阅读说明：本技术 非氟嵌段共聚物 (Non-fluorine block copolymer ) 是由 盐谷优子 吉田知弘 川部琢磨 山本育男 于 2019-09-27 设计创作，主要内容包括：本发明的非氟嵌段共聚物具有至少1个嵌段链段(A),嵌段链段(A)具有由具有碳原子数7～40的长链烃基的1种或2种以上的丙烯酸单体形成的重复单元,该非氟嵌段共聚物能够对纤维等的基材赋予优异的拨液性。非氟嵌段共聚物优选具有链段(B),链段(B)为(B1)、(B2)和(B3)中的至少1种,(B1)具有由与链段(A)不同的具有碳原子数7～40的长链烃基的丙烯酸单体形成的重复单元的嵌段链段；(B2)具有由不具有长链烃基的丙烯酸单体形成的重复单元的嵌段链段；(B3)由至少2种丙烯酸单体形成的无规链段。(The non-fluorine block copolymer of the present invention has at least 1 block segment (A) having a repeating unit formed from 1 or 2 or more kinds of acrylic monomers having a long chain hydrocarbon group having 7 to 40 carbon atoms, and can impart excellent liquid repellency to a substrate such as a fiber. The non-fluorine block copolymer preferably has a segment (B) which is at least 1 of (B1), (B2) and (B3), and the segment (B1) is a block segment having a repeating unit formed from an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms, which is different from the segment (A); (B2) a block segment having a repeating unit formed of an acrylic monomer having no long-chain hydrocarbon group; (B3) a random segment formed from at least 2 acrylic monomers.)

1. A non-fluorine block copolymer having at least 1 block segment (a), said non-fluorine block copolymer being characterized by:

the block segment (A) has a repeating unit formed from 1 or 2 or more acrylic monomers having a long-chain hydrocarbon group having 7 to 40 carbon atoms.

2. The non-fluorinated block copolymer of claim 1, wherein:

the non-fluorine block copolymer has a segment (B) different from the block segment (A),

the segment (B) has at least 1 of the following (B1), (B2), and (B3):

(B1) a block segment having a repeating unit formed from an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms, which is different from the segment (A);

(B2) a block segment having a repeating unit formed of an acrylic monomer having no long-chain hydrocarbon group;

(B3) a random segment formed from at least 2 acrylic monomers.

3. The non-fluorinated block copolymer of claim 1 or 2, wherein:

the acrylic monomer having a long-chain hydrocarbon group is a monomer represented by the following formula:

CH₂＝C(－R¹²)－C(＝O)－Y¹¹－(R¹¹)_k

in the formula, R¹¹A hydrocarbon group having 7 to 40 carbon atoms,

R¹²is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom,

Y¹¹is selected from 2-4 valence alkyl radical with 1 carbon atom, -C₆H₄－、－O－、－C(＝O)－、－S(＝O)₂At least 1 or more of-NH-excluding the case where the alkyl group is solely present,

k is 1 to 3.

4. The non-fluorinated block copolymer of claim 3, wherein:

in the acrylic monomer having a long-chain hydrocarbon group,

Y¹¹are-Y ' -, -Y ' -C (═ O) -, -C (═ O) -Y ' -, -Y ' -R ' -Y ' -C (═ O) -, -Y ' -R ' -C (═ O) -Y ' -, -Y ' -R ' -Y ' -O) -Y ' -or-Y ' -R ' -Y ' -R ' -,

wherein Y' is independently a bondO-, -NH-or-S (═ O)₂－，

R' are each independently- (CH)₂)_mA straight-chain hydrocarbon group having an unsaturated bond and having 1 to 5 carbon atoms, a branched-chain hydrocarbon group having 1 to 5 carbon atoms, or- (CH)₂)_l－C₆H₄－(CH₂)_l-, formula- (CH)₂)_mWherein m is an integer of 1 to 5, formula- (CH)₂)_l－C₆H₄－(CH₂)_lIn the formula, l is an integer of 0 to 5, respectively, and-C₆H₄-is phenylene.

5. The non-fluorinated block copolymer of claim 3, wherein:

in the acrylic monomer having a long-chain hydrocarbon group,

Y¹¹is-O-, -NH-, -O-C (═ O) -, -NH-C (═ O) -, -O-C (═ O) -NH-, -NH-C (═ O) -O-, -NH-C (═ O) -NH-, -O-C₆H₄－、－NH－C₆H₄－、－O－(CH₂)_m－O－、－NH－(CH₂)_m－NH－、－O－(CH₂)_m－NH－、－NH－(CH₂)_m－O－、－O－(CH₂)_m－O－C(＝O)－、－O－(CH₂)_m－C(＝O)－O－、－NH－(CH₂)_m－O－C(＝O)－、－NH－(CH₂)_m－C(＝O)－O－、－O－(CH₂)_m－O－C(＝O)－NH－、－O－(CH₂)_m－NH－C(＝O)－O－、－O－(CH₂)_m－C(＝O)－NH－、－O－(CH₂)_m－NH－C(＝O)－、－O－(CH₂)_m－NH－C(＝O)－NH－、－O－(CH₂)_m－O－C₆H₄－、－O－(CH₂)_m－NH－S(＝O)₂－、－O－(CH₂)_m－S(＝O)₂－NH－、－NH－(CH₂)_m－O－C(＝O)－NH－、－NH－(CH₂)_m－NH－C(＝O)－O－、－NH－(CH₂)_m－C(＝O)－NH－、－NH－(CH₂)_m－NH－C(＝O)－、－NH－(CH₂)_m－NH－C(＝O)－NH－、－NH－(CH₂)_m－O－C₆H₄－、－NH－(CH₂)_m－NH－C₆H₄－、－NH－(CH₂)_m－NH－S(＝O)₂-or-NH- (CH)₂)_m－S(＝O)₂－NH－，

Wherein m is an integer of 1 to 5.

6. The non-fluorinated block copolymer according to any one of claims 1 to 5, wherein: the acrylic monomer having a long-chain hydrocarbon group is at least 1 monomer selected from the group consisting of (a1) and (a2) below,

(a1) formula (II): CH (CH)₂＝C(－R²²)－C(＝O)－Y²¹－R²¹The compound shown in the formula (I) is shown in the specification,

in the formula, R²¹A hydrocarbon group having 7 to 40 carbon atoms,

R²²is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom,

Y²¹is-O-or-NH-;

(a2) formula (II): CH (CH)₂＝C(－R³²)－C(＝O)－Y³¹－Z³¹(－Y³²－R³¹)_nThe compound shown in the formula (I) is shown in the specification,

in the formula, R³¹A hydrocarbon group having 7 to 40 carbon atoms,

R³²is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom,

Y³¹is-O-or-NH-,

Y³²is selected from-C₆H₄－、－O－、－C(＝O)－、－S(＝O)₂At least 1 or more of-or-NH-,

Z³¹is a 2-or 3-valent carbon atomA hydrocarbon group having a number of 1 to 5,

n is 1 or 2.

7. The non-fluorinated block copolymer of claim 6, wherein:

among the acrylic monomers (a1),

R²²is a hydrogen atom, a methyl group or a chlorine atom,

among the acrylic monomers (a2),

R³²is a hydrogen atom, a methyl group or a chlorine atom,

Y³²is a bond, -O-, -NH-, -O-C (═ O) -, -C (═ O) -O-, -C (═ O) -NH-, -NH-C (═ O) -, -NH-S (═ O)₂－、－S(＝O)₂－NH－、－O－C(＝O)－NH－、－NH－C(＝O)－O－、－NH－C(＝O)－NH－、－O－C₆H₄－、－NH－C₆H₄－、－O－(CH₂)_m－O－、－NH－(CH₂)_m－NH－、－O－(CH₂)_m－NH－、－NH－(CH₂)_m－O－、－O－(CH₂)_m－O－C(＝O)－、－O－(CH₂)_m－C(＝O)－O－、－NH－(CH₂)_m－O－C(＝O)－、－NH－(CH₂)_m－C(＝O)－O－、－O－(CH₂)_m－O－C(＝O)－NH－、－O－(CH₂)_m－NH－C(＝O)－O－、－O－(CH₂)_m－C(＝O)－NH－、－O－(CH₂)_m－NH－C(＝O)－、－O－(CH₂)_m－NH－C(＝O)－NH－、－O－(CH₂)_m－O－C₆H₄－、－NH－(CH₂)_m－O－C(＝O)－NH－、－NH－(CH₂)_m－NH－C(＝O)－O－、－NH－(CH₂)_m－C(＝O)－NH－、－NH－(CH₂)_m－NH－C(＝O)－、－NH－(CH₂)_m－NH－C(＝O)－NH－、－NH－(CH₂)_m－O－C₆H₄-or-NH－(CH₂)_m－NH－C₆H₄In the formula, m is an integer of 1 to 5,

Z³¹is-CH₂－、－CH₂CH₂－、－CH₂CH₂CH₂－、－CH₂CH₂CH₂CH₂－、－CH₂CH₂CH₂CH₂CH₂-CH having a branched structure₂CH ═ CH having a branched structure₂(CH－)CH₂-CH having a branched structure₂CH₂CH ═ CH having a branched structure₂CH₂CH₂CH₂CH ═ CH having a branched structure₂CH₂(CH－)CH₂-, or-CH having a branched structure₂CH₂CH₂CH＝。

8. The non-fluorinated block copolymer according to any one of claims 1 to 7, wherein: in the acrylic monomer having a long-chain hydrocarbon group, the long-chain hydrocarbon group is a linear or branched alkyl group having 10 to 40 carbon atoms, the acrylic monomer having no long-chain hydrocarbon group is an acrylic monomer having a short-chain hydrocarbon group having 1 to 6 carbon atoms, an acrylic monomer having a dimethylsiloxane moiety in a side chain, an acrylic monomer having a hydrophilic group, an acrylic monomer having a cyclic hydrocarbon group, an acrylic monomer having a crosslinking moiety, or a halogenated olefin, and the hydrophilic group is an OH group or an NH group₂A group, a COOH group, a sulfonic acid group or a phosphoric acid group, an alkali metal or alkaline earth metal salt group of carboxylic acid.

9. The non-fluorinated block copolymer of claim 8, wherein:

the acrylic monomer with short chain alkyl of 1-6 carbon atoms is of the formula CH₂＝C(－R⁵²)－C(＝O)－Y⁵¹－R⁵¹The compound shown in the formula (I) is shown in the specification,

in the formula, R⁵¹A hydrocarbon group of 1 to 6 carbon atoms which may contain an oxygen atom,

R⁵²is a hydrogen atomA monovalent organic group, or a halogen atom other than a fluorine atom,

Y⁵¹is-O-or-NH-;

the acrylic monomer having a hydrophilic group is of the formula CH₂＝C(－R⁶²)－C(＝O)－Y⁶¹－R⁶¹－(－Y⁶²)_qThe compound shown in the formula (I) is shown in the specification,

in the formula, R⁶¹A hydrocarbon group having 1 to 6 carbon atoms or a single bond,

R⁶²is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom,

Y⁶¹is-O-or-NH-,

Y⁶²is a hydrophilic group, and is a hydrophilic group,

q is a number of 1 to 3.

10. The non-fluorinated block copolymer according to any one of claims 1 to 9, wherein: the molar ratio of the block segment (a) (the molar ratio of the repeating units) is 30 mol% or more relative to the repeating units of the copolymer.

11. A method for producing a non-fluorine block copolymer according to any one of claims 1 to 10, the method comprising:

the non-fluorine block copolymer is produced by a first-stage polymerization step of polymerizing one of an acrylic monomer having a long-chain hydrocarbon group or an acrylic monomer having no long-chain hydrocarbon group, and a second-stage polymerization step of subsequently polymerizing the other of the acrylic monomer having a long-chain hydrocarbon group or the acrylic monomer having no long-chain hydrocarbon group.

12. A surface treating agent, characterized by comprising:

(1) the non-fluorine block copolymer according to any one of claims 1 to 10; and

(2) a liquid medium, a liquid-state medium,

the liquid medium is an organic solvent, or water, an organic solvent or a mixture of water and an organic solvent.

13. The surface treating agent according to claim 12, wherein:

the surface treating agent is a water repellent agent.

14. A substrate, characterized by:

which is a substrate to which the non-fluorine block copolymer in the surface treatment agent according to claim 12 or 13 is attached.

15. A method of manufacturing a treated substrate, comprising:

a step of applying the surface treatment agent according to claim 12 or 13 to a substrate.

Technical Field

The present invention relates to a non-fluorine block copolymer containing no fluorine atom.

Background

Fluorine-containing water-and oil-repellent agents containing fluorine compounds are known. The water-and oil-repellent agent exhibits excellent water-and oil-repellency when used for treating a base material such as a textile product.

Further, it is known that the fluorine-containing block polymer improves liquid repellency.

On the other hand, acrylic block copolymers containing no fluorine have been reported. However, most of the reports on a block copolymer having a block of a hydrophilic monomer have made no description about improvement of liquid repellency by the block copolymer.

Patent document 1 (japanese patent application laid-open No. 2004-124088) discloses a block copolymer having a hydrophilic polymer component (e.g., poly (ethylene oxide)) and a hydrophobic polymer component (e.g., poly (methacrylic acid ester) having a mesogen side chain or a long-chain alkyl side chain).

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2004-124088

Disclosure of Invention

Technical problem to be solved by the invention

The purpose of the present invention is to provide a fluorine atom-free block copolymer which imparts excellent liquid repellency.

Technical solution for solving technical problem

The present invention provides a non-fluorine block copolymer having at least 1 block segment (A) having a repeating unit formed from an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms.

The present invention also provides a method for producing a non-fluorine block copolymer, which comprises a first-stage polymerization step of polymerizing one of an acrylic monomer having a long-chain hydrocarbon group and an acrylic monomer having no long-chain hydrocarbon group, and a second-stage polymerization step of subsequently polymerizing the other of the acrylic monomer having a long-chain hydrocarbon group and the acrylic monomer having no long-chain hydrocarbon group.

Further, the present invention provides a surface treatment agent comprising:

(1) the above-mentioned non-fluorine block copolymer; and

(2) the liquid medium is an organic solvent, or water, an organic solvent or a mixture of water and an organic solvent.

Preferred embodiments of the present invention are as follows.

[1] A non-fluorine block copolymer having at least 1 block segment (A),

the block segment (A) has a repeating unit formed from 1 or 2 or more acrylic monomers having a long-chain hydrocarbon group having 7 to 40 carbon atoms.

[2] The non-fluorine block copolymer according to [1], wherein the non-fluorine block copolymer has a segment (B) different from the block segment (A), the segment (B) having at least 1 of the following (B1), (B2) and (B3):

(B1) a block segment having a repeating unit formed from an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms, which is different from the segment (A);

(B2) a block segment having a repeating unit formed of an acrylic monomer having no long-chain hydrocarbon group;

(B3) a random segment formed from at least 2 acrylic monomers.

[3] The non-fluorine block copolymer according to [1] or [2], wherein the acrylic monomer having a long chain hydrocarbon group is a monomer represented by the following formula:

CH₂＝C(－R¹²)－C(＝O)－Y¹¹－(R¹¹)_k

[ in the formula, R¹¹A hydrocarbon group having 7 to 40 carbon atoms,

R¹²is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom,

Y¹¹is selected from 2-4 valence alkyl radical with 1 carbon atom, -C₆H₄－、－O－、－C(＝O)－、－S(＝O)₂At least 1 or more constituent groups of-or-NH- (excluding the case of a hydrocarbon group only),

k is 1 to 3. ].

[4] The non-fluorine block copolymer according to [3], wherein, in the acrylic monomer having a long chain hydrocarbon group,

Y¹¹are-Y ' -, -Y ' -C (═ O) -, -C (═ O) -Y ' -, -Y ' -R ' -Y ' -C (═ O) -, -Y ' -R ' -C (═ O) -Y ' -, -Y ' -R ' -Y ' -C (═ O) -Y ' -, or-Y ' -R ' -Y ' -R ' -,

[ wherein Y' are each independently a bond, -O-, -NH-, or-S (═ O)₂－，

R' are each independently- (CH)₂)_m- (m is an integer of 1 to 5), a straight-chain hydrocarbon group having an unsaturated bond and having 1 to 5 carbon atoms, a hydrocarbon group having a branched structure and having 1 to 5 carbon atoms, or- (CH)₂)_l－C₆H₄－(CH₂)_l- (l is each independently an integer of 0 to 5, -C₆H₄-is phenylene).]。

[5]Such as [3]]The non-fluorine block copolymer, wherein Y¹¹is-O-, -NH-, -O-C (═ O) -, -NH-C (═ O) -, -O-C (═ O) -NH-, -NH-C (═ O) -O-, -NH-C (═ O) -NH-, -O-C₆H₄－、－NH－C₆H₄－、－O－(CH₂)_m－O－、－NH－(CH₂)_m－NH－、－O－(CH₂)_m－NH－、－NH－(CH₂)_m－O－、－O－(CH₂)_m－O－C(＝O)－、－O－(CH₂)_m－C(＝O)－O－、－NH－(CH₂)_m－O－C(＝O)－、－NH－(CH₂)_m－C(＝O)－O－、－O－(CH₂)_m－O－C(＝O)－NH－、－O－(CH₂)_m－NH－C(＝O)－O－、－O－(CH₂)_m－C(＝O)－NH－、－O－(CH₂)_m－NH－C(＝O)－、－O－(CH₂)_m－NH－C(＝O)－NH－、－O－(CH₂)_m－O－C₆H₄－、－O－(CH₂)_m－NH－S(＝O)₂－、－O－(CH₂)_m－S(＝O)₂－NH－、－NH－(CH₂)_m－O－C(＝O)－NH－、－NH－(CH₂)_m－NH－C(＝O)－O－、－NH－(CH₂)_m－C(＝O)－NH－、－NH－(CH₂)_m－NH－C(＝O)－、－NH－(CH₂)_m－NH－C(＝O)－NH－、－NH－(CH₂)_m－O－C₆H₄－、－NH－(CH₂)_m－NH－C₆H₄－、－NH－(CH₂)_m－NH－S(＝O)₂-, or-NH- (CH)₂)_m－S(＝O)₂－NH－，

[ in the formula, m is an integer of 1 to 5. ].

[6] The non-fluorine block copolymer according to any one of [1] to [5], wherein the acrylic monomer having a long chain hydrocarbon group is at least 1 monomer selected from the group consisting of (a1) and (a2) below,

(a1) formula (II): CH (CH)₂＝C(－R²²)－C(＝O)－Y²¹－R²¹The compound shown in the formula (I) is shown in the specification,

[ in the formula, R²¹A hydrocarbon group having 7 to 40 carbon atoms,

R²²is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom,

Y²¹is-O-or-NH-.]；

(a2) Formula (II): CH (CH)₂＝C(－R³²)－C(＝O)－Y³¹－Z³¹(－Y³²－R³¹)_nThe compound shown in the formula (I) is shown in the specification,

[ in the formula, R³¹A hydrocarbon group having 7 to 40 carbon atoms,

R³²is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom,

Y³¹is-O-or-NH-,

Y³²each independently is selected from the group consisting of a bond, -C₆H₄－、－O－、－C(＝O)－、－S(＝O)₂At least 1 or more of-or-NH-,

Z³¹a C1-5 hydrocarbon group having a valence of 2 or 3,

n is 1 or 2. ].

[7] The non-fluorine block copolymer according to [6], wherein,

among the acrylic monomers (a1),

R²²is a hydrogen atom, a methyl group or a chlorine atom,

among the acrylic monomers (a2),

R³²is a hydrogen atom, a methyl group or a chlorine atom,

Y³²is a bond, -O-, -NH-, -O-C (═ O) -, -C (═ O) -O-, -C (═ O) -NH-, -NH-C (═ O) -, -NH-S (═ O)₂－、－S(＝O)₂－NH－、－O－C(＝O)－NH－、－NH－C(＝O)－O－、－NH－C(＝O)－NH－、－O－C₆H₄－、－NH－C₆H₄－、－O－(CH₂)_m－O－、－NH－(CH₂)_m－NH－、－O－(CH₂)_m－NH－、－NH－(CH₂)_m－O－、－O－(CH₂)_m－O－C(＝O)－、－O－(CH₂)_m－C(＝O)－O－、－NH－(CH₂)_m－O－C(＝O)－、－NH－(CH₂)_m－C(＝O)－O－、－O－(CH₂)_m－O－C(＝O)－NH－、－O－(CH₂)_m－NH－C(＝O)－O－、－O－(CH₂)_m－C(＝O)－NH－、－O－(CH₂)_m－NH－C(＝O)－、－O－(CH₂)_m－NH－C(＝O)－NH－、－O－(CH₂)_m－O－C₆H₄－、－NH－(CH₂)_m－O－C(＝O)－NH－、－NH－(CH₂)_m－NH－C(＝O)－O－、－NH－(CH₂)_m－C(＝O)－NH－、－NH－(CH₂)_m－NH－C(＝O)－、－NH－(CH₂)_m－NH－C(＝O)－NH－、－NH－(CH₂)_m－O－C₆H₄-or- (CH)₂)_m－NH－C₆H₄－，

[ in the formula, m is an integer of 1 to 5. ],

Z³¹is-CH₂－、－CH₂CH₂－、－CH₂CH₂CH₂－、－CH₂CH₂CH₂CH₂－、－CH₂CH₂CH₂CH₂CH₂-CH having a branched structure₂CH ═ CH having a branched structure₂(CH－)CH₂-CH having a branched structure₂CH₂CH ═ CH having a branched structure₂CH₂CH₂CH₂CH ═ CH having a branched structure₂CH₂(CH－)CH₂-, or-CH having a branched structure₂CH₂CH₂CH＝。

[8] The non-fluorinated block copolymer according to any one of [1] to [7], wherein the long-chain hydrocarbon group in the acrylic monomer having a long-chain hydrocarbon group is a linear or branched alkyl group having 10 to 40 carbon atoms.

[9]Such as [1]]～[8]The non-fluorine block copolymer, wherein the acrylic monomer having no long chain hydrocarbon group is an acrylic monomer having a short chain hydrocarbon group having 1 to 6 carbon atoms and having dimethylsiloxane in a side chainA site acrylic monomer, an acrylic monomer having a hydrophilic group, an acrylic monomer having a cyclic hydrocarbon group, an acrylic monomer having a crosslinking site, or a halogenated olefin, the hydrophilic group being an OH group, NH₂A group, a COOH group, a sulfonic acid group or a phosphoric acid group, an alkali metal or alkaline earth metal salt group of carboxylic acid.

[10]Such as [9 ]]The non-fluorine block copolymer is characterized in that the acrylic monomer with short-chain alkyl of 1-6 carbon atoms is of the formula CH₂＝C(－R⁵²)－C(＝O)－Y⁵¹－R⁵¹The compound shown in the formula (I) is shown in the specification,

[ in the formula, R⁵¹A hydrocarbon group having 1 to 6 carbon atoms (which may contain an oxygen atom),

R⁵²is a hydrogen atom, a monovalent organic group or a halogen atom other than a fluorine atom,

Y⁵¹is-O-or-NH-.]

The acrylic monomer having a hydrophilic group is of the formula CH₂＝C(－R⁶²)－C(＝O)－Y⁶¹－R⁶¹－(－Y⁶²)_qThe compound shown in the formula (I) is shown in the specification,

[ in the formula, R⁶¹A hydrocarbon group having 1 to 6 carbon atoms or a single bond (valence bond),

R⁶²is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom,

Y⁶¹is-O-or-NH-,

Y⁶²is a hydrophilic group, and is a hydrophilic group,

q is a number of 1 to 3. ].

[11] The non-fluorinated block copolymer according to any one of [1] to [10], wherein the molar ratio of the block segment (A) (the molar ratio of the repeating unit) is 30 mol% or more based on the repeating unit of the copolymer.

[12] The method for producing a non-fluorine block copolymer according to any one of [1] to [11], which comprises a first-stage polymerization step of polymerizing one of an acrylic monomer having a long-chain hydrocarbon group and an acrylic monomer having no long-chain hydrocarbon group, and a second-stage polymerization step of subsequently polymerizing the other of the acrylic monomer having a long-chain hydrocarbon group and the acrylic monomer having no long-chain hydrocarbon group.

[13] A surface treatment agent comprising:

(1) the non-fluorine block copolymer according to any one of [1] to [11 ]; and

(2) the liquid medium is an organic solvent, or water, an organic solvent or a mixture of water and an organic solvent.

[14] The surface treating agent according to [13], wherein the surface treating agent is a water-repellent agent.

[15] A substrate to which the non-fluorine block copolymer of the surface treatment agent according to [13] or [14] is attached.

[16] A method of manufacturing a treated substrate, comprising: a step of applying the surface treatment agent as described in [13] or [14] to a substrate.

ADVANTAGEOUS EFFECTS OF INVENTION

The block copolymer of the present invention is excellent in liquid repellency, that is, water repellency and oil repellency, particularly water repellency. The block copolymer has high crystallinity and has a melting point of 25 ℃ or higher. The block copolymer has good film forming property.

Block copolymers exhibit better properties, such as liquid repellency, than random copolymers formed from the same monomers.

Detailed Description

(1) Non-fluorine block copolymer

The block copolymer of the present invention has a block segment (A) and other segments (B). The block copolymer is a non-fluorine block copolymer having no fluorine atom.

In the present specification, a copolymer having a block segment (a) is referred to as a "block copolymer". In the present specification, "non-fluorine" means "not containing a fluorine atom".

(A) Block chain segment

The block segment (A) has a repeating unit formed from an acrylic monomer (a) having a long-chain hydrocarbon group having 7-40 carbon atoms. The block segment (A) preferably contains a repeating unit formed from 1 acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms, but the block segment (A) may have a repeating unit formed from 2 or more (for example, 2 or 3) acrylic monomers having a long-chain hydrocarbon group having 7 to 40 carbon atoms. The block segment (A) is preferably formed from an acrylic monomer having 1 long-chain hydrocarbon group having 7 to 40 carbon atoms. The long-chain hydrocarbon group having 7 to 40 carbon atoms is preferably a straight-chain or branched hydrocarbon group having 7 to 40 carbon atoms. The number of carbon atoms of the long-chain hydrocarbon group is preferably 10 to 40, for example 12 to 30, and particularly preferably 16 to 26. The long-chain hydrocarbon group is particularly preferably a stearyl group, an eicosyl group or a docosyl group.

(a) Acrylic acid monomer

The acrylic monomer having a long-chain hydrocarbon group is preferably a monomer represented by the following formula:

CH₂＝C(－R¹²)－C(＝O)－Y¹¹－(R¹¹)_k

[ in the formula, R¹¹Each independently a hydrocarbon group having 7 to 40 carbon atoms,

R¹²is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom,

Y¹¹is selected from a 2-4 valence C1 hydrocarbon group (especially-CH)₂-, -CH ═ and-C ≡), -C₆H₄－、－O－、－C(＝O)－、－S(＝O)₂At least 1 or more constituent groups of-or-NH- (excluding the case where only a 2-valent hydrocarbon group is present),

k is 1 to 3. ].

k is 1, 2 or 3. But in Y¹¹In the case of a hydrocarbon group having 1 carbon atom having a valence of 4, k is 3. At Y¹¹In the case of a hydrocarbon group having 1 carbon atom having 3 valences, k is 2. At Y¹¹In the case of a hydrocarbon group having 1 carbon atoms not having 3 or 4 valences (e.g., Y)¹¹A hydrocarbon group having (for example, 1 to 6) 2-valent carbon atoms of 1 (-CH)₂-) is 1.

R¹²May be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. R¹²Examples of (b) are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. The more rigid the main chain of the resulting polymer, the less the crystallinity of the side chain is hindered, and therefore R¹²Preferably a hydrogen atom, a methyl group or a chlorine atom, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

Y¹¹Preferably a 2-valent group. Examples of the C1 hydrocarbon group having 2 to 4 valences are-CH₂-, -CH-having a branched structure and-C.ident.having a branched structure.

Y¹¹May be-Y ' -, -Y ' -C (═ O) -, -C (═ O) -Y ' -, -Y ' -R ' -Y ' -C (═ O) -, -Y ' -R ' -C (═ O) -Y ' -, -Y ' -R ' -Y ' -C (═ O) -Y ' -, or-Y ' -R ' -,

[ wherein Y' are each independently a bond, -O-, -NH-, or-S (═ O)₂－，

R' is- (CH)₂)_m- (m is an integer of 1 to 5), a straight-chain hydrocarbon group having an unsaturated bond and having 1 to 5 carbon atoms, a hydrocarbon group having a branched structure and having 1 to 5 carbon atoms, or- (CH)₂)_l－C₆H₄－(CH₂)_l- (l is each independently an integer of 0 to 5, -C₆H₄-is phenylene).]。

Y¹¹Specific examples of (a) are-O-, -NH-, -O-C (═ O) -, -NH-C (═ O) -, -O-C (═ O) -NH-, -NH-C (═ O) -O-, -NH-C (═ O) -NH-, -O-C₆H₄－、－NH－C₆H₄－、－O－(CH₂)_m－O－、－NH－(CH₂)_m－NH－、－O－(CH₂)_m－NH－、－NH－(CH₂)_m－O－、－O－(CH₂)_m－O－C(＝O)－、－O－(CH₂)_m－C(＝O)－O－、－NH－(CH₂)_m－O－C(＝O)－、－NH－(CH₂)_m－C(＝O)－O－、－O－(CH₂)_m－O－C(＝O)－NH－、－O－(CH₂)_m－NH－C(＝O)－O－、－O－(CH₂)_m－C(＝O)－NH－、－O－(CH₂)_m－NH－C(＝O)－、－O－(CH₂)_m－NH－C(＝O)－NH－、－O－(CH₂)_m－O－C₆H₄－、－O－(CH₂)_m－NH－S(＝O)₂－、－O－(CH₂)_m－S(＝O)₂－NH－、－NH－(CH₂)_m－O－C(＝O)－NH－、－NH－(CH₂)_m－NH－C(＝O)－O－、－NH－(CH₂)_m－C(＝O)－NH－、－NH－(CH₂)_m－NH－C(＝O)－、－NH－(CH₂)_m－NH－C(＝O)－NH－、－NH－(CH₂)_m－O－C₆H₄－、－NH－(CH₂)_m－NH－C₆H₄－、－NH－(CH₂)_m－NH－S(＝O)₂-, or-NH- (CH)₂)_m－S(＝O)₂-NH- [ wherein m is an integer of 1 to 5, in particular 2 or 4.]。

Y¹¹preferably-O-, -NH-, -O- (CH)₂)_m－O－C(＝O)－、－O－(CH₂)_m－NH－C(＝O)－、－O－(CH₂)_m－O－C(＝O)－NH－、－O－(CH₂)_m－NH－C(＝O)－O－、－O－(CH₂)_m－NH－C(＝O)－NH－、－O－(CH₂)_m－NH－S(＝O)₂-or-O- (CH)₂)_m－S(＝O)₂－NH－、－NH－(CH₂)_m－O－C(＝O)－、－NH－(CH₂)_m－NH－C(＝O)－、－NH－(CH₂)_m－O－C(＝O)－NH－、－NH－(CH₂)_m－NH－C(＝O)－O－、－NH－(CH₂)_m－NH－C(＝O)－NH－、－NH－(CH₂)_m－NH－S(＝O)₂－、－NH－(CH₂)_m－S(＝O)₂－NH－，

[ in the formula, m is an integer of 1 to 5, particularly 2 or 4. ].

Y¹¹More preferably-O-, -O- (CH)₂)_m－O－C(＝O)－NH－、－O－(CH₂)_m－NH－C(＝O)－O－、－O－(CH₂)_m－NH－C(＝O)－、－O－(CH₂)_m－NH－S(＝O)₂-or-O- (CH)₂)_m－S(＝O)₂-NH-, in particular-O- (CH)₂)_m－NH－C(＝O)－。

R¹¹Preferably a linear or branched hydrocarbon group. The hydrocarbon group may be a linear hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly preferably a saturated aliphatic hydrocarbon group, and particularly preferably an alkyl group. If the hydrocarbon group is short, crystallinity of the side chains decreases, and water repellency also decreases. Further, if the hydrocarbon group is too long, the melting point of the monomer having the hydrocarbon group increases, and therefore, there is a possibility that the solubility of the monomer decreases or the emulsion is unstable during polymerization. Thus, the number of carbon atoms of the hydrocarbon group is preferably 12 to 30, for example 16 to 26, and particularly preferably 18 to 22.

Examples of the acrylic monomer having a long-chain hydrocarbon group are the following (a1) and (a2),

(a1) formula (II): CH (CH)₂＝C(－R²²)－C(＝O)－Y²¹－R²¹The acrylic acid monomers shown are, in general,

[ in the formula, R²¹A hydrocarbon group having 7 to 40 carbon atoms,

R²²is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom,

Y²¹is-O-or-NH-.]；

(a2) Formula (II): CH (CH)₂＝C(－R³²)－C(＝O)－Y³¹－Z³¹(－Y³²－R³¹)_nThe acrylic acid monomers shown are, in general,

[ in the formula, R³¹Each independently has 7 to 40 carbon atomsThe hydrocarbon group of (a) is,

R³²is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom,

Y³¹is-O-or-NH-,

Y³²each independently is a bond selected from the group consisting of a bond, -O-, -C (═ O) -, -S (═ O)₂At least 1 or more of-or-NH-,

Z³¹a valence bond, or a C1-5 hydrocarbon group having a valence of 2 or 3,

n is 1 or 2. ].

(a1) Acrylic acid monomer

The acrylic monomer (a1) is a compound represented by the following formula:

CH₂＝C(－R²²)－C(＝O)－Y²¹－R²¹

[ in the formula, R²¹A hydrocarbon group having 7 to 40 carbon atoms,

R²²is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom,

Y²¹is-O-or-NH-.]。

The acrylic monomer (a1) is Y²¹A long chain acrylate monomer of-O-, or Y²¹A long chain acrylamide monomer that is-NH-.

R²¹Preferably a linear or branched hydrocarbon group. The hydrocarbon group may be a linear hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly preferably a saturated aliphatic hydrocarbon group, and particularly preferably an alkyl group. If the hydrocarbon group is short, crystallinity of the side chains decreases, and water repellency also decreases. Further, if the hydrocarbon group is too long, the melting point of the monomer having the hydrocarbon group is increased, and therefore, there is a possibility that the solubility of the monomer is lowered or the emulsion is unstable during polymerization. Thus, the number of carbon atoms is preferably 12 to 30, 16 to 26, and particularly preferably 18 to 22.

R²²Can be hydrogen atom, methyl, halogen atom except fluorine atom, substituted or unsubstituted benzyl, substituted or unsubstitutedA phenyl group of (a). R²²Examples of (B) are hydrogen, methyl, Cl, Br, I, CN. The more rigid the main chain of the resulting polymer, the less the crystallinity of the side chain is hindered, and therefore, R²²Hydrogen, methyl and Cl are preferred, hydrogen and methyl are preferred, and hydrogen is more preferred.

Preferred specific examples of the long-chain acrylate monomer are stearyl (meth) acrylate, eicosyl (meth) acrylate, docosyl (meth) acrylate, stearyl α -chloroacrylate, eicosyl α -chloroacrylate, and docosyl α -chloroacrylate.

Preferred specific examples of the long-chain acrylamide monomer are stearyl (meth) acrylamide, eicosyl (meth) acrylamide, and docosyl (meth) acrylamide.

(a2) Acrylic acid monomer

The acrylic monomer (a2) is a monomer having a structure selected from the group consisting of-O-, -C (═ O) -, -S (═ O)₂(meth) acrylate or (meth) acrylamide of at least 1 or more constituent groups of-or-NH-.

The acrylic monomer (a2) may be a compound represented by the following formula:

CH₂＝C(－R³²)－C(＝O)－Y³¹－Z³¹(－Y³²－R³¹)_n

[ in the formula, R³¹Each independently a hydrocarbon group having 7 to 40 carbon atoms,

R³²is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom,

Y³¹is-O-or-NH-,

Y³²each independently is a bond selected from the group consisting of a bond, -O-, -C (═ O) -, -S (═ O)₂At least 1 or more of-or-NH-,

Z³¹a valence bond, or a C1-5 hydrocarbon group having a valence of 2 or 3,

n is 1 or 2. ].

R³¹Preferably a linear or branched hydrocarbon group. The hydrocarbon radical may in particular be straight-chainA hydrocarbon group in the form of a cyclic ether. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly preferably a saturated aliphatic hydrocarbon group, and particularly preferably an alkyl group. If the hydrocarbon group is short, crystallinity of the side chains decreases, and water repellency also decreases. Further, if the hydrocarbon group is too long, the melting point of the monomer having the hydrocarbon group is increased, and therefore, there is a possibility that the solubility of the monomer is lowered or the emulsion is unstable during polymerization. Thus, the number of carbon atoms is preferably 12 to 30, 16 to 26, and particularly preferably 18 to 22.

R³²May be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. R³²Examples of (B) are hydrogen, methyl, Cl, Br, I, CN. The more rigid the main chain of the resulting polymer, the less the crystallinity of the side chain is hindered, and therefore R³²Hydrogen, methyl and Cl are preferred, hydrogen and methyl are preferred, and hydrogen is more preferred.

Y³²May be-Y ' -, -Y ' -C (═ O) -, -C (═ O) -Y ' -, -Y ' -R ' -Y ' -C (═ O) -, -Y ' -R ' -C (═ O) -Y ' -, -Y ' -R ' -Y ' -C (═ O) -Y ' -, or-Y ' -R ' -,

[ wherein Y' are each independently a bond, -O-, -NH-, or-S (═ O)₂－，

R' is- (CH)₂)_m- (m is an integer of 1 to 5), a straight-chain hydrocarbon group having an unsaturated bond and having 1 to 5 carbon atoms, a hydrocarbon group having a branched structure and having 1 to 5 carbon atoms, or- (CH)₂)_l－C₆H₄－(CH₂)_l- (l is each independently an integer of 0 to 5, -C₆H₄-is phenylene).]。

Y³²Specific examples of the (a) are a bond, -O-, -NH-, -O-C (═ O) -, -C (═ O) -O-, -C (═ O) -NH-, -NH-C (═ O) -, -NH-S (═ O)₂－、－S(＝O)₂－NH－、－O－C(＝O)－NH－、－NH－C(＝O)－O－、－NH－C(＝O)－NH－、－O－C₆H₄－、－NH－C₆H₄－、－O－(CH₂)_m－O－、－NH－(CH₂)_m－NH－、－O－(CH₂)_m－NH－、－NH－(CH₂)_m－O－、－O－(CH₂)_m－O－C(＝O)－、－O－(CH₂)_m－C(＝O)－O－、－NH－(CH₂)_m－O－C(＝O)－、－NH－(CH₂)_m－C(＝O)－O－、－O－(CH₂)_m－O－C(＝O)－NH－、－O－(CH₂)_m－NH－C(＝O)－O－、－O－(CH₂)_m－C(＝O)－NH－、－O－(CH₂)_m－NH－C(＝O)－、－O－(CH₂)_m－NH－C(＝O)－NH－、－O－(CH₂)_m－O－C₆H₄－、－NH－(CH₂)_m－O－C(＝O)－NH－、－NH－(CH₂)_m－NH－C(＝O)－O－、－NH－(CH₂)_m－C(＝O)－NH－、－NH－(CH₂)_m－NH－C(＝O)－、－NH－(CH₂)_m－NH－C(＝O)－NH－、－NH－(CH₂)_m－O－C₆H₄－、－NH－(CH₂)_m－NH－C₆H₄－，

[ in the formula, m is an integer of 1 to 5. ].

Y³²Preferred are-O-, -NH-, -O-C (═ O) -, -C (═ O) -O-, -C (═ O) -NH-, -NH-C (═ O) -, -NH-S (═ O)₂－、－S(＝O)₂－NH－、－O－C(＝O)－NH－、－NH－C(＝O)－O－、－NH－C(＝O)－NH－、－O－C₆H₄－。

Z³¹The hydrocarbon group having 1 to 5 carbon atoms, which is a valence bond or a valence of 2 or 3, may have a linear structure or a branched structure. Z³¹The number of carbon atoms of (A) is preferably 2 to 4, particularly preferably 2. Z³¹Specific example of (a) is a valence bond, -CH₂－、－CH₂CH₂－、－CH₂CH₂CH₂－、－CH₂CH₂CH₂CH₂－、－CH₂CH₂CH₂CH₂CH₂-CH having a branched structure₂CH ═ CH having a branched structure₂(CH－)CH₂-CH having a branched structure₂CH₂CH ═ CH having a branched structure₂CH₂CH₂CH₂CH ═ CH having a branched structure₂CH₂(CH－)CH₂-CH having a branched structure₂CH₂CH₂CH＝。

Z³¹Preferably not a valence bond, Y³²And Z³¹Not simultaneously being a bond.

The acrylic monomer (a2) is preferably CH₂＝C(－R³²)－C(＝O)－O－(CH₂)_m－NH－C(＝O)－R³¹、CH₂＝C(－R³²)－C(＝O)－O－(CH₂)_m－O－C(＝O)－NH－R³¹、CH₂＝C(－R³²)－C(＝O)－O－(CH₂)_m－NH－C(＝O)－O－R³¹、CH₂＝C(－R³²)－C(＝O)－O－(CH₂)_m－NH－C(＝O)－NH－R³¹[ wherein R³¹And R³²The same as above.]. The acrylic monomer (a2) is particularly preferably CH₂＝C(－R³²)－C(＝O)－O－(CH₂)_m－NH－C(＝O)－R³¹。

The acrylic monomer (a2) can be produced by reacting a hydroxyalkyl (meth) acrylate or hydroxyalkyl (meth) acrylamide with a long-chain alkyl isocyanate. Examples of the long-chain alkyl isocyanate include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate.

Alternatively, the acrylic monomer (a2) can also be produced by reacting a (meth) acrylate having an isocyanate group in a side chain, for example, 2-methacryloyloxyethyl methacrylate, with a long-chain alkylamine or a long-chain alkyl alcohol. Examples of the long-chain alkylamine include dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, and docosylamine. Examples of the long-chain alkyl alcohol include dodecanol, tetradecanol, hexadecanol, octadecanol, oleyl alcohol, and behenyl alcohol.

Specific examples of the acrylic monomer (a2) are shown below. The compound of the following formula is an acrylic compound having a hydrogen atom at the α -position, and specific examples thereof include a methacrylic compound having a methyl group at the α -position and an α -chloroacrylic acid compound having a chlorine atom at the α -position.

[ in the formula, m is an integer of 1 to 5, and n is an integer of 7 to 40. ]

The acrylic monomer (a) may be R³¹As a separate monomer (e.g. only R)³¹A compound having 17 carbon atoms), or R³¹In a plurality of combinations (e.g. R)³¹A compound of (2) and R³¹A mixture of compounds having 15 carbon atoms).

Of the acrylic monomers (a2), an example of the amide group-containing monomer is carboxylic acid amide alkyl (meth) acrylate.

Specific examples of the amide group-containing monomer include palmitoylamidoethyl (meth) acrylate, stearic acid amidoethyl (meth) acrylate, behenamidoethyl (meth) acrylate, myristic acid amidoethyl (meth) acrylate, lauric acid amidoethyl (meth) acrylate, isostearic acid ethylamide (meth) acrylate, oleic acid ethylamide (meth) acrylate, t-butylcyclohexylhexanoic acid amidoethyl (meth) acrylate, adamantanecarboxylic acid ethylamide (meth) acrylate, naphthalenecarboxylic acid amidoethyl (meth) acrylate, anthracenecarboxylic acid amidoethyl (meth) acrylate, palmitic acid amidopropyl (meth) acrylate, stearic acid amidopropyl (meth) acrylate, palmitic acid amidoethyl vinyl ether, stearic acid amidoethyl (meth) acrylate, stearic, Palmitamidoethyl allyl ether, stearamidoethyl allyl ether, or mixtures thereof.

The amide group-containing monomer is preferably stearic acid amide ethyl (meth) acrylate. The amide group-containing monomer may be a mixture comprising stearic acid amide ethyl (meth) acrylate. In the mixture containing stearic acid amide ethyl (meth) acrylate, the amount of stearic acid amide ethyl (meth) acrylate is preferably 55 to 99% by weight based on the weight of the entire amide group-containing monomer. The remaining monomer may be, for example, palmitoylamide ethyl (meth) acrylate.

(B) Other chain segments

The block copolymer has a segment (B) other than the block segment (A).

The block copolymer may be an A-B block polymer having 1 block segment (A) and 1 other segment (B), an A-B-A block polymer having 2 block segments (A) and 1 other segment (B), or a B-A-B block polymer having 1 block segment (A) and 2 other segments (B). The block copolymer may have a block segment (a) and an additional segment (C) other than the other segment (B). The block copolymer may be, for example, an A-B-C block copolymer or a B-A-C block polymer.

Examples of the other segment (B) are at least 1 segment of (B1), (B2), and (B3):

(B1) a block segment having a repeating unit formed from an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms, which is different from the segment (A);

(B2) a block segment having a repeating unit formed of an acrylic monomer having no long-chain hydrocarbon group;

(B3) a random segment formed from at least 2 acrylic monomers.

(B1) Block chain segment

The block segment (B1) has a repeating unit formed from an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms, which is different from an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms, which forms the segment (A). That is, the acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms forming the block segment (B1) is different from the acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms forming the block segment (A).

The preferable mode of the acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms for forming the block segment (B1) is the same as that of the acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms for forming the block segment (A).

Examples of preferable combinations of the acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms for forming the block segment (A) and the acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms for forming the block segment (B1) are:

in CH₂＝C(－R¹²)－C(＝O)－Y¹¹－(R¹¹)_kIn (1),

(A) is Y¹¹is-NH-, -O- (CH)₂)_m－O－C(＝O)－NH－、－O－(CH₂)_m-NH-C (═ O) -O-or-O- (CH)₂)_m-NH-C (═ O) -, (B1) is Y¹¹A monomer which is-O- (e.g.stearyl acrylate).

(B2) Block chain segment

The block segment (B2) has a repeating unit formed of an acrylic monomer having no long-chain hydrocarbon group.

Examples of the acrylic monomer having no long-chain hydrocarbon group are acrylic monomers having a short-chain hydrocarbon group having 1 to 6 carbon atoms, acrylic monomers having a hydrophilic group, acrylic monomers having a cyclic hydrocarbon group, and halogenated olefins. Other examples of the acrylic monomer having no long-chain hydrocarbon group are an acrylic monomer having a dimethylsiloxane moiety in a side chain, and a divinyl compound represented by a compound having 2 acrylic groups.

The acrylic monomer is an acrylate monomer or an acrylamide monomer.

Preferred examples of the acrylic monomer having a short-chain hydrocarbon group having 1 to 6 carbon atoms are compounds represented by the following formula:

CH₂＝C(－R⁵²)－C(＝O)－Y⁵¹－R⁵¹

[ in the formula, R⁵¹A hydrocarbon group having 1 to 6 carbon atoms (which may contain an oxygen atom),

R⁵²is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom,

Y⁵¹is-O-or-NH-.]。

R⁵¹Is a straight chain or branched chain hydrocarbon group. The number of carbon atoms of the linear or branched hydrocarbon group is 1 to 6. The linear or branched hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and is usually a saturated aliphatic hydrocarbon group, and is particularly preferably an alkyl group. In addition, oxygen atoms may be included. An example of the hydrocarbon group containing an oxygen atom is a glycidyl group.

R⁵²May be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. R⁵²Examples of (B) are hydrogen, methyl, Cl, Br, I, CN. The more rigid the main chain of the resulting polymer, the less the crystallinity of the side chain of the block segment (A) is hindered, and therefore R is⁵²Hydrogen, methyl and Cl are preferred, hydrogen and methyl are more preferred, and hydrogen is more preferred.

Particularly preferred specific examples of short-chain acrylic monomers are methyl (meth) acrylate, methyl α -chloroacrylate, ethyl (meth) acrylate, ethyl α -chloroacrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-butyl α -chloroacrylate, t-butyl α -chloroacrylate, methyl (meth) acrylamide, n-butyl (meth) acrylamide, t-butyl (meth) acrylamide, glycidyl (meth) acrylate, glycidyl (meth) acrylamide.

Preferred examples of the acrylic monomer having a hydrophilic group are compounds represented by the following formula:

CH₂＝C(－R⁶²)－C(＝O)－Y⁶¹－(R⁶¹)_p(－X⁶¹)_q

[ in the formula, R⁶¹A hydrocarbon group having 1 to 10 carbon atoms,

R⁶²is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom,

Y⁶¹is-O-or-NH-,

X⁶¹is a hydrophilic group, and is a hydrophilic group,

p is 0 or 1, and p is,

q is a number of 1 to 4. ].

Hydrophilic group (X)⁶¹) Examples of (b) are OH groups, NH₂A group, a COOH group, a sulfonic acid group or a phosphoric acid group, an alkali metal or alkaline earth metal salt group of carboxylic acid. By adding a polar group such as a hydrophilic group, a phase separation structure is easily formed, and the liquid repellency of the obtained copolymer is improved. In addition, the adhesion to a substrate such as cloth or glass is improved, and the water repellency and durability of the water repellency are improved.

R⁶¹Is a linear, branched or cyclic hydrocarbon group. R⁶¹The number of carbon atoms in (b) may be 1 to 6.

R⁶²May be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. R⁶²Examples of (B) are hydrogen, methyl, Cl, Br, I, CN. Since the more rigid the main chain, the less the crystallinity of the side chain of the block segment (A) is hindered, R is⁶²Hydrogen, methyl and Cl are preferred, hydrogen and methyl are more preferred, and hydrogen is more preferred.

Preferred specific examples of the acrylic monomer having a hydrophilic group are hydroxyethyl (meth) acrylate, hydroxyethyl (meth) acrylamide, (meth) acrylic acid, hydroxypropyl (meth) acrylate, hydroxypropyl (meth) acrylamide, hydroxybutyl (meth) acrylate, hydroxybutyl (meth) acrylamide, carboxyethyl (meth) acrylate, carboxyethyl (meth) acrylamide, carboxypropyl (meth) acrylate, carboxypropyl (meth) acrylamide, carboxybutyl (meth) acrylate, and carboxybutyl (meth) acrylamide.

Preferred examples of the cyclic hydrocarbon group-containing acrylate monomer are compounds represented by the following formula:

CH₂＝C(R⁷²)－C(＝O)－Y⁷¹－R⁷¹

[ in the formula, R⁷¹A hydrocarbon group containing a group of a cyclic hydrocarbon having 4 to 30 carbon atoms,

R⁷²is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom,

Y⁷¹is-O-or-NH-.]。

The cyclic hydrocarbon group-containing acrylic monomer is preferably a monomer whose homopolymer has a glass transition temperature to such an extent that the crystallinity of the block segment (a) is not impaired (for example, 25 ℃ or lower).

The cyclic hydrocarbon group-containing acrylic monomer has no fluoroalkyl group.

R⁷¹The hydrocarbon group may have a chain group (for example, a linear or branched hydrocarbon group). Examples of the cyclic hydrocarbon group include saturated or unsaturated, monocyclic group, polycyclic group, bridged ring group, and the like. The cyclic hydrocarbon group is preferably a saturated cyclic hydrocarbon group. The number of carbon atoms of the cyclic hydrocarbon group is 4 to 30, preferably 4 to 20. Examples of the cyclic hydrocarbon group are cyclic aliphatic groups having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and particularly 5 to 12 carbon atoms; an aromatic hydrocarbon group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms; an araliphatic hydrocarbon group having 7 to 30 carbon atoms, preferably 7 to 20 carbon atoms.

Examples of the cyclic hydrocarbon group include saturated or unsaturated, monocyclic group, polycyclic group, bridged ring group, and the like. The cyclic hydrocarbon group is preferably a saturated cyclic hydrocarbon group.

The number of carbon atoms of the cyclic hydrocarbon group is particularly preferably 15 or less, for example, 10 or less.

R⁷²May be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. R⁷²Examples of (B) are hydrogen, methyl, Cl, Br, I, CN. The more rigid the main chain of the resulting polymer, the less the crystallinity of the side chain is hindered, and therefore R⁷²Hydrogen, methyl and Cl are preferred, hydrogen and methyl are preferred, and hydrogen is more preferred.

Specific examples of the cyclic hydrocarbon group include cyclohexyl, t-butylcyclohexyl, isobornyl, dicyclopentyl, dicyclopentenyl and adamantyl. The acrylate group is preferably an acrylate group or a methacrylate group, and the acrylate group is particularly preferred. Specific examples of the monomer having a cyclic hydrocarbon group include cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl ethyl (meth) acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, and 2-ethyl-2-adamantyl (meth) acrylate.

The halogenated olefin may be C2-20 halogenated olefin substituted with 1-10 chlorine, bromine or iodine atoms. The halogenated olefin is preferably a C2-20 chlorinated olefin, particularly a C2-5 olefin having 1-5 chlorine atoms. Preferred examples of the halogenated olefin are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. The halogenated olefin has no fluorine atom.

The block segment (B2) may be a segment containing a silicon-containing monomer (silicon-containing compound). Examples of the silicon-containing monomer include monomers having a dimethylsiloxy group. The monomers having a dimethylsiloxy group are preferably compounds having a dimethylsiloxy group and an olefinic carbon-carbon double bond, in particular a (meth) acrylic group or a vinyl group.

Specific examples of the monomer having a dimethylsiloxane group are as follows.

CH₂＝C(CH₃)CO₂(CH₂)₃Si(CH₃)₂〔OSi(CH₃)₂〕_nOSi(CH₃)₂C₄H₉、

CH₂＝CHCO₂(CH₂)₃Si(CH₃)₂〔OSi(CH₃)₂〕_nOSi(CH₃)₂C₄H₉

The longer the dimethylsiloxane group length (n), the lower the glass transition temperature of the resulting copolymer, and the higher the flexibility, texture, and water-rolling properties of the coating film formed from the copolymer. On the other hand, if n is too long, the polymerization reactivity of the monomer having a dimethylsiloxy group is lowered. The length (n) of the dimethylsiloxane group is preferably 1 to 50, more preferably 3 to 30, and still more preferably 3 to 20.

Specific examples of the acrylic monomer having 2 acrylic groups and divinyl compound are tripropylene glycol di (meth) acrylate, divinylbenzene, tetramethylene glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate (1, 6-bisacryloylhexane), nonanediol di (meth) acrylate, decanediol di (meth) acrylate, glycerol dimethacrylate, 1- (acryloyloxy) -3- (methacryloyloxy) -2-propanol, ethylene glycol di (meth) acrylate, 1, 4-bis [ 4- (3-acryloyloxypropyloxy) benzoyloxy ] -2-methylbenzene. A trivinyl compound and a tetravinyl compound may be contained, and pentaerythritol tetraacrylate and the like are exemplified. In the case of a divinyl compound (or a tetravinyl or trivinyl compound), the compound has a structure containing a large number of branched sites, which is generally called a star shape. In the present specification, "block copolymer" having a block segment (a) also includes a case of having a star structure.

(B3) Random chain segment

The random segment (B3) is formed from at least 2 acrylic monomers. The acrylic monomer may be any of the acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms, the acrylic monomer having a short-chain hydrocarbon group having 1 to 6 carbon atoms, the acrylic monomer having a hydrophilic group, the acrylic monomer having a cyclic hydrocarbon group, the halogenated olefin, and the monomer having a dimethylsiloxy group. Other examples of the acrylic monomer are divinyl compounds, silicon-containing compounds. Examples of the divinyl compound include ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, divinylbenzene, tetramethylene glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, nonanediol di (meth) acrylate, decanediol di (meth) acrylate, glycerol dimethacrylate, 1- (acryloyloxy) -3- (methacryloyloxy) -2-propanol, ethylene glycol dimethacrylate, and 1, 4-bis [ 4- (3-acryloyloxypropyl) benzoyloxy ] -2-methylbenzene. Trivinyl compounds and tetravinyl compounds may also be contained, and pentaerythritol tetraacrylate is exemplified.

In the case of a divinyl compound (or a tetravinyl or trivinyl compound), the compound has a structure containing a large number of branched sites, which is generally called a star shape. In the present specification, "block copolymer" having a block segment (a) also includes a case of having a star structure.

Specific examples of the combination of 2 kinds of acrylic monomers are:

stearyl (meth) acrylate/(hydroxyethyl (meth) acrylate),

T-butyl (meth) acrylate/(hydroxyethyl (meth) acrylate),

Stearyl (meth) acrylate/(hydroxybutyl (meth) acrylate),

T-butyl (meth) acrylate/(hydroxybutyl (meth) acrylate),

Stearyl (meth) acrylate/(tert-butyl (meth) acrylate)

Hydroxyethyl (meth) acrylate/hydroxybutyl methacrylate glycidyl ether,

Hydroxybutyl (meth) acrylate/hydroxybutyl methacrylate glycidyl ethers,

Hydroxyethyl (meth) acrylate/(glycidyl (meth) acrylate),

Hydroxybutyl (meth) acrylate/(glycidyl (meth) acrylate),

Stearyl (meth) acrylate/divinyl compounds (or tetravinyl, trivinyl compounds),

Hydroxyethyl (meth) acrylate/divinyl compounds (or tetravinyl, trivinyl compounds),

Hydroxybutyl (meth) acrylate/divinyl compounds (or tetravinyl, trivinyl compounds),

Tert-butyl (meth) acrylate/divinyl compounds (or tetravinyl, trivinyl compounds).

Silicon-containing compounds can be used as monomers or chain transfer agents. One or both of a silicon-containing monomer and a silicon-containing chain transfer agent may be used.

Examples of the silicon-containing monomer include monomers having a silane group. The monomer having a silane group is preferably a compound having a silane group (particularly a terminal silane group) and an olefinic carbon-carbon double bond (particularly a (meth) acrylic group or a vinyl group). The monomer having a silane group may be a monomer having a terminal silane coupling group, or a monomer having a silane coupling group in a side chain.

The silicon-containing monomer may be a monomer having 1 (meth) acrylic group or vinyl group and 1 silane group. The 1 (meth) acrylic group or vinyl group is preferably bonded to the 1 silyl group through a (2-valent) bonding group such as a valence bond, an alkylene group having 1 to 10 carbon atoms, or a siloxane group. In the case of a (meth) acrylic group, the bonding group is preferably an alkylene group having 1 to 10 carbon atoms or a siloxane group. In the case of a vinyl group, the bonding group is preferably a bond.

Specific examples of the monomer having a silane group are as follows:

CH₂＝CHCO₂(CH₂)₃Si(OCH₃)₃、

CH₂＝CHCO₂(CH₂)₃Si(OC₂H₅)₃、

CH₂＝C(CH₃)CO₂(CH₂)₃Si(OCH₃)₃、

CH₂＝C(CH₃)CO₂(CH₂)₃Si(OC₂H₅)₃、

CH₂＝CHCO₂(CH₂)₃SiCH₃(OC₂H₅)₂、

CH₂＝C(CH₃)CO₂(CH₂)₃SiCH₃(OC₂H₅)₂、

CH₂＝C(CH₃)CO₂(CH₂)₃SiC₂H₅(OCH₃)₂、

CH₂＝CHCO₂(CH₂)₃SiC₂H₅(OCH₃)₂、

CH₂＝C(CH₃)CO₂(CH₂)₃Si(CH₃)₂(OC₂H₅)、

CH₂＝C(CH₃)CO₂(CH₂)₃Si(CH₃)₂(OCH₃)、

CH₂＝C(CH₃)CO₂(CH₂)₃Si(CH₃)₂OH、

CH₂＝CHCO₂(CH₂)₃SiCH₃〔ON(CH₃)C₂H₅〕₂、

CH₂＝C(CH₃)CO₂(CH₂)₃SiC₆H₅〔ON(CH₃)C₂H₅〕₂、

CH₂＝C(CH₃)CO₂(CH₂)₃Si(CH₃)₂〔OSi(CH₃)₂〕_nOSi(CH₃)₂C₄H₉、

CH₂＝CHCO₂(CH₂)₃Si(CH₃)₂〔OSi(CH₃)₂〕_nOSi(CH₃)₂C₄H₉、

CH₂＝CHSi(OCH₃)₃、

CH₂＝CHSi(OC₂H₅)₃、

CH₂＝CHSiCH₃(OCH₃)₂、

CH₂＝CHSi(CH₃)₂(OC₂H₅)、

CH₂＝CHSi(CH₃)₂SiCH₃(OCH₃)₂、

CH₂＝CHSiCH₃〔ON(CH₃)C₂H₅〕₂

vinyl trichlorosilane,

Vinyltris (2-methoxyethoxy) silane.

Silicon-containing compounds can be used as chain transfer agents. The silicon-containing chain transfer agent may be a mercapto-functional organopolysiloxane. By polymerizing the monomers in the presence of a silicon-containing chain transfer agent, a block copolymer having siloxane groups can be obtained. In 1 embodiment, the mercapto-functional organopolysiloxane comprises siloxane units having the average formula:

(R₂SiO)_a(RR^NSiO)_b(RR^SSiO)_c

[ in the formula, a is 0 to 4000, or 0 to 1000, or 0 to 400,

b is 1 to 1000, or 1 to 100, or 1 to 50,

c is 1 to 1000, or 1 to 100, or 1 to 50;

r is independently a monovalent organic group,

or R is a hydrocarbon having 1 to 30 carbon atoms,

or R is a C1-12 monovalent alkyl group,

or, R is methyl;

R^Nis a monovalent amino-functional organic radical,

R^Sis a monovalent mercapto-functional organic radical.]

Amino-functional organic radicals R as organofunctional groups^NMay be prepared by having the formula: -R¹NHR²And the formula: -R¹NR₂ ²Or the formula: -R¹NHR¹NHR²(wherein each R is¹Independently a divalent hydrocarbon group having 2 or more carbon atoms, R²Is hydrogen or an alkyl group having 1 to 20 carbon atoms. ) The groups of (a) are exemplified. Each R is¹Typically an alkylene group having 2 to 20 carbon atoms.

Several examples of preferred amino-functional hydrocarbyl groups are:

－CH₂CH₂NH₂、－CH₂CH₂CH₂NH₂、

－CH₂CHCH₃NH₂、－CH₂CH₂CH₂CH₂NH₂、

－CH₂CH₂CH₂CH₂CH₂NH₂、

－CH₂CH₂CH₂CH₂CH₂CH₂NH₂、

－CH₂CH₂NHCH₃、－CH₂CH₂CH₂NHCH₃、

－CH₂(CH₃)CHCH₂NHCH₃、－CH₂CH₂CH₂CH₂NHCH₃、

－CH₂CH₂NHCH₂CH₂NH₂、

－CH₂CH₂CH₂NHCH₂CH₂CH₂NH₂、

－CH₂CH₂CH₂CH₂NHCH₂CH₂CH₂CH₂NH₂、

－CH₂CH₂NHCH₂CH₂NHCH₃、

－CH₂CH₂CH₂NHCH₂CH₂CH₂NHCH₃、

－CH₂CH₂CH₂CH₂NHCH₂CH₂CH₂CH₂NHCH₃and, and

－CH₂CH₂NHCH₂CH₂NHCH₂CH₂CH₂CH₃. Typically, the amino-functional group is-CH₂CH₂CH₂NH₂。

R^SCan be obtained by the formula: -R¹SR²(wherein each R is¹Independently a divalent hydrocarbon group having 2 or more carbon atoms, R²Is hydrogen or an alkyl group having 1 to 20 carbon atoms. In the formula, each R¹And R²As described above. ) The groups shown are illustrative. Each R is¹Typically an alkylene group having 2 to 20 carbon atoms. Examples of mercapto-functional groups are shown below:

－CH₂CH₂CH₂SH、－CH₂CHCH₃SH、－CH₂CH₂CH₂CH₂SH、－CH₂CH₂CH₂CH₂CH₂SH、－CH₂CH₂CH₂CH₂CH₂CH₂SH、－CH₂CH₂SCH₃. Typically, the mercapto-functional group is-CH₂CH₂CH₂SH。

In the present specification, the acrylic monomer is usually a (meth) acrylate or a (meth) acrylamide.

In the present specification, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acrylamide" means acrylamide or methacrylamide.

The amount of the acrylic monomer (a) having a long-chain hydrocarbon group having 7 to 40 carbon atoms may be 30 mol% or more, and preferably 35 mol% or more, based on the repeating unit of the block copolymer. The amount of the monomer (a) may be 99 mol% or less with respect to the repeating unit of the block copolymer.

The molar ratio of the repeating units in the block segment (a) and the other segment (B) may be, for example, 30: 70-99: 1, preferably 35: 65-90: 10, in particular 40: 60-90: 10. when the block segment (C) is present, the amount of the repeating unit in the block segment (C) may be 0.1 to 30 mol%, for example, 1 to 20 mol%, based on the repeating units of the entire block copolymer.

The number average molecular weight (Mn) of the block copolymer may be usually 1000 to 1000000, for example 5000 to 500000, preferably 8000 to 200000, more preferably 8000 to 100000. The number average molecular weight (Mn) of the block copolymer is generally determined by GPC (gel permeation chromatography). The copolymer synthesized by an active polymerization method such as ATRP or RAFT method shows a monomodal peak, and the molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) is narrow, and is usually 3.0 or less, preferably 2.0 or less.

The thermal properties of the block copolymer of the present invention such as melting point, glass transition temperature, crystallization temperature, melting energy and the like can be measured by Differential Scanning Calorimetry (DSC). It is known that a block copolymer generally exhibits a melting point or a glass transition temperature equivalent to that of a homopolymer composed of only monomers of its structural units. The block copolymer of the present invention also exhibits the same melting point as that of the homopolymer of the monomer of the structural unit of the block segment (a), and in the case of a copolymer having no random structure of the block segment (a), exhibits a melting point lower than that of the homopolymer of the monomer of the structural unit. In the case of a polymer comprising an acrylic monomer having a long chain hydrocarbon group, the melting point is derived from its long chain hydrocarbon group. The high melting point of the long-chain hydrocarbon group is preferable because the liquid repellency of the coating film made of the polymer is improved. Therefore, the block copolymer of the present invention, which shows the same melting point as that of a homopolymer composed only of an acrylic monomer having a long-chain hydrocarbon group, is more preferable than the random copolymer.

The block copolymer preferably has a melting point within-15 ℃ (e.g., 0 to 15 ℃ lower), more preferably within-10 ℃, and even more preferably within-5 ℃ than the melting point exhibited by the homopolymer.

For example, since the melting point (Tm) of a homopolymer comprising a stearyl acrylate as an acrylic monomer is 50.3 ℃, the case of an acrylic monomer having a stearyl acrylate as a block segment (A)In this case, the melting point of the block copolymer is preferably 35.3 ℃ or higher, more preferably 40.3 ℃ or higher, and particularly preferably 45.3 ℃ or higher (the upper limit of the melting point of the block copolymer is the maximum value of the melting points of the individual homopolymers of the monomers constituting the block copolymer). Also by CH₂＝CHCO₂－CH₂CH₂－O－C(＝O)－NH－C₁₈H₃₇The melting point (Tm) of a homopolymer, which is an acrylic monomer, is 72.3 ℃ and therefore has a CH₂＝CHCO₂－CH₂CH₂－O－C(＝O)－NH－C₁₈H₃₇In the case of the acrylic monomer as the block segment (A), the melting point of the block copolymer is preferably 57.3 ℃ or higher, more preferably 62.3 ℃ or higher, and particularly preferably 67.3 ℃ or higher. Also by CH₂＝CHCO₂－CH₂CH₂－NH－C(＝O)－C₁₇H₃₅The melting point (Tm) of a homopolymer, which is an acrylic monomer, is 93.6 ℃ and therefore has a CH₂＝CHCO₂－CH₂CH₂－NH－C(＝O)－C₁₇H₃₅In the case of the acrylic monomer as the block segment (A), the melting point of the block copolymer is preferably 78.6 ℃ or higher, more preferably 83.6 ℃ or higher, and particularly preferably 88.6 ℃ or higher. When the block segment has 2 or more kinds of acrylic monomers, the melting point of each homopolymer is preferably within 15 ℃ or lower (0 to 15 ℃ or lower), more preferably within 10 ℃ or lower, and particularly preferably within 5 ℃ or lower (the upper limit of the melting point of the copolymer is the highest value of the melting point of each homopolymer of the monomers constituting the block copolymer).

From the viewpoint of liquid repellency, a higher melting point is better, but if the melting point of the corresponding monomer is high, there is a possibility that the solubility of the monomer decreases or the emulsification is unstable during polymerization. Thus, the block copolymer preferably has a melting point of 40 to 200 ℃, more preferably 45 to 180 ℃, and preferably 50 to 170 ℃. The liquid repellency of the copolymer can be evaluated by the difference between the melting point of the copolymer and that of the homopolymer and the value of the melting point itself. However, even if the melting point satisfies the above temperature range, it is preferable that the preferable conditions of the dynamic and static contact angles of water described later are also satisfied in order to make the coating film formed of the block polymer exhibit good water repellency. Similarly, in order to make a coating film formed of a block polymer exhibit good oil repellency, it is preferable to satisfy preferable conditions of dynamic and static contact angles of hexadecane described later.

The liquid repellency of the block polymer can be evaluated by dissolving the polymer in a solvent, applying the solution to a substrate by a spin coating method or the like to prepare a smooth coating film, and measuring the static and dynamic contact angles of the coating film. In the case of the static contact angle of water, it is preferably 107 ° or more, more preferably 108 ° or more, and particularly preferably 110 ° or more. In the case of a dynamic contact angle of water, the roll-off angle is preferably 20 ° or less, more preferably 18 ° or less, and particularly preferably 15 ° or less. In order for the polymer to exhibit water repellency, it is preferable that both the static and dynamic contact angles of water satisfy the above-mentioned ranges. However, when the roll off angle of water is 8 ° or less, and thus the rolling off property is very high, if the static contact angle is 103 ° or more, it can be judged that the water repellent property is good. The static contact angle of hexadecane is preferably 40 ° or more, and the dynamic contact angle of hexadecane is preferably 9 ° or less, more preferably 7 ° or less, and particularly preferably 5 ° or less. In order for the polymer to exhibit oil repellency, both the static and dynamic contact angles of hexadecane are preferred to satisfy the above conditions.

The water repellency of the cloth coated with the block copolymer of the present invention was evaluated by a spray water repellency test (JIS-L-1092 (AATCC-22): described below). The water repellency is in the order of from poor to excellent, 0, 50, 70, 80, 90 and 100 minutes, preferably 70 minutes or more.

The strong water repellency of the cloth coated with the block copolymer of the present invention can be evaluated visually from the ease of repelling water from the cloth and the speed of water flowing down from the cloth, even when tested by the spray method of JIS-L-1092 (AATCC-22). The strong water repellency is in the order of from poor to excellent, 1, 2, 3, 4 and 5 points, preferably 2 points or more.

The preferable mode in the above-mentioned spray water repellency test and the strong water repellency test is an index of the water repellency of the cloth, and is a preferable mode of the present invention.

In the present invention, the monomer is copolymerized to obtain a composition in which the copolymer is dispersed or dissolved in a medium.

(2) Liquid medium

The liquid medium is at least 1 selected from water and organic solvent. The liquid medium may be an organic solvent alone. Alternatively, the liquid medium may be an aqueous medium. The aqueous medium may be water alone or a mixture of water and a (water-miscible) organic solvent. The amount of the water-miscible organic solvent is 30 wt% or less, for example, 10 wt% or less, based on the liquid medium.

The amount of the liquid medium may be 30 to 99.5 wt%, particularly 50 to 99.3 wt%, based on the surface treatment agent.

(3) Other ingredients

The surface treatment agent may contain other components.

When the surface treatment agent is an aqueous emulsion, it preferably contains an emulsifier. The emulsifier may be at least 1 selected from the group consisting of a nonionic emulsifier, a cationic emulsifier, an anionic emulsifier and an amphoteric emulsifier.

Nonionic surfactant

Examples of the nonionic surfactant include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides.

Examples of ethers are compounds having oxyalkylene groups (preferably polyoxyethylene groups).

Examples of esters are esters of alcohols with fatty acids. Examples of the alcohol include 1 to 6-membered (particularly 2 to 5-membered) alcohols (e.g., aliphatic alcohols) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). Examples of the fatty acid include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

Examples of the ester ether are compounds obtained by adding an alkylene oxide (particularly ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of the alcohol include 1 to 6-membered (particularly 2 to 5-membered) alcohols (e.g., aliphatic alcohols) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). Examples of the fatty acid include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolamide. Examples of the fatty acid include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

The polyhydric alcohol may be a 2-5-membered alcohol having 10-30 carbon atoms.

The amine oxide may be an oxide (e.g., 5 to 50 carbon atoms) of an amine (secondary or preferably tertiary).

The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms of the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is preferably 2 to 100 in general.

The nonionic surfactant is selected from ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.

The nonionic surfactant may be an alkylene oxide adduct of a linear and/or branched aliphatic (saturated and/or unsaturated) group, a polyalkylene glycol ester of a linear and/or branched fatty acid (saturated and/or unsaturated), a Polyoxyethylene (POE)/polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of an acetylene glycol, or the like. Among these, nonionic surfactants having a structure of Polyoxyethylene (POE), polyoxypropylene (POP) or POE/POP copolymer (random copolymer or block copolymer) as the alkylene oxide addition moiety and the polyalkylene glycol moiety are preferable.

In addition, the nonionic surfactant is preferably a structure containing no aromatic group in view of environmental problems (biodegradability, environmental hormone, etc.).

The nonionic surfactant may be a compound represented by the formula:

R¹O－(CH₂CH₂O)_p－(R²O)_q－R³

[ in the formula, R¹Is an alkyl group having 1 to 22 carbon atoms or an alkenyl group or acyl group having 2 to 22 carbon atoms,

R²independently of each other, the same or different alkylene groups having 3 or more carbon atoms (for example, 3 to 10 carbon atoms),

R³is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms,

p is a number of 2 or more,

q is 0 or a number of 1 or more. ].

R¹Preferably 8 to 20 carbon atoms, and particularly preferably 10 to 18 carbon atoms. As R¹Preferable specific examples of (d) include lauryl, tridecyl and oleyl (oleyl).

R²Examples of (B) are propylene and butylene.

In the nonionic surfactant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (e.g., 5 to 200). Namely, - (R)²O)_qPolyoxyalkylene chains can be formed.

The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (in particular, a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, and among them, an oxypropylene chain is preferable.

Preferred nonionic surfactants are those of the formula:

R¹O－(CH₂CH₂O)_p－H

[ in the formula, R¹And p has the same meaning as above.]。

Specific examples of the nonionic surfactant are:

C₁₀H₂₁O－(CH₂CH₂O)_p－(C₃H₆O)_q－H

C₁₂H₂₅O－(CH₂CH₂O)_p－(C₃H₆O)_q－H

C₁₆H₃₁O－(CH₂CH₂O)_p－(C₃H₆O)_q－H

C₁₆H₃₃O－(CH₂CH₂O)_p－(C₃H₆O)_q－H

C₁₈H₃₅O－(CH₂CH₂O)_p－(C₃H₆O)_q－H

C₁₈H₃₇O－(CH₂CH₂O)_p－(C₃H₆O)_q－H

C₁₂H₂₅O－(CH₂CH₂O)_p－(C₃H₆O)_q－C₁₂H₂₅

C₁₆H₃₁O－(CH₂CH₂O)_p－(C₃H₆O)_q－C₁₆H₃₁

C₁₆H₃₃O－(CH₂CH₂O)_p－(C₃H₆O)_q－C₁₂H₂₅

iso－C₁₃H₂₇O－(CH₂CH₂O)_p－(C₃H₆O)_q－H

C₁₀H₂₁COO－(CH₂CH₂O)_p－(C₃H₆O)_q－H

C₁₆H₃₃COO－(CH₂CH₂O)_p－(C₃H₆O)_q－C₁₂H₂₅

[ in the formula, p and q have the same meanings as described above. And the like.

Specific examples of the nonionic surfactant include ethylene oxide, hexylphenol and isooctanePhenol, hexadecanol, oleic acid, alkane (C)₁₂－C₁₆) Thiol, sorbitan mono fatty acid (C)₇－C₁₉) Or alkyl (C)₁₂－C₁₈) Amine, and the like.

The proportion of the polyoxyethylene block may be 5 to 80% by weight, for example 30 to 75% by weight, particularly 40 to 70% by weight, based on the molecular weight of the nonionic surfactant (copolymer).

The average molecular weight of the nonionic surfactant is usually 300 to 5,000, for example 500 to 3,000.

The nonionic surfactant may be used alone in an amount of 1 kind or in combination of 2 or more kinds.

The nonionic surfactant is preferably a combination of 2 or more. In combinations of 2 or more, at least 1 nonionic surfactant can be R¹Radical (and/or R)³Radical) is a branched alkyl radical (e.g. isotridecyl radical)¹O－(CH₂CH₂O)_p－(R²O)_q－R³[ especially R ]¹O－(CH₂CH₂O)_p－H]The compounds shown. R¹The amount of the nonionic surfactant having a branched alkyl group may be 5 to 100 parts by weight, for example, 8 to 50 parts by weight, particularly 10 to 40 parts by weight, based on 100 parts by weight of the total of the nonionic surfactants (B2). In combinations of 2 or more, the other nonionic surfactant may be R¹Radical (and/or R)³Alkyl) is a (saturated and/or unsaturated) straight chain alkyl (e.g. lauryl (n-lauryl)) R¹O－(CH₂CH₂O)_p－(R²O)_q－R³[ especially R ]¹O－(CH₂CH₂O)_p－H]The compounds shown.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, fatty acid alkanolamides, alkyl alkanolamides, acetylene glycols, oxyethylene adducts of acetylene glycols, polyethylene glycol-polypropylene glycol block copolymers, and the like.

Since the aqueous emulsion has a low dynamic surface tension (that is, the aqueous emulsion easily penetrates into the substrate), the nonionic surfactant is preferably an alkynol (particularly an alkynediol) or an oxyethylene adduct of an alkynol (particularly an alkynediol).

Preferred nonionic surfactants are alcohols having an unsaturated triple bond or alkylene oxide adducts of the alcohols (both the alcohols and the alkylene oxide adducts are referred to as "alkynol compounds"). Particularly preferred nonionic surfactants are alkylene oxide adducts of monohydric or polyhydric alcohols having an unsaturated triple bond.

The alkynol compound is a compound containing 1 or more triple bonds and 1 or more hydroxyl groups. The alkynol compound may be a compound comprising a polyoxyalkylene moiety. Examples of the polyoxyalkylene moiety include polyoxyethylene, polyoxypropylene, a random addition structure of polyoxyethylene and polyoxypropylene, and a block addition structure of polyoxyethylene and polyoxypropylene.

The alkynol compound may be a compound represented by the following formula:

HO－CR¹¹R¹²－C≡C－CR¹³R¹⁴-OH, or

HO－CR¹⁵R¹⁶－C≡C－H，

[ in the formula, R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶Each independently represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms.]. The alkynol compound may be an alkylene oxide adduct of the compound represented by the formula. The alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and particularly preferably a linear or branched alkyl group having 6 to 12 carbon atoms. Examples thereof include methyl, ethyl, propyl, butyl, and isobutyl. In addition, as an epoxyThe alkane is preferably an alkylene oxide having 1 to 20 (particularly 2 to 5) carbon atoms such as ethylene oxide and propylene oxide, and the number of addition of the alkylene oxide is preferably 1 to 50.

Specific examples of the alkynol compound include acetylene diol, propynol (propargyl alcohol), 2, 5-dimethyl-3-hexyne-2, 5-diol, 3, 6-dimethyl-4-octyne-3, 6-diol, 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, 3, 5-dimethyl-1-hexyne-3-ol, 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyn-3-ol, 3-hexyne-2, 5-diol, and 2-butyne-1, 4-diol. Polyethoxylates and ethylene oxide adducts of these specific compounds can also be mentioned.

The nonionic surfactant may have no triple bond, or may have a triple bond. The nonionic surfactant may be only one of a nonionic surfactant having no triple bond or a nonionic surfactant having a triple bond, or may be a combination of a nonionic surfactant having no triple bond and a nonionic surfactant having a triple bond. In the combination of the nonionic surfactant having no triple bond and the nonionic surfactant having triple bond, the weight ratio of the nonionic surfactant having no triple bond (e.g., the nonionic surfactant having oxyalkylene group) and the nonionic surfactant having triple bond (e.g., the alkynol compound) may be 10: 90-90: 10, for example 20: 80-80: 20.

cationic surfactant

The cationic surfactant is preferably a compound having no amide group.

Examples of the cationic surfactant include amines, amine salts, quaternary ammonium salts, imidazolines, and imidazolinium salts.

The cationic surfactant is preferably an amine salt, a quaternary ammonium salt, or an oxyethylene addition type ammonium salt. Specific examples of the cationic surfactant include, but are not particularly limited to, amine salt type surfactants such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines, quaternary ammonium salt type surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride, and the like.

Examples of cationic surfactants are

R²¹－N⁺(－R²²)(－R²³)(－R²⁴)X^－

[ in the formula, R²¹、R²²、R²³And R²⁴Independently, the same or different are hydrogen atoms or hydrocarbon groups having 1 to 50 carbon atoms, and X is an anionic group.]The compound of (1). The hydrocarbon group may have an oxygen atom, and may be an oxyalkylene group such as a polyoxyalkylene group (the number of carbon atoms in the alkylene group is, for example, 2 to 5.). R²¹、R²²、R²³And R²⁴Preferably a hydrocarbon group having 1 to 30 carbon atoms (for example, an aliphatic hydrocarbon, an aromatic hydrocarbon or an araliphatic hydrocarbon).

R²¹、R²²、R²³And R²⁴Specific examples of (b) are alkyl groups (e.g., methyl, butyl, stearyl, palmityl), aryl groups (e.g., phenyl), and aralkyl groups (e.g., benzyl (phenylmethyl), phenethyl (phenylethyl)).

Specific examples of X include halogen (e.g., chlorine), acid (e.g., inorganic acid such as hydrochloric acid, and organic acid (particularly fatty acid)) such as acetic acid.

The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (having 4 to 30 carbon atoms in the alkyl group).

The cationic surfactant is preferably an ammonium salt, and particularly preferably a quaternary ammonium salt. The cationic surfactant may be an ammonium salt represented by the following formula:

R³¹ _p－N⁺R³² _qX^－

[ in the formula, R³¹Each independently, identically or differently, is C12 or more (e.g. is C₁₂～C₅₀) The linear and/or branched aliphatic (saturated and/or unsaturated) group of (A),

R³²independently of each other, the same or different are H or C1-4 alkyl, benzyl, polyoxyalkyleneThe number of ethyl groups (oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50) (particularly preferably CH₃、C₂H₅)，

X is a halogen atom (e.g. chlorine and bromine), C₁～C₄The fatty acid radical of (a) is,

p is 1 or 2, q is 2 or 3, and p + q is 4.]。R³¹The number of carbon atoms in (b) may be 12 to 50, for example 12 to 30.

Specific examples of the cationic surfactant include: dodecyl trimethyl ammonium acetate, trimethyl tetradecyl ammonium chloride, hexadecyl trimethyl ammonium bromide, trimethyl octadecyl ammonium chloride, (dodecyl methylbenzyl) trimethyl ammonium chloride, benzyl dodecyl dimethyl ammonium chloride, methyl dodecyl di (hydrogen polyoxyethylene) ammonium chloride, and benzyl dodecyl di (hydrogen polyoxyethylene) ammonium chloride.

Examples of the amphoteric surfactant include alanine, imidazolinium betaine, amidobetaine, and acetate betaine, and specifically include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethyl glycine betaine, and fatty acid amidopropyl dimethyl glycine betaine.

The surfactant may be an amidoamine surfactant which is a compound having an amide group and an amino group.

The amidoamine surfactant is preferably a compound of the formula:

R¹¹－C(＝O)(R¹²－)N－(CH₂)_n－N－(－R¹³)(－R¹⁴)

[ in the formula, R¹¹、R¹²、R¹³And R¹⁴Independently of each other, the same or different are a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms,

n is 0 to 10. ].

R¹¹Preferably an alkyl or alkenyl group. R¹¹The number of carbon atoms in (b) may be 8 to 30, for example 12 to 24. R¹²、R¹³And R¹⁴Preferably a hydrogen atom or an alkyl group. R¹²、R¹³And R¹⁴The number of carbon atoms of (A) is preferably 1 to 6, and particularly preferably 1 to 4. n is 0 to 10, such as 1 to 10, especially 2 to 5.

Specific examples of the amidoamine surfactant include diethylaminoethylamide isostearate, dimethylaminoethylamide oleate, dimethylaminopropylamide oleate, diethylaminoethylamide oleate, diethylaminopropylamide oleate, diethylaminoethylamide stearate, diethylaminopropylamide stearate, dibutylaminoethylamide stearate, dibutylaminopropylamide stearate, dipropylaminopropylamide stearate, dipropylaminoethylamide stearate, dimethylaminoethylamide stearate, dimethylaminopropylamide stearate, diethylaminoethylamide palmitate, diethylaminopropylamide palmitate, dimethylaminoethylamide palmitate, dimethylaminopropylamide palmitate, diethylaminoethylamide behenate, diethylaminopropylamide behenate, and mixtures thereof, Behenic acid dimethylaminopropylamide, and the like.

The amidoamine surfactant may be a nonionic or ionic (cationic) surfactant, preferably a nonionic surfactant. In the case of nonionic property, it is preferable to use the compound by adding an ionic compound such as an acid to the compound for ionization.

The nonionic surfactant, the cationic surfactant and the amphoteric surfactant may each be a combination of 1 kind or 2 or more.

The amount of the surfactant may be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight, based on 100 parts by weight of the polymer.

The surface treatment agent may contain an additive as another component.

Examples of additives are silicon-containing compounds, waxes, acrylic emulsions, etc. Other examples of the additives are fluoropolymers, drying speed regulators, crosslinking agents, film-forming aids, solubilizers, surfactants, anti-freezing agents, viscosity regulators, ultraviolet absorbers, antioxidants, pH regulators, anti-foaming agents, texture regulators, slip regulators, antistatic agents, hydrophilizing agents, antibacterial agents, preservatives, insect-proofing agents, fragrances, flame retardants, and the like.

The amount of the other component may be 0.1 to 70% by weight, for example, 0.5 to 50% by weight, based on the surface treatment agent.

[ method for producing Block copolymer ]

The block copolymer is preferably produced by using a living polymerization method, for example, a living radical polymerization method, a living anion polymerization method, or a living cation polymerization method. Living radical polymerization is particularly preferred.

The living radical polymerization method is based on the action of heat, light, a metal catalyst, etc., and establishes a rapid balance between a small number of growing radical (free radical) species and a large number of Dormant (Dormant) species in the growth reaction. Various forms of living radical polymerization via Dormant (Dormant) chains are proposed.

For example, there have been proposed an ATRP method (atom transfer radical polymerization) using a halogenated alkyl group as a dormant species, a RAFT method (reversible addition fragmentation chain transfer) using a thioester, and an NMP method (nitroxide mediated polymerization) using an alkoxyamine.

The ATRP method (atom transfer radical polymerization) is a method of polymerizing a vinyl monomer using a polymerization initiator having a highly reactive carbon-halogen bond and a transition metal complex as a polymerization catalyst (Japanese patent application laid-open No. 2000-514479, Zebra et al, Macromolecules 1995, 28, 1721).

The RAFT method is a method of polymerizing a vinyl monomer by adding a chain transfer agent having a high chain transfer constant, called RAFT agent, to a general radical polymerization system (m.g. head et al, Macromolecules 1998, 31, 5559). As the RAFT agent, thioesters can be used.

The NMP method is a method in which alkoxyamines are thermally cleaved to generate stable nitroxides and polymer radicals, and vinyl monomers are polymerized on the polymer radicals (m.k. georges et al, Macromolecules 1993, 26, 2987). The cleaved nitroxides do not initiate polymerization but only react with carbon-centered free radicals. The nitroxide can be stably present as a dormant species by recombination with the polymer radical reacted with the monomer. Living radical polymerization was carried out in the procedure described above.

The ATRP method (atom transfer radical polymerization method) is described in detail below.

In the ATRP method, a vinyl monomer is polymerized using a polymerization initiator having a highly reactive carbon-halogen bond and a transition metal complex as a polymerization catalyst.

Examples of the polymerization initiator are benzyl halides, halogenated alkanes, halogenated esters, halogenated ketones, halogenated nitriles and sulfonyl halides. Examples of the benzyl halide include 1-phenylethyl chloride and 1-bromoethylbenzene. Examples of the halogenated alkane include chloroform and carbon tetrachloride. Examples of the halogenated ester include ethyl 2-bromoisobutyrate and ethyl 2-bromopropionate. Examples of the halogenated ketone include bromoacetone and bromoacetophenone. As the halogenated nitrile, 2-bromopropionitrile may be mentioned. Examples of the sulfonyl halide include p-toluenesulfonyl chloride.

The amount of the polymerization initiator used is not particularly limited, and the concentration in the reaction system is usually 0.001 to 10 mol/liter, preferably 0.010 to 5 mol/liter.

The transition metal complex is not particularly limited, and is a metal complex having a transition metal (M) selected from groups 7 to 11 of the periodic table as a central metal.

Specific examples of the transition metal (M) include Cu⁰、Cu⁺、Ni⁰、Ni⁺、Ni²⁺、Pd⁰、Pd⁺、Pt⁰、Pt⁺、Pt²⁺、Rh⁺、Rh²⁺、Rh³⁺、Co⁺、Co²⁺、Ir⁰、Ir⁺、Ir²⁺、Ir³⁺、Fe²⁺、Ru²⁺、Ru³⁺、Ru⁴⁺、Ru⁵⁺、Os²⁺、Os³⁺、Re²⁺、Re³⁺、Re⁴⁺、Re⁶⁺、Mn²⁺、Mn³⁺. Among these, from the catalyst activityFrom the viewpoint of degree, Cu is preferred⁺、Ni²⁺、Fe²⁺、Ru²⁺。

Examples of the metal compound used for the transition metal complex compound are given. Examples of the copper compound having 1-valent metallic copper include cuprous chloride, cuprous bromide, cuprous iodide, and cuprous cyanide, examples of the nickel compound having 2-valent nickel include nickel dichloride, nickel dibromide, and nickel diiodide, examples of the iron compound having divalent iron include iron dichloride, iron dibromide, and iron diiodide, and examples of the ruthenium compound having 2-valent ruthenium include ruthenium dichloride, ruthenium dibromide, and ruthenium diiodide.

The organic ligand is preferably coordinated to the transition metal (M) from the viewpoint of achieving solubilization in a polymerization solvent and reversible change of the redox conjugated complex compound and improving the catalyst activity. Examples of the coordinating atom on the metal include a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, and the like, and a nitrogen atom or a phosphorus atom is preferable. Specific examples of the organic ligand include 2,2' -bipyridine and derivatives thereof, 1, 10-phenanthroline and derivatives thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, tris (dimethylaminoethyl) amine, triphenylphosphine, tributylphosphine, and the like. The amount of the organic ligand used is not particularly limited, and is usually 0.1 to 100 times, preferably 1 to 10 times, the amount of the transition metal (M).

The amount of the transition metal (M) used is not particularly limited, and is usually 0.01 to 100mol, preferably 0.1 to 50mol, and more preferably 0.1 to 10mol, based on 1mol of the polymerization initiation end of the polymerization initiator.

The atom transfer radical polymerization may be conducted in the presence of a reducing agent for the transition metal. By allowing a reducing agent to coexist, it is possible to reduce the deactivation of the catalyst or to carry out polymerization without strictly controlling the deoxidation. In addition, the amount of the transition metal used can be reduced, or the transition metal can be easily removed from the product, and there is an advantage in terms of cost. Examples of the reducing agent include 0-valent copper, ascorbic acid, sodium ascorbate, stannous and sugar. The amount of the reducing agent is usually about 10 molar equivalents to the transition metal catalyst. In addition, a radical polymerization initiator such as an azo compound may be added as a reducing agent.

The atom transfer radical polymerization can be carried out in the absence of a solvent, but may be carried out in the presence of a solvent. Examples of the solvent to be used as needed include water; ethers such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile, and benzonitrile; ester compounds or carbonate compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethylene carbonate, and propylene carbonate; alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol, and isoamyl alcohol; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as chlorobenzene, dichloromethane, chloroform, chlorobenzene, and trifluorotoluene.

The amount of the solvent used is not particularly limited, and is usually 30 to 5000 parts by weight, preferably 50 to 2000 parts by weight, and more preferably 50 to 1000 parts by weight, based on 100 parts by weight of the monomer charge.

The atom transfer radical polymerization is usually carried out at a temperature of-50 to 200 ℃, preferably 0 to 150 ℃, more preferably 20 to 130 ℃. The order of addition of the respective substances is not particularly limited, and any of them may be used, and it is preferable that substances other than the polymerization initiator are dissolved to prepare a uniform solution, and then the initiator is added to the solution immediately before the temperature is raised to the polymerization temperature to perform polymerization.

After completion of the polymerization, it is a common practice in industry to supply the polymerization reaction liquid as it is to the next step (for example, the step of forming the second block chain). However, the first block chain may be separated from the polymerization reaction liquid as needed. For example, distillation removal of residual monomers or solvents, reprecipitation in an appropriate solvent, filtration or centrifugal separation of the precipitated polymer, washing and drying of the polymer can be carried out according to a known method.

The transition metal complex and the organic ligand used as the catalyst can be removed from the reaction solution by diluting the polymerization solution with a good solvent for forming a polymer, for example, Tetrahydrofuran (THF), toluene, or the like, and passing the diluted solution through a column (column) or a plate (pad) of alumina, silica, or clay. Further, a method of treating the transition metal and the organic ligand contained in the reaction solution by an extraction operation such as liquid separation, or a method of dispersing a metal adsorbent in the reaction solution and treating the resulting dispersion may be employed.

The RAFT (reversible addition-fragmentation chain transfer polymerization) method is described in detail below.

In the RAFT method, a dithiocarbamate derivative (RAFT agent), a vinyl monomer, and a radical polymerization initiator are polymerized in the presence of each other. The generated radical is added to a C ═ S bond at the end of the thioester compound or the generated polymer, and the original radical species are converted into the same thioester type. Thus, polymerization proceeds via exchange chain transfer which reversibly repeats radical addition and cleavage on thioester.

The RAFT agent can be of any type known to those skilled in the art. The following formula a represents the structure of a representative RAFT agent. The most suitable functional groups Z and R are determined according to the kind of monomers to be polymerized.

R is selected from-CH₂R¹、－CHR¹R'¹and-CR¹R'¹R”¹，R¹、R'¹And R "¹Independently of one another, are selected from the group consisting of an alkyl group which may be substituted, a saturated or unsaturated or aromatic carbocyclic or heterocyclic ring, an alkylthio group which may be substituted, an alkoxy group which may be substituted, a dialkylamino group which may be substituted, an organometallic group, an acyl group, an acyloxy group, a carboxyl group (and esters and/or salts thereof), a sulfonic acid (and salts and/or sulfonates thereof), an alkoxy group or an aryloxycarbonyl group, and a polymer chain formed by an arbitrary polymerization mechanism, and may be the same as or different from each other,

z is selected from hydrogen, halogen (chlorine, bromine, iodine), alkyl which may be substituted, aryl which may be substituted, heterocycle which may be substituted, -SR²An alkoxycarbonyl group which may be substituted, an aryloxycarbonyl group (-COOR) which may be substituted²) A carboxyl group (-COOH), an acyloxy group (-OCOR) which may be substituted (-OCOR)²) Carbamoyl group which may be substituted, -CONHR²、－CONR²R³Cyano (-CN), dialkyl OR diaryl phosphonates [ -P (═ O) OR² ₂]Dialkyl or diaryl phosphinates [ -P (═ O) R² ₂]Polymer chain produced by any polymerization mechanism, -OR²Radical and-NR²R³Radical, R²And R³Selected from C1-C18 alkyl and C₂～C₁₈Alkenyl radical, C⁶～C₁₈Aryl, heterocycle, aralkyl, alkaryl, which may be the same or different from each other, may be substituted as desired, and the substituent is selected from the group consisting of epoxy, hydroxy, alkoxy, acyl, acyloxy, carboxy (and esters and/or salts thereof), sulfonic acid (and salts and/or sulfonates thereof), alkoxy or aryloxycarbonyl, isocyanate, cyano, silyl, halogen, and dialkylamino.

The amount of RAFT agent is determined according to the molecular weight of the target polymer. Since the RAFT agent is bonded to the end of each monomer, about 1 mol% (0.5 to 3 mol%) of the RAFT agent is used relative to 100 mol% of the monomer when a 100-mer polymer is the target. When the RAFT agent of trithiocarbonate type of bilaterally symmetrical structural formula is used, a triblock of a-B-a type is formed, and the trithiocarbonate group derived from the RAFT agent is located not only at the terminal but also at the center. The amount of the three-block type RAFT agent is determined in the same manner as in the RAFT agent described above.

The radical polymerization initiator is well known to those skilled in the art, and can be any type of radical polymerization initiator selected from azo compounds, peroxides, and redox initiators. A conventional chemical species capable of producing a free radical is referred to as a radical polymerization initiator.

Examples of the azo compound include 2,2 '-Azobisisobutyronitrile (AIBN), 2' -azobis-2, 4-dimethylvaleronitrile, 2 '-azobis (2-methylpropionamidine) dihydrochloride, and 4,4' -azobis (4-cyanovaleric acid). Examples of peroxide compounds include tert-butyl peroxyacetate, tert-butyl peroxybenzoate (TBPO), dicumyl peroxide or dibenzoyl peroxide. Examples of the redox compound include persulfate salts such as potassium persulfate, sodium persulfate and ammonium persulfate, and can be used together with metabisulfite such as sodium metabisulfite if necessary.

The polymerization initiator is used in an amount of usually 1 to 50 mol%, preferably 2 to 35 mol%, based on the weight of the RAFT agent.

The reaction in the RAFT method is determined by the radical polymerization initiator used, and is usually carried out at 40 to 150 ℃. Although polymerization is usually carried out under atmospheric pressure, polymerization may be carried out under elevated pressure.

The RAFT process can be carried out in the absence of a solvent, but can also be carried out in the presence of a solvent. The solvent used as needed is the same as in the ATRP method described above. The reaction may be carried out in water, or in emulsion polymerization. As the emulsifier used in this case, nonionic, cationic, and anionic emulsifiers that can be used in ordinary emulsion polymerization can be used.

The properties such as melting point and water repellency of the block copolymer obtained do not depend on the method of synthesis. The terminal of the obtained copolymer has a structure derived from the synthesis method thereof (for example, a thioester group or the like in the case of RAFT), and the melting point and the physical properties such as water repellency of the obtained copolymer are the same as long as the copolymer does not have a specific functional group (hydrophilic group).

The obtained block copolymer can be prepared into any form such as an emulsion, an organic solvent solution, an aerosol, or the like, after being diluted or dispersed in water, an organic solvent, or the like as necessary.

The surface treatment agent of the present invention may be in the form of a solution, an emulsion (particularly, an aqueous dispersion), or an aerosol. The surface treatment agent comprises a block copolymer (active ingredient of the surface treatment agent) and a medium (particularly a liquid medium such as an organic solvent and/or water). The amount of the medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight, based on the surface treatment agent.

The concentration of the copolymer in the surface treatment agent may be 0.01 to 70% by weight, for example, 0.1 to 50% by weight.

The surface treatment agent can be used as a water-repellent oil-repellent agent, an antifouling agent, a stain-removing agent, a release agent or a mold release agent. The surface treatment agent is particularly suitable as a water-repellent agent.

The surface treatment agent can be applied to the object to be treated by a conventionally known method. In general, the surface treatment agent is dispersed in an organic solvent or water, diluted, adhered to the surface of the object to be treated by a conventional method such as dip coating, spray coating, foam coating, or the like, and dried. If necessary, the curing agent may be used together with an appropriate crosslinking agent (e.g., blocked isocyanate) to cure the resin. Further, the surface treatment agent of the present invention may be used together with an insect repellent, a softening agent, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixative, an anti-wrinkle agent, and the like. The concentration of the copolymer in the treatment liquid to be brought into contact with the substrate may be 0.01 to 10% by weight (particularly in the case of dip coating), for example, 0.05 to 10% by weight.

Examples of the object to be treated with the surface treatment agent (for example, water-repellent oil-repellent agent) of the present invention include fiber products, stone materials, filters (for example, electrostatic filters), dust covers, parts of fuel cells (for example, gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramics, plastics, painted surfaces, and plaster (plaster). Various examples of the fiber product can be cited. Examples thereof include natural fibers of animals and plants 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, inorganic fibers such as glass fibers, carbon fibers and asbestos fibers, and mixed fibers thereof.

The fiber product may be in any form of fiber, cloth, or the like.

The water repellent composition of the present invention can also be used as an antifouling agent, a release agent, and a release agent (for example, an internal release agent or an external release agent). For example, the surface of the substrate can be easily peeled off from another surface (another surface in the substrate or a surface of another substrate).

The block copolymer can be applied to a fibrous substrate (e.g., a fibrous article, etc.) by any method known for treating fibrous articles with liquids. When the fiber product is a cloth, the cloth may be impregnated with the solution, or the solution may be attached to or sprayed on the cloth. The treated textile product is dried to exhibit liquid repellency (water repellency and/or oil repellency), and is preferably heated to, for example, 80 to 200 ℃.

Alternatively, the block copolymer may be applied to the fibrous article by a cleaning process, for example, may be applied to the fibrous article in a laundry application or in a dry cleaning process or the like.

The treated fibrous articles are typically cloths including woven, knitted and non-woven fabrics, clothing-like cloths and blankets, but may also be fibers or yarns or intermediate fibrous articles (e.g. slivers or rovings, etc.). The fibrous article material may be natural fibers (e.g., cotton or wool, etc.), chemical fibers (e.g., viscose rayon or lyocell, etc.), or synthetic fibers (e.g., polyester, polyamide, acrylic, etc.), or may be a mixture of fibers (e.g., a mixture of natural and synthetic fibers, etc.). In addition, the process of the present invention generally renders the fibrous product hydrophobic and water repellent.

Alternatively, the fibrous substrate may be leather. In order to render the leather hydrophobic and oleophobic, the manufacturing polymer may be applied to the leather from an aqueous solution or emulsion during various stages of leather processing, such as during the wetting process of the leather or during the finishing process of the leather.

Alternatively, the fibrous substrate may be paper. The make polymer may be applied to the preformed paper or may be applied during various stages of papermaking, such as during the drying of the paper.

The "treatment" means applying the surface treatment agent to the object to be treated by dipping, spraying, coating, or the like. By the treatment, the copolymer as an active ingredient of the surface treatment agent is impregnated into the inside of the object to be treated and/or attached to the surface of the object to be treated.

Examples

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Hereinafter, unless otherwise specified, parts or% or ratio means parts or% or ratio by weight.

The procedure of the test is as follows.

[ number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw/Mn) ]

The number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) were determined by Gel Permeation Chromatography (GPC). GPC used tetrahydrofuran as a developing solution, and KF-606M, KF-601 and KF-800D available from Shodex as columns to calculate molecular weights and the like in terms of polystyrene.

[ composition of copolymer obtained by NMR (Nuclear magnetic resonance method) ]

In the 1H-NMR (nuclear magnetic resonance) measurement, deuterated chloroform was used as a solvent.

[ measurement of thermophysical Properties by Differential Scanning Calorimetry (DSC) ]

The melting point of the copolymer was calculated by Differential Scanning Calorimetry (DSC). DSC measurement was carried out under a nitrogen atmosphere, after cooling to-30 ℃, heating to 170 ℃ at 10 ℃/min, cooling again to-30 ℃, then heating to 170 ℃ at 10 ℃/min, and measuring the melting point observed in the process. Among polymers having a plurality of melting peaks, the peak having the largest heat of fusion from melting of the long-chain alkyl group is taken as the melting point.

[ static contact Angle, dynamic contact Angle (roll off Angle) measurement ]

A chloroform solution having a solid content concentration of 1.0% of the obtained copolymer was spin-coated on a silicon wafer substrate, and dynamic and static contact angles were measured with respect to the sample which was air-dried only and after annealing at respective temperatures (40 ℃, 45 ℃, 80 ℃, 120 ℃) for 15 minutes, respectively. Static contact Angle the contact angle 1 second after dropping was measured by dropping 2. mu.L of water or hexadecane on the coating film. The dynamic contact angle (roll off angle) was measured by dropping 20. mu.L of water or 5. mu.L of n-hexadecane on the coating film, tilting the substrate at a speed of 2 ℃ per second, and determining the angle at which the droplet starts to roll off as the roll off angle. "> 85" indicates that the droplet did not roll off even if the substrate was tilted by 85 °. The annealing temperature "none" in table 1 indicates the measured value of the sample that was air-dried only.

[ Water repellency test ]

A treatment solution having a solid content of 1.5% was prepared using chloroform as a solvent, and the water repellency of the test cloth after heat treatment was evaluated by passing the test cloth through a cloth calender after dipping the cloth in the treatment solution. The water repellency of the treated fabric was evaluated by the spraying method according to JIS-L-1092 (AATCC-22). The water repellency is represented by a water repellency No. as shown in the following table. The larger the fraction, the better the water repellency. The "+" marked on a number indicates that it is better than the number, and the "-" indicates that it is worse than the number. The evaluation was performed using polyester cloth (PET) and nylon cloth (Ny).

[ Strong Water repellency test ]

The degree of easiness of water repellency against the cloth and the speed of water flow-off from the cloth were visually evaluated in a test by the spraying method of JIS-L-1092 (AATCC-22). The larger the fraction, the better the strong water repellency.

EXAMPLE 1 Synthesis of StA/HEA by ATRP method

Into a reaction vessel after nitrogen substitution were charged 3.0ml of toluene, 14mg of Cu (0), 60mg of CuBr (I), 179mg of 2,2' -bipyridine, 4.3g of stearyl acrylate (StA) as a first monomer, and 28. mu.l of ethyl 2-bromoisobutyrate, and the mixture was heated and stirred at 110 ℃ to effect a reaction. By passing¹After confirming the consumption of the first monomer by H NMR measurement, hydroxyethyl acrylate (HEA) was added as a second monomer. By passing¹H NMR measurement, confirming that unreacted monomers are consumed, separating the polymerization solution with ammonia to remove Cu catalystAfter the reaction, the resulting copolymer was reprecipitated in acetone to obtain a block copolymer (1). The reaction proceeded quantitatively.

Example 2 > StA/HEA

A block copolymer (2) was obtained in the same manner as in example 1, except that 1mol equivalent of Cu (0), 2mol equivalents of cubr (i), 6mol equivalents of 2,2' -bipyridine, 50mol equivalents of StA as the first monomer, and 50mol equivalents of HEA as the second monomer were used with respect to 1mol equivalent of ethyl 2-bromoisobutyrate as the initiator.

Example 3 > StA/AA

A block copolymer (3') was obtained in the same manner as in example 2 except that 50mol equivalent of StA as a first monomer and 50mol equivalent of t-butyl acrylate (tBuA) as a second monomer were used with respect to 1mol equivalent of ethyl 2-bromoisobutyrate as an initiator. Then, 5 equivalents of trifluoroacetic acid was reacted with tBuA1 units to carry out deprotection reaction, followed by reprecipitation in acetone to obtain block copolymer (3).

Example 4 > StA/DMS

With respect to 1mol equivalent of ethyl 2-bromoisobutyrate as an initiator, 50mol equivalents of StA as a first monomer and CH as a second monomer were used₂＝C(CH₃)CO₂(CH₂)₃Si(CH₃)₂〔OSi(CH₃)₂〕_nOSi(CH₃)₂C₄H₉A block copolymer (4) was obtained by performing the reaction in the same manner as in example 2 except that (DMS) had 4mol equivalent.

Example 5 > StA/HEMA

A block copolymer (5) was obtained in the same manner as in example 2, except that 50mol equivalent of StA as the first monomer and 50mol equivalent of hydroxyethyl methacrylate (HEMA) as the second monomer were used with respect to 1mol equivalent of ethyl 2-bromoisobutyrate as the initiator.

Comparative example 1 > StA/HEA

A random copolymer (1) was obtained in the same manner as in example 2, except that the first monomer and the second monomer were simultaneously added to the reaction vessel using StA 60mol equivalent as the first monomer and HEA 40mol equivalent as the second monomer with respect to 1mol equivalent of ethyl 2-bromoisobutyrate as the initiator.

Comparative example 2 > StA/AA

A random copolymer (2') was obtained in the same manner as in example 2 except that the first monomer and the second monomer were simultaneously added to the reaction vessel using 50mol equivalent of StA as the first monomer and 50mol equivalent of tBuA as the second monomer with respect to 1mol equivalent of ethyl 2-bromoisobutyrate as the initiator. Then, 5 equivalents of trifluoroacetic acid was reacted with tBuA1 units to carry out deprotection reaction, followed by reprecipitation in acetone to obtain a random copolymer (2).

Example 6 > C18URA/HEA

1mol equivalent of ethyl 2-bromoisobutyrate relative to the initiator, CH as the first monomer was used₂＝CHCO₂－CH₂CH₂－O－C(＝O)－NH－C₁₈H₃₇A block copolymer (6) was obtained by performing the reaction in the same manner as in example 2 except that (C18URA) was reacted at 50mol equivalent and HEA as the second monomer at 50mol equivalent.

Example 7 > C18UA/HEA

1mol equivalent of ethyl 2-bromoisobutyrate relative to the initiator, CH as the first monomer was used₂＝CHCO₂－CH₂CH₂－NH－C(＝O)－O－C₁₈H₃₇(C18UA) A block copolymer (7) was obtained by performing the reaction in the same manner as in example 2 except that the molar equivalent of (C18UA) was changed to 50mol and the molar equivalent of HEA as the second monomer was changed to 50 mol.

Example 8 > C18URA/tBuA

A block copolymer (8) was obtained in the same manner as in example 2 except that 50mol equivalents of C18URA as a first monomer and 50mol equivalents of tBuA as a second monomer were used based on 1mol equivalent of ethyl 2-bromoisobutyrate as an initiator.

Example 9 > C18URA/AA

The tBuA1 unit of the block copolymer (8) was reacted with 5 equivalents of trifluoroacetic acid to carry out deprotection reaction, and reprecipitated in acetone to obtain a block copolymer (9).

Example 10 > C18URA/DMA

With respect to 1mol equivalent of ethyl 2-bromoisobutyrate as an initiator, 40mol equivalents of C18URA as a first monomer and CH as a second monomer were used₂＝C(CH₃)CO₂(CH₂)₃Si(CH₃)₂〔OSi(CH₃)₂〕_nOSi(CH₃)₂C₄H₉A block copolymer (10) was obtained by performing the reaction in the same manner as in example 2 except that (DMS) had 4mol equivalents.

EXAMPLE 11 Synthesis of C18URA/StA by RAFT method

In the reaction vessel after nitrogen substitution, 35mg of cyanomethyldodecyltrithiocararbonate serving as a RAFT initiator, 0.lmol equivalent, 65mol equivalent of 2,2' -Azobisisobutyronitrile (AIBN) and C18URA serving as a first monomer were added to the RAFT initiator, and 3.0ml of toluene was added, and the mixture was reacted with stirring under heating at 70 ℃. By passing¹After confirming the consumption of the first monomer by H NMR measurement, 35mol equivalents of StA (relative to RAFT initiator) was added as the second monomer. By passing¹H NMR measurement confirmed that the unreacted monomer was consumed, and then the polymer was reprecipitated in acetone to obtain a block copolymer (11). The reaction proceeded quantitatively.

Example 12 > C18URA/StA

A block copolymer (12) was obtained in the same manner as in example 11, except that 50mol equivalents of C18URA as the first monomer and 50mol equivalents of StA as the second monomer were used based on 1mol equivalent of cyanomethyldodecyltrithiocarboxylate as the RAFT initiator.

Comparative example 3 > C18URA/HEA

A random copolymer (3) was obtained in the same manner as in example 11, except that the first monomer and the second monomer were simultaneously added to the reaction vessel using 50mol equivalents of C18URA as the first monomer and 50mol equivalents of HEA as the second monomer with respect to 1mol equivalent of cyanomethyldodecyltrithiocarboxylate as the RAFT initiator.

< comparative example 4 > C18URA/tBuA

A random copolymer (4) was obtained in the same manner as in example 11, except that the first monomer and the second monomer were simultaneously added to the reaction vessel using 50mol equivalents of C18URA as the first monomer and 50mol equivalents of tBuA as the second monomer with respect to 1mol equivalent of cyanomethyldodecyltrithiocarbonate as the RAFT initiator.

< comparative example 5 > C18URA/AA

The tBuA1 unit of the random copolymer (4) was reacted with 5 equivalents of trifluoroacetic acid to carry out deprotection reaction, and reprecipitated in acetone to obtain a random copolymer (5).

Comparative example 6 > C18URA/StA

A random copolymer (6) was obtained in the same manner as in example 11, except that the first monomer and the second monomer were simultaneously added to the reaction vessel using 50mol equivalents of C18URA as the first monomer and 50mol equivalents of StA as the second monomer with respect to 1mol equivalent of cyanomethyldodecyltrithiocarbonate as the RAFT initiator.

Example 13 > C18URA/HEA/StA

In the reaction vessel after nitrogen substitution, 35mg of cyanomethyldodecyltrithiocararbonate serving as a RAFT initiator, 0.lmol equivalent and 30mol equivalent of 2,2' -Azobisisobutyronitrile (AIBN) and 3.0ml of C18URA and toluene serving as first monomers were charged and reacted with heating and stirring at 70 ℃. By passing¹H NMR measurement confirmed consumption of the first monomer, and then 40mol equivalents of HEA (relative to RAFT initiator) was added as the second monomer. By passing¹After confirming that the unreacted monomer was consumed by H NMR measurement, 30mol equivalent of StA (relative to RAFT initiator) was added as a third monomer. By passing¹H NMR measurement confirmed that the unreacted monomer was consumed, and then the polymer was reprecipitated in acetone to obtain a block copolymer (13). The reaction proceeded quantitatively.

Example 14 > StA/diA

A block copolymer (14) was obtained in the same manner as in example 11, except that 100mol equivalent of StA as the first monomer and 1mol equivalent of 1, 6-bisacryloxy hexane (diA) as the second monomer were used to 1mol equivalent of cyanomethyldodecyltrithiocarbonate as the RAFT initiator.

Example 15 > C18URA/diA

A block copolymer (15) was obtained in the same manner as in example 11 except that 100mol equivalent of C18URA as the first monomer and 1mol equivalent of 1, 6-bisacryloxy hexane (diA) as the second monomer were used with respect to 1mol equivalent of cyanomethyldodecyltrithiocarbonate as a RAFT initiator.

EXAMPLE 16 emulsion polymerization StA/tBuA

Adding RAFT initiator 2- [ (dodecyl mercapto carbonyl) mercapto into the reaction vessel after nitrogen replacement]27mg of propionic acid, 0.lmol equivalent and 32mol equivalent of 4,4' -azobis (4-cyanovaleric acid) to the RAFT initiator, StA as the first monomer, 2.5 wt% of polyethylene glycol monooleyl ether to StA, and 3.0ml of pure water were prepared into an emulsion solution by applying ultrasonic waves, and then reacted with stirring at 70 ℃. By passing¹After confirming the consumption of the first monomer by H NMR measurement, tBuA 18mol equivalent (relative to RAFT initiator) as the second monomer was added. By passing¹H NMR measurement confirmed that the unreacted monomer was consumed, and then the polymer was reprecipitated in acetone to obtain a block copolymer (16). The reaction proceeded quantitatively. The weight average molecular weight (Mw) of the block copolymer (16) was 14300 and the molecular weight distribution (Mw/Mn) was 1.15.

EXAMPLE 17 emulsion polymerization StA/HEA

A block copolymer (17) was obtained in the same manner as in example 16, except that 50mol equivalent of StA as the first monomer and 5mol equivalent of HEA as the second monomer were used to 1mol equivalent of 2- [ (dodecylmercaptothiocarbonyl) mercapto ] propionic acid as the RAFT initiator. The weight average molecular weight (Mw) of the block copolymer (17) was 14800, and the molecular weight distribution (Mw/Mn) was 1.17.

The results of the number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), copolymer composition, melting point, static and dynamic contact angles, water repellency test, and strong water repellency test of examples 1 to 15 and comparative examples 1 to 6 are shown in Table 1.

[ Table 1]

Example 18 > StA/HEA

A block copolymer (18) was obtained in the same manner as in example 11, except that 1mol equivalent of the RAFT initiator cyanomethyldodecyltrithiocarbonate was used, and 80mol equivalents of StA as the first monomer and 20mol equivalents of HEA as the second monomer were used.

Example 19 > StA/(HBA/HBAGE)

A block copolymer (19) was obtained in the same manner as in example 11, except that 2 monomers of StA 80mol equivalent as the first monomer, hydroxybutyl acrylate (HBA)10mol equivalent as the second monomer, and hydroxybutyl acrylate glycidyl ether (HBAGE)10mol equivalent were simultaneously added to RAFT initiator cyanomethyldodecyltrithiocarboxylate 1mol equivalent. In the water repellency test of the block copolymer (19), the fabric washed 20 times after coating was also 95 minutes (PET) and 95-minutes (Ny), and the water repellency was maintained after washing.

Comparative example 7 > StA/HEA

A random copolymer (7) was obtained in the same manner as in example 11, except that the first monomer and the second monomer were simultaneously added to the reaction vessel using StA 80mol equivalent and HEA 20mol equivalent as the second monomer with respect to 1mol equivalent of the RAFT initiator cyanomethyldodecyltrithiocarbonate.

Comparative example 8 > StA/GMA/HEA

4.0ml of toluene, 18.3mg of AIBN, 2.2g of StA as a monomer, 0.39g of HEA, and 0.16g of Glycidyl Methacrylate (GMA) were charged into the reaction vessel after nitrogen substitution, and the reaction was carried out by heating and stirring at 65 ℃. By passing¹H NMR measurement confirmed that unreacted monomers were consumed, and then reprecipitated in acetone to obtain a random co-polymerA polymer (8). The reaction proceeded quantitatively.

Example 20 > C18AmEA/HEA

1mol equivalent of CH as a first monomer to cyanomethyldodecyltrithiocarbonate as RAFT initiator₂＝CHCO₂－CH₂CH₂－NH－C(＝O)－C₁₇H₃₅A block copolymer (20) was obtained by performing the reaction in the same manner as in example 11, except that (C18 amaa) was 40mol equivalent and HEA as a second monomer was 60mol equivalent.

Example 21 > C18AmEA/HEA

A block copolymer (21) was obtained in the same manner as in example 11, except that 50mol equivalents of C18AmEA as the first monomer and 50mol equivalents of HEA as the second monomer were used based on 1mol equivalent of cyanomethyldodecyltrithiocarboxylate as the RAFT initiator.

Example 22 > C18AmEA/HEA

A block copolymer (22) was obtained in the same manner as in example 11, except that 100mol equivalents of C18AmEA as the first monomer and 100mol equivalents of HEA as the second monomer were used based on 1mol equivalent of cyanomethyldodecyltrithiocarboxylate as the RAFT initiator.

Example 23 > C18AmEA/HEA

For 1mol equivalent of ethyl 2-bromoisobutyrate as an initiator, 69mol equivalents of C18 amaa as a first monomer and 31mol equivalents of HEA as a second monomer were used. Otherwise, a block copolymer (23) was obtained by performing the reaction in the same manner as in example 2.

Example 24 > C18AmEA/(StA/HEA)

A block copolymer (24) was obtained in the same manner as in example 11, except that 2 monomers of 30mol equivalents of C18AmEA as the first monomer, 40mol equivalents of StA as the second monomer, and 30mol equivalents of HEA were simultaneously added to 1mol equivalent of cyanomethyldodecyltrithiocarboxylate as the RAFT initiator.

Example 25 > C18AmEA/(GMA/HEA)

A block copolymer (25) was obtained in the same manner as in example 11, except that 1mol equivalent of cyanomethyldodecyltrithiocarboxylate as a RAFT initiator was added with 70mol equivalents of C18AmEA as a first monomer, 6mol equivalents of GMA as a second monomer, and 24mol equivalents of HEA as 2 monomers.

Example 26 > C18AmEA/tBuA

A block copolymer (26) was obtained in the same manner as in example 2, except that 60mol equivalents of C18AmEA as a first monomer and 40mol equivalents of tBuA as a second monomer were used based on 1mol equivalent of ethyl 2-bromoisobutyrate as an initiator.

Example 27 > C18AmEA/tBuA

A block copolymer (27) was obtained in the same manner as in example 2 except that 47mol equivalent of C18AmEA as a first monomer and 53mol equivalent of tBuA as a second monomer were used to 1mol equivalent of ethyl 2-bromoisobutyrate as an initiator.

Example 28 > C18AmEA/AA

The tBuA1 unit of the block copolymer (26) was reacted with 5 equivalents of trifluoroacetic acid to carry out deprotection reaction, and reprecipitated in acetone to obtain a block copolymer (28).

Example 29 > C18AmEA/StA

A block copolymer (29) was obtained in the same manner as in example 11, except that 30mol equivalents of C18AmEA as the first monomer and 70mol equivalents of StA as the second monomer were used based on 1mol equivalent of cyanomethyldodecyltrithiocarboxylate as the RAFT initiator.

Example 30 > C18AmEA/StA

A block copolymer (30) was obtained in the same manner as in example 11, except that 50mol equivalents of C18AmEA as the first monomer and 50mol equivalents of StA as the second monomer were used based on 1mol equivalent of cyanomethyldodecyltrithiocarboxylate as the RAFT initiator.

< comparative example 9 > C18AmEA/HEA

A block copolymer (9) was obtained in the same manner as in example 11, except that 10mol equivalents of C18AmEA as the first monomer and 90mol equivalents of HEA as the second monomer were used with respect to 1mol equivalent of cyanomethyldodecyltrithiocarboxylate as the RAFT initiator.

Comparative example 10 > C18AmEA/HEA

A block copolymer (10) was obtained in the same manner as in example 11, except that 20mol equivalents of C18AmEA as the first monomer and 80mol equivalents of HEA as the second monomer were used per 1mol equivalent of cyanomethyldodecyltrithiocarboxylate as the RAFT initiator.

< comparative example 11 > C18AmEA/HEA

A random copolymer (11) was obtained in the same manner as in example 2, except that the first monomer and the second monomer were simultaneously added to the reaction vessel using 46mol equivalents of C18 amaa as the first monomer and 54mol equivalents of HEA as the second monomer with respect to 1mol equivalent of ethyl 2-bromoisobutyrate as the initiator.

Comparative example 12 > C18AmEA/HEA

A random copolymer (12) was obtained by performing the reaction in the same manner as in comparative example (8) except that 50mol equivalents of C18AmEA and 50mol equivalents of HEA were used as monomers with respect to 1mol equivalent of AIBN of the initiator. The obtained polymer had low solubility in chloroform or toluene, and it was difficult to produce a uniform coating film for contact angle and cloth evaluation.

Comparative example 13 > C18AmEA/HEA

A random copolymer (13) was obtained in the same manner as in comparative example (8) except that 70mol equivalents of C18AmEA and 30mol equivalents of HEA were used as monomers with respect to 1mol equivalent of AIBN of the initiator. The obtained polymer had low solubility in chloroform or toluene, and it was difficult to produce a uniform coating film for contact angle and cloth evaluation.

< comparative example 14 > C18AmEA/HEA

A random copolymer (14) was obtained in the same manner as in comparative example (8) except that the monomer used was C18AmEA80mol equivalent and HEA 20mol equivalent to AIBN 1mol equivalent of the initiator. The obtained polymer had low solubility in chloroform or toluene, and it was difficult to produce a uniform coating film for contact angle and cloth evaluation.

Comparative example 15 StA/GMA/HEA

A random copolymer (15) was obtained in the same manner as in comparative example (8) except that 60mol equivalent of StA, 10mol equivalent of GMA and 30mol equivalent of HEA were used as monomers based on 1mol equivalent of AIBN of the initiator.

Comparative example 16 > C18AmEA/GMA/HEA

A random copolymer (16) was obtained in the same manner as in example 11, except that 60mol equivalents of C18AmEA as a first monomer, 10 equivalents of GMA as a second monomer, and 30mol equivalents of HEA as a third monomer were used with respect to 1mol equivalent of cyanomethyldodecyltrithiocarboxylate as a RAFT initiator, and the first monomer, the second monomer, and the third monomer were simultaneously added to the reaction vessel.

< comparative example 17 > C18AmEA/tBuA

A random copolymer (17) was obtained in the same manner as in example 2, except that the first monomer and the second monomer were simultaneously added to the reaction vessel using 53mol equivalents of C18AmEA as the first monomer and 47mol equivalents of tBuA as the second monomer with respect to 1mol equivalent of ethyl 2-bromoisobutyrate as the initiator.

Comparative example 18 > C18AmEA/AA

The tBuA1 unit of the random copolymer (17) was reacted with 5 equivalents of trifluoroacetic acid to carry out deprotection reaction, and reprecipitated in acetone to obtain a random copolymer (18).

Comparative example 19 > C18AmEA/StA

A random copolymer (19) was obtained in the same manner as in example 11, except that the first monomer and the second monomer were simultaneously added to the reaction vessel using 30mol equivalents of C18AmEA as the first monomer and 70mol equivalents of HEA as the second monomer with respect to 1mol equivalent of cyanomethyldodecyltrithiocararbonate as the RAFT initiator.

Example 31 > C18AmEA/HEA/diA

1mol equivalent of cyanomethyldodecyltrithiocarboxylate as a first monomer, C18AmEA 100 was usedmol equivalent, HEA1mol equivalent as second monomer, CH as third monomer₂＝CHCO₂－C₆H₁₂－CO₂CH＝CH₂(diA) A block copolymer (31) was obtained by performing the reaction in the same manner as in example 11 except that 1mol equivalent of the second monomer was used and the third monomer was added after confirming the consumption of the second monomer.

Example 32 > C18AmEA/tBuA/diA

A block copolymer (32) was obtained in the same manner as in example 11, except that 100mol equivalent of C18AmEA as the first monomer, 1mol equivalent of tBuA as the second monomer, and diA1mol equivalent as the third monomer were used with respect to 1mol equivalent of cyanomethyldodecyltrithiocarbonate as the RAFT initiator, and after confirming the consumption of the second monomer, the third monomer was added.

Example 33 > C18AmEA/AA/diA

The tBuA1 unit of the block copolymer (32) was reacted with 5 equivalents of trifluoroacetic acid to carry out deprotection reaction, and reprecipitated in acetone to obtain a block copolymer (33).

Example 34 > C18AmEA/HEA/diA

A block copolymer (34) was obtained in the same manner as in example 11, except that 38mol equivalent of C18 amaa as the first monomer, 51mol equivalent of HEA as the second monomer, and 11mol equivalent of StA as the third monomer were used to confirm consumption of the second monomer with respect to 1mol equivalent of cyanomethyldodecyltrithiocarbonate as the RAFT initiator, and then the third monomer was added.

Example 35 > C18AmEA/diA

A block copolymer (35) was obtained in the same manner as in example 11, except that 100mol equivalents of C18AmEA as the first monomer and diA1mol equivalents of the second monomer were used per 1mol equivalent of cyanomethyldodecyltrithiocarboxylate as the RAFT initiator.

Example 36 > C18AmEA/HEA

A block copolymer (36) was obtained in the same manner as in example 16, except that 50mol equivalent of C18AmEA as the first monomer and 5mol equivalent of HEA as the second monomer were used to 1mol equivalent of 2- [ (dodecylmercaptothiocarbonyl) mercapto ] propionic acid as the RAFT initiator.

< example 37 > (C18AmEA/StA)/HEA

A block copolymer (37) was obtained in the same manner as in example 11, except that 40mol equivalents of C18 amaa and 4040 mol equivalents of StA as the first monomer and 20mol equivalents of HEA as the second monomer were used based on 1mol equivalent of cyanomethyldodecyltrithiocarboxylate as the RAFT initiator. In the water repellency test of the block copolymer (37), the fabric washed 20 times after coating was 95 minutes (PET) and 95+ minutes (Ny), and the water repellency was maintained after washing.

The results of the number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), copolymer composition, melting point, static and dynamic contact angles, water repellency test, and strong water repellency test of examples 16 to 37 and comparative examples 7 to 19 are shown in Table 2.

[ Table 2]

Industrial applicability

The surface treatment agent of the present invention can be used as a water-and oil-repellent agent or an antifouling agent. The surface treatment agent can be suitably used for a base material of a fiber product, a masonry, or the like, and can impart excellent water-and oil-repellency to the base material.