NS-11, betamycin LF-K, betamycin NS-19, betamycin LF-55P cone, betamycin NS -210 L, BETAMAKIN NS-200, and BETAKAMINE NF-3, UNILESIN GS-20E manufactured by Union Kakako Kogyo Co., Ltd., Riken Resin RG series manufactured by MIKI RIKEN KOGYO KABUSHIKI KAISHA, and Riken Resin MS Series And the like.

As the melamine resin and the glyoxal resin, it is preferable to use a catalyst from the viewpoint of accelerating the reaction. The catalyst is not particularly limited as long as it is a commonly used catalyst, and examples thereof include borofluoride compounds such as ammonium borofluoride and zinc borofluoride, neutral metal salt catalysts such as magnesium chloride and magnesium sulfate, inorganic acids such as phosphoric acid, hydrochloric acid and boric acid And the like. To these catalysts, if necessary, organic acids such as citric acid, tartaric acid, malic acid, maleic acid and lactic acid may be used as co-catalysts. Examples of such catalysts include Catalysts ACX, Catalyst 376, Catalyst O, Catalyst M, Catalyst G (GT), Catalyst X-110, Catalyst GT-3, NIKA CATALYST 3-P and UNIKA CATALYST MC-109 manufactured by Union Ka Kako Kogyo Co., Ltd., Riken Picker RC Series, Riken Picker MX Series manufactured by MIKI RIKEN KOGYO CO., LTD. RIKEN RICKER RZ-5 and the like.

When the water and oil repellent composition of the present embodiment contains at least one member selected from the group consisting of a melamine resin, an isocyanate compound and a glyoxal resin, the water and oil repellency and its durability (especially washing resistance and abrasion resistance) From the viewpoint of the strength and the like, it is preferable that the sum of the mass (effective component) thereof is 0.4 to 3,000 parts by mass relative to 100 parts by mass of the copolymer according to the present embodiment.

When the water and oil repellent composition of the present embodiment is used for a fiber product containing 40% by mass or more of synthetic fibers, from the viewpoints of water and oil repellency and durability (in particular, washing resistance and abrasion resistance), the melamine resin and / Or an isocyanate compound is preferably used, and it is more preferable to use a melamine resin and an isocyanate compound in combination. In this case, the blending amount (effective component) of the melamine resin and / or isocyanate compound is preferably 0.4 to 300 parts by mass, more preferably 1 to 50 parts by mass, per 100 parts by mass of the copolymer according to the present embodiment. If the amount is the above amount, the effect of improving water and oil repellency and durability (especially washing resistance and abrasion resistance) corresponding to the usage amount can be easily obtained.

When the water and oil repellent composition of the present embodiment is used for a fiber product having a synthetic fiber content of less than 40% by mass, the glyoxal resin and / or the glyoxal resin is preferably used in view of water and oil repellency and durability (particularly wash resistance and abrasion resistance) Or an isocyanate compound is preferably used. In this case, the blending amount (effective component) of the glyoxal resin and / or the isocyanate compound is preferably 10 to 3,000 parts by mass, more preferably 10 to 2,000 parts by mass, per 100 parts by mass of the copolymer according to the present embodiment . If the amount is the above amount, the effect of improving water and oil repellency and durability (especially washing resistance and abrasion resistance) corresponding to the usage amount can be easily obtained.

The treatment liquid according to the present embodiment can be produced, for example, by mixing water, an organic solvent, and the water and oil repellent composition of the present invention. In this case, the order of mixing is not particularly limited, but from the viewpoint of processing stability, a method of mixing the organic solvent diluted with water and the water and oil-repellent agent composition of the present embodiment diluted with water, or a method of mixing organic solvent or foot It is preferable to dilute one of the water and oil repellent compositions with water and mix the other.

The method for producing a water- and oil-repellent fiber product of the present embodiment includes a step of treating a fiber product with a treatment liquid containing the water and oil repellent composition of the present embodiment.

As a method of treating the fiber product with the treatment liquid, a conventionally conducted method can be used without limitation. For example, the fiber product is treated with a treatment liquid by a pad method, a dipping method, a spraying method, a bubble processing method, a coating method, or the like, and then dried. After drying, a curing (heat treatment) step may be incorporated as needed. As the drying method, a conventionally used method can be used without limitation, either dry heat method or wet heat method.

The material of the fiber product to which the manufacturing method according to the present embodiment can be applied is not particularly limited and natural fibers such as cotton, hemp, dog, wool, semi-synthetic fibers such as rayon and acetate, nylon, polyester , Synthetic fibers such as polyurethane and polypropylene, conjugated fibers thereof, and blended fibers. The form of the fiber product may be any of cloth, knitted fabric, thread, non-woven fabric, paper and the like.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto at all.

[Synthesis of monomer (A)

(Synthesis Example 1)

In a 1000 ml flask, 380 g of perfluorohexylethyl alcohol, 150 g of cyclohexane, 10 g of p-toluenesulfonic acid and 32 g of itaconic acid were added. These were heated and refluxed at about 85 캜 for 10 hours. Thereafter, cyclohexane was removed by distillation, and 400 g of ion-exchanged water and 5 g of sodium carbonate were added to neutralize. Next, the water phase was removed, followed by washing twice with ion-exchanged water. Thereafter, distillation was carried out under reduced pressure to obtain a compound represented by the following formula (7) (hereinafter abbreviated as C6FIA) as the monomer (A). GC measurement was carried out, and the purity was 99.9%.

(7)

(Example 1)

[Preparation of water and oil-repellent composition]

72 g of the C6FIA obtained in Synthesis Example 1 as the monomer (A), 18 g of stearyl acrylate (hereinafter abbreviated as SA) as the monomer (B), 5 g of polyoxyethylene alkyl ether (hereinafter abbreviated as POA) 1 g of aryltrimethylammonium chloride (hereinafter abbreviated as STMAC), 30 g of propylene glycol (hereinafter abbreviated as PPG), and 261.7 g of ion-exchanged water were put and stirred and mixed at 40 占 폚. This was emulsified and dispersed in an ultrasonic emulsifier, cooled to 30 ° C or lower, and transferred to a 500 ml stainless steel autoclave vessel. To this, 0.3 g of dodecylmercaptan was added and nitrogen replacement was carried out for 10 minutes. Then, 0.3 g of V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the temperature was raised and the reaction was carried out at 60 DEG C for 6 hours to obtain a water and oil repellent composition.

The obtained water and oil repellent composition had a non-volatile content of 31.5%. The melt viscosity of the copolymer contained in the water and oil repellent composition at 105 ° C was about 5800 Pa · s.

The melt viscosity of the copolymer can be measured by using a flow tester CFT-500D (manufactured by SHIMADZU) for a sample obtained by adding an organic solvent such as methanol or acetone to the water and oil-repellent composition, emulsifying and breaking the solid component, And measured at a measurement temperature of 105 ° C.

[One. Preparation of treatment liquid A and production of water-repellent and oil-repellent fiber product A]

The water and oil-repellent composition obtained above was diluted with ion-exchanged water to prepare a treatment liquid A containing the water and oil-repellent composition at a concentration of 2 g / l, 4 g / l, and 6 g / l, respectively. To this treatment liquid A, a dyed polyester fabric cloth (120 g / m 2) and a nylon fabric cloth (120 g / m 2) were immersed and squeezed out with water. At this time, the wet pickup ratio of the polyester fabric cloth was 60%, and the wet pickup ratio of the nylon fabric cloth was 40%. Thereafter, the treated cloth was dried at 120 DEG C for 60 seconds and further at 180 DEG C for 60 seconds to obtain a water and oil repellent fiber product A, respectively. The water repellency of the water-repellent, oil-based fiber product A was evaluated by the following method. The results are shown in Table 5.

[2. Adjustment of treatment liquid B and production of water-repellent and oil-repellent textile product B]

The water and oil-repellent composition obtained above and NK assist FU (trade name, block isocyanate crosslinking agent, manufactured by Nikka Chemical Co., Ltd.) were diluted with ion-exchanged water to prepare 40 g / l of the water and oil repellent composition and 8 g / l of NK assisted FU Was prepared. The dyed polyester fabric (120 g / m 2) was immersed in this treatment liquid B, and the water was squeezed at a pick-up rate of 60% by mangling, and dried at 120 ° C. for 60 seconds and further at 180 ° C. for 60 seconds , And water-repellent and oil-based textile product B were obtained. The durability and water repellency of this water-repellent, oily fiber product B was evaluated by the following method. The results are shown in Table 5.

[3. Adjustment of treatment liquid C and production of water-repellent and oil-repellent, oily fiber product C]

The water and oil-repellent composition obtained above was diluted with ion-exchange water to prepare a treatment liquid C containing 30 g / l of the water and oil repellent composition. The dyed polyester fabric (120 g / m 2) was immersed in the treatment liquid C, the water was squeezed at a pick-up rate of 60% by mangling, dried at 120 ° C for 60 seconds and further at 180 ° C for 60 seconds , Water-repellent and oil-based textile product C was obtained. The oil repellency and feel of the water-repellent and oil-based textile product C were evaluated by the following methods. The results are shown in Table 5.

[Evaluation of water repellency]

The water repellency of the water-repellent and oil-repellent fiber product A in the water repellency No. by the spray method of JIS L-1092 shown in the following Table 1 was shown.

Water repellency No. condition 5 No wetting on the surface 4 Very slight adhesion wetting on the surface 3 Representing partial wetting on the surface 2 Wet on the surface One Wetting on the entire surface

In addition, the water repellency No. indicates that the performance is slightly better, and the -signature indicates that the performance is slightly inferior.

[Evaluation of durability of water repellency]

The water repellency of the water-repellent and viscous fiber product B after initial washing, after washing 5 times, after washing 10 times, and after washing 20 times was evaluated according to JIS L 0217 (1995).

[Evaluation of oil repellency]

According to AATCC_TM-118 (1966), the test solutions shown in the following Table 2 were placed in five test pieces (water and oil repellent fiber product C), and the oiliness was judged by the penetration state after 30 seconds.

Oil repellency No. Test solution 8 n-heptane 7 n-octane 6 n-decane 5 n-dodecane 4 n-tetradecane 3 n-hexadecane 2 n-hexadecane / Nouzol (65/35) mixed solution One Nursing 0 Less than 1

[Evaluation of abrasion resistance]

Wear of the water-repellent and oil-based textile product B was performed in accordance with ISO 5470-1 (2002). A 5135 ABRASER (Rotary Platform Abraser) (manufactured by TABER INDUSTRIES) and a CS-10 (manufactured by TABER INDUSTRIES) were used as wear wheels. Thereafter, according to AATCC TM-118 (2002), the oil repellency No. 4 The test solution was visually observed when a drop was placed on the fabric (fabric), and evaluated according to the following criteria (see Fig. 1 of AATCC Tecnical Manual / 2006, p.192).

A: A clear well-rounded drop with high contact angle.

B: Rounding drop with partial darkening, partly accompanied by darkness.

C: Wicking with loss of contact angle

D: complete wetting

[Texture evaluation]

The feeling of the water-repellent and oil-based textile product C was judged according to the criteria shown in Table 3 to evaluate the feel.

Texture No. Texture One Harder than cloth before water-repellant processing 2 It is a bit stiff compared to cloth before water-repellant processing 3 Same as cloth before water-repellant processing 4 It is slightly soft compared to cloth before water-repellent oiling process 5 It is softer than cloth before water-repellent oiling process.

[Processing Stability]

The resulting water and oil-repellent composition was diluted with ion-exchanged water to a concentration of the water / oil repellent composition of 10 g / L, and 300 g of the test liquid was prepared. The temperature of the test solution which had been raised to 40 3 占 폚 was stirred with a homomixer at 6000 rpm for 10 minutes and filtered with a black cotton cloth. The amount of the residue remaining on the cotton cloth was visually judged according to the criteria in Table 4 to evaluate the stability.

stability Amount of residue One The more filtrate, the more residue there is. 2 More than half of the cotton area is covered with residue 3 Less than half the area of cotton is covered with residue 4 There is some residue 5 No residue

(Examples 2 to 9 and Comparative Examples 1 to 8)

The same procedures as in Example 1 were carried out except that the kinds and amounts of monomers (the values in the table represent the ratio (mass%) in the total monomer amount of 90 g) were changed as shown in Tables 5 and 6 and Tables 9 and 10, The water and oil-repellent compositions of Examples 2 to 9 and Comparative Examples 1 to 8, and the water and oil repellent fiber products A to C, respectively.

The water and oil repellent composition and the water and oil repellent fiber products A to C were evaluated in the same manner as in Example 1. The results are shown in Tables 5 and 6 and Tables 9 and 10.

(Examples 10 to 15)

The water and oil-repellent composition was prepared in the same manner as in Example 1 except that the kinds and amounts of the monomers were changed as shown in Tables 7 and 8 to prepare a water and oil-repellent composition. To 40 g of the water / (g), a melamine resin / catalyst, or a glyoxal resin / catalyst were used in the same manner as in Example 1 to obtain water- and oil-repellent fiber products B, respectively.

The water repellent and oil repellent fiber product B obtained above was evaluated for endurance water repellency and abrasion resistance in the same manner as in Example 1. The results are shown in Tables 7 and 8.

(Comparative Examples 9 to 10)

Except that the water and oil-repellent agent composition was prepared in the same manner as in Example 1 except that the kind of the monomer and the amount of the monomer used were changed as shown in Table 11, To obtain a water- and oil-repellent fiber product B, respectively.

The water repellent and oil repellent fiber product B obtained above was evaluated for durability against water repellency and abrasion resistance in the same manner as in Example 1. The results are shown in Table 11.

The symbols in the tables indicate the following compounds.

C6FIA: Compound of Synthesis Example 1

C6FMA: Perfluorohexylethyl methacrylate

SA: stearyl acrylate

VA: Behenyl acrylate

VCM: vinyl chloride monomer

St: Styrene

BA: butyl acrylate

NK assistant IS-100: Isocyanate-based cross-linking agent (trade name, manufactured by Nikka Kagaku K.K.)

UNIKA RESIN 380K: Melamine resin (trade name, manufactured by Union Kakako Kogyo Co., Ltd.)

UniCatalyst 3-P: Catalyst for melamine resin (trade name, manufactured by Union Kakako Kogyo Co., Ltd.)

Unirezin GS-20E: glyoxal resin (trade name, manufactured by Union Kakako Kogyo Co., Ltd.)

Unika Catalyst MC-109: Catalyst for glyoxal resin (trade name, manufactured by Union Kakako Kogyo Co., Ltd.)

The water and oil-repellent composition of Examples 1 to 15, which comprises the copolymer containing the monomer (A) and the monomer (B) as copolymer components, has sufficient water and oil repellency and processing stability, Water-repellent and oil-repellent and durability (especially wash resistance and abrasion resistance) and feel.

According to the present invention, there can be provided a water and oil repellent composition capable of imparting good water and oil repellency, durability and feel, and a method for producing a water and oil repellent fiber product using the same. The water and oil repellent composition of the present invention can impart good water and oil repellency and durability and feel to a textile product as compared with conventional water and oil repellent components having a perfluoroalkyl group having 6 or less carbon atoms. The durability of the water and oil repellency imparted by the water and oil repellent composition of the present invention is excellent in washing resistance and abrasion resistance. That is, the water and oil repellency imparted to the textile product by the water and oil repellent composition of the present invention may be less likely to be deteriorated by washing, friction or the like.

Claims (6)

(B) at least one monomer selected from the group consisting of a monomer (A) represented by the following formula (1), a monomer represented by the following formula (2) and a monomer represented by the following formula (3) Wherein the copolymer comprises a copolymer obtained by copolymerizing a monomer composition.
(1)

Wherein R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or a methyl group, R ³ and R ⁴ each independently represent an alkyl group having at least one kind selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group Or a monovalent hydrocarbon group of 1 to 30 carbon atoms which does not contain a fluorine atom and may contain at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group, a monovalent hydrocarbon group R < ³ > and R < ⁴ > At least one of them is a monovalent fluorinated hydrocarbon group which may contain at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group, X ¹ and X ² each independently represents a divalent organic group or a group Lt; / RTI >
(2)

Wherein R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom or a methyl group, and R ⁷ is a group having a number of carbon atoms, which may contain at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group, 1 to 30 monovalent hydrocarbon groups or monovalent fluorinated hydrocarbon groups, R ⁸ represents a hydrogen atom, a halogen atom or a methyl group, and X ³ represents a divalent organic group or a single bond]
(3)

Wherein R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom or a methyl group, and R ¹¹ and R ¹² are each independently at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group And X ⁴ and X ⁵ each independently represent a divalent organic group or a single bond, which may be the same or different and each independently represent a hydrogen atom or a monovalent hydrocarbon group of 1 to 30 carbon atoms, The positive resist composition according to claim 1, wherein R ³ and R ⁴ in the formula (1) are a monovalent fluorinated hydrocarbon group which may contain at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group, Water and emulsion composition. The positive resist composition as claimed in claim 1 or 2, wherein R ³ and R ⁴ in the formula (1) are each independently a perfluoroalkyl group having 2 to 18 carbon atoms, a group represented by the following formula (4) (5). ≪ / RTI >
(4)
C _m F _{(2m + 1)} (CH ₂ ) _p O (R ¹³ O) _n -
Wherein m represents 2 to 18, p represents 0 or 1 to 5, R ¹³ represents a perfluoroalkylene group having 2 to 5 carbon atoms, and n represents a perfluoroalkyl group represented by (R ¹³ O) The average addition mole number of the phenoxy group is 1 to 10]
(5)
F (R < ¹⁴ > O) _s-
[, R ¹⁴ in the formula is an alkylene group of a perfluoroalkyl group having 1 to 5, s is (R ¹⁴ O) a perfluoroalkyl represents an average addition mole number of the alkylene group represented by, from 1 to 10; The positive resist composition according to any one of claims 1 to 3, wherein R ⁷ in the formula (2) and R ¹¹ and R ¹² in the formula (3) are a linear alkyl group having 8 to 30 carbon atoms, Branched alkyl group having 1 to 30 carbon atoms, or a cyclic alkyl group having 8 to 30 carbon atoms. The water and oil repellent composition according to any one of claims 1 to 4, wherein the monomer composition further comprises at least one monomer (C) selected from the group consisting of vinyl chloride and vinylidene chloride. A process for producing a water- and oil-repellent fiber product, which comprises a step of treating a fiber product with a treatment liquid comprising the water and oil-repellent agent composition according to any one of claims 1 to 5.