NON-FLUORINATED BLOCK COPOLYMER

1 . A fluorine-free block copolymer comprising (A) at least one block segment,

wherein the block segment (A) has a repeating unit formed from one or at least two acrylic monomers having a long-chain hydrocarbon group having 7 to 40 carbon atoms.

2 . The fluorine-free block copolymer according to claim 1 , wherein

the fluorine-free block copolymer has (B) a segment which is different from the block segment (A),

wherein the segment (B) has at least one of:

(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 from an acrylic monomer free from long-chain hydrocarbon group; and

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

3 . The fluorine-free block copolymer according to claim 1 , wherein

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

CH 2 ═C(—R 12 )—C(═O)—Y 11 —(R 11 ) k

wherein R 11 is a hydrocarbon group having 7 to 40 carbon atoms,

R 12 is a hydrogen atom, a monovalent organic group, or a halogen atom exclusive of a fluorine atom,

Y 11 is a group comprised of at least one selected from a divalent to tetravalent hydrocarbon group having 1 carbon atom, —C 6 H 4 —, —O—, —C(═O)—, —S(═O) 2 —, and —NH— (excluding a hydrocarbon group alone), and

k is 1 to 3.

4 . The fluorine-free block copolymer according to claim 3 , wherein

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

Y 11 is —Y′—, —Y′—Y′—, —Y′—C(═O)—, —C(═O)—Y′—, —Y′—C(═O)—Y′—, —Y′—R′—, —Y′—R′—Y′—, —Y′—R′—Y′—C(═O)—, —Y′—R′—C(═O)—Y′—, —Y′—R′—Y′—C(═O)—Y′—, or —Y′—R′—Y′—R′—

wherein each Y′ is independently a direct bond, —O—, —NH— or —S(═O) 2 —, and

each R′ is independently —(CH 2 ) m —, where m is an integer of 1 to 5, a linear hydrocarbon group having 1 to 5 carbon atoms having an unsaturated bond, a hydrocarbon group having 1 to 5 carbon atoms having a branched structure, or —(CH 2 ) 1 —C 6 H 4 —(CH 2 ) 1 —, where each 1 is independently an integer of 0 to 5, and —C 6 H 4 — is a phenylene group.

5 . The fluorine-free block copolymer according to claim 3 , wherein

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

Y 11 is —O—, —NH—, —O—C(═O)—, —NH—C(═O)—, —O—C(═O)—NH—, —NH—C(═O)—O—, —NH—C(═O)—NH—, —O—C 6 H 4 —, —NH—C 6 H 4 —, —O—(CH 2 ) m —O—, —NH—(CH 2 ) m —NH—, —O—(CH 2 ) m —NH—, —NH—(CH 2 ) m —O—, —O—(CH 2 ) m —O—C(═O)—, —O—(CH 2 ) m —C(═O)—O—, —NH—(CH 2 ) m —O—C(═O)—, —NH—(CH 2 ) m —C(═O)—O—, —O—(CH 2 ) m —O—C(═O)—NH—, —O—(CH 2 ) m —NH—C(═O)—O—, —O—(CH 2 ) m —C(═O) m —NH—, —O—(CH 2 ) m —NH—C(═O)—, —O—(CH 2 ) m —NH—C(═O)—NH—, —O—(CH 2 ) m —O—C 6 H 4 —, —O—(CH 2 ) m —NH—S(═O) 2 —, —O—(CH 2 ) m —S(═O) 2 —NH—, —NH—(CH 2 ) m —O—C(═O)—NH—, —NH—(CH 2 ) m —NH—C(═O)—O—, —NH—(CH 2 ) m —C(═O)—NH—, —NH—(CH 2 ) m —NH—C(═O)—, —NH—(CH 2 ) m —NH—C(═O)—NH—, —NH—(CH 2 ) m —O—C 6 H 4 —, —NH—(CH 2 ) m —NH—C 6 H 4 —, —NH—(CH 2 ) 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 fluorine-free block copolymer according to claim 1 , wherein

the acrylic monomer having a long-chain hydrocarbon group is at least one monomer selected from the group consisting of:

(a1) a compound represented by the formula:

CH 2 ═C(—R 22 )—C(═O)—Y 21 —R 21

wherein R 21 is a hydrocarbon group having 7 to 40 carbon atoms,

R 22 is a hydrogen atom, a monovalent organic group, or a halogen atom exclusive of a fluorine atom, and

Y 21 is —O— or —NH—, and

(a2) a compound represented by the formula:

CH 2 ═C(—R 32 )—C(═O)—Y 31 —Z 31 (—Y 32 —R 31 ) n

wherein R 31 is a hydrocarbon group having 7 to 40 carbon atoms,

R 32 is a hydrogen atom, a monovalent organic group, or a halogen atom exclusive of a fluorine atom,

Y 31 is —O— or —NH—,

Y 32 is a group comprised of at least one selected from —C 6 H 4 —, —O—, —C(═O)—, —S(═O) 2 —, and —NH—,

Z 31 is a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and

n is 1 or 2.

7 . The fluorine-free block copolymer according to claim 6 , wherein

in the acrylic monomer (a1),

R 22 is a hydrogen atom, a methyl group, or a chlorine atom, and

in the acrylic monomer (a2),

R 32 is a hydrogen atom, a methyl group, or a chlorine atom, and

Y 32 is a direct 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—C 6 H 4 —, —NH—C 6 H 4 —, —O—(CH 2 ) m —O—, —NH—(CH 2 ) m —NH—, —O—(CH 2 ) m —NH—, —NH—(CH 2 ) m —O—, —O—(CH 2 ) m —O—C(═O)—, —O—(CH 2 ) m —C(═O)—O—, —NH—(CH 2 ) m —O—C(═O)—, —NH—(CH 2 ) m —C(═O)—O—, —O—(CH 2 ) m —O—C(═O)—NH—, —O—(CH 2 ) m —NH—C(═O)—O—, —O—(CH 2 ) m —C(═O)—NH—, —O—(CH 2 ) m —NH—C(═O)—, —O—(CH 2 ) m —NH—C(═O)—NH—, —O—(CH 2 ) m —O—C 6 H 4 —, —NH—(CH 2 ) m —O—C(═O)—NH—, —NH—(CH 2 ) m —NH—C(═O)—O—, —NH—(CH 2 ) m —C(═O)—NH—, —NH—(CH 2 ) m —NH—C(═O)—, —NH—(CH 2 ) m —NH—C(═O)—NH—, —NH—(CH 2 ) m —O—C 6 H 4 —, or —NH—(CH 2 ) m —NH—C 6 H 4 —

wherein m is an integer of 1 to 5, and

Z 31 is —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH=having a branched structure, —CH 2 (CH—)CH 2 — having a branched structure, —CH 2 CH 2 CH=having a branched structure, —CH 2 CH 2 CH 2 CH 2 CH=having a branched structure, —CH 2 CH 2 (CH—)CH 2 — having a branched structure, or —CH 2 CH 2 CH 2 CH=having a branched structure.

8 . The fluorine-free block copolymer according to claim 1 , 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 free from 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 portion 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 portion, or a halogenated olefin, and the hydrophilic group is an OH group, an NH 2 group, a COOH group, a sulfone group or a phosphoric acid group, or an alkali metal or alkaline earth metal salt group of a carboxylic acid.

9 . The fluorine-free block copolymer according to claim 8 , wherein,

the acrylic monomer having a short-chain hydrocarbon group having 1 to 6 carbon atoms is a compound represented by the formula:

CH 2 ═C(—R 52 )—C(═O)—Y 51 —R 51

wherein R 51 is a hydrocarbon group having 1 to 6 carbon atoms, optionally comprising an oxygen atom,

R 52 is a hydrogen atom, a monovalent organic group, or a halogen atom exclusive of a fluorine atom, and

Y 51 is —O— or —NH—, and

the acrylic monomer having a hydrophilic group is a compound represented by the formula:

CH 2 ═C(—R 62 )—C(═O)—Y 61 —R 61 —(—Y 62 ) q

wherein R 61 is a hydrocarbon group having 1 to 6 carbon atoms or a single bond,

R 62 is a hydrogen atom, a monovalent organic group, or a halogen atom exclusive of a fluorine atom,

Y 61 is —O— or —NH—,

Y 62 is a hydrophilic group, and

q is a number of 1 to 3.

10 . The fluorine-free block copolymer according to claim 1 , wherein a molar ratio of the block segment (A) (molar ratio of the repeating unit) is 30 mol % or more, based on the repeating units of the copolymer.

11 . A method for producing the fluorine-free block copolymer according to claim 1 , which comprises:

a first polymerization step of polymerizing one of an acrylic monomer having a long-chain hydrocarbon group or an acrylic monomer free from long-chain hydrocarbon group in a first stage, and then,

a second polymerization step of polymerizing the other of the acrylic monomer having a long-chain hydrocarbon group or the acrylic monomer free from long-chain hydrocarbon group in a second stage, to produce the fluorine-free block copolymer.

12 . A surface treatment agent comprising:

(1) the fluorine-free block copolymer according to claim 1 , and

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

13 . The surface treatment agent according to claim 12 , being a water-repellent agent.

14 . A substrate comprising the fluorine-free block copolymer in the surface treatment agent according to claim 12 adhering to the substrate.

15 . A method for producing a treated substrate, comprising applying the surface treatment agent according to claim 12 to the substrate.