JP6686396B2 - Fluorine-containing block copolymer composition - Google Patents

Description

  The present invention relates to a fluorine-containing block copolymer and a fluorine-containing block copolymer composition.

  Fluorine-based resins can impart slipperiness and water / oil repellency to various objects to be processed, and are used in various fields. For example, by utilizing the slidability and water / oil repellency of a fluororesin, it is possible to impart slidability and stain resistance to paints, fibers, printed paper, leather and the like.

  Patent Documents 1 and 2 describe water- and oil-repellent compositions containing a fluorine-based homopolymer or a fluorine-based random copolymer as an organic fluorine compound. Further, Patent Document 3 describes a water- and oil-repellent composition containing a fluorine-based block copolymer.

JP-A-6-17034 JP 2012-72296 A JP, 9-328677, A

  However, in the resin molded products described in Patent Documents 1 to 3, since the compatibility between the organic fluorine compound or the low molecular weight fluorine compound and the curable resin is very poor, it is difficult to uniformly mix the two. is there. Further, the organic fluorine compound and the low molecular weight fluorine compound are easily released on the surface even after the coating treatment or the molding. Therefore, the organic fluorine compound and the low molecular weight fluorine compound on the surface easily fall off, and it is difficult to maintain the desired water / oil repellency.

  Further, when a fluorine-based random copolymer is used as the organic fluorine compound as in Patent Documents 1 and 2, the compatibility with the synthetic resin decreases when the amount of fluorine is large, and a phenomenon similar to the above phenomenon occurs. Therefore, it is difficult to maintain the water and oil repellency. On the other hand, if the amount of fluorine is decreased to increase the compatibility with the synthetic resin, the orientation of the fluorine-based random copolymer on the surface will be poor, and the desired slipperiness and water / oil repellency will be ensured. Will be difficult.

  Furthermore, in the fluorine-containing block copolymer described in Patent Document 3, a fluorine-containing monomer having a perfluoroalkyl group having 8 carbon atoms (C8 fluorine monomer) is used for the polymerization of the fluorine segment, and thus fluorine The amount is large and the compatibility with synthetic resins with a small amount of fluorine is poor. Further, it is desirable to avoid the use of C8 fluorine monomer from the viewpoint of the environment, and it is expected that it will be difficult to obtain it in the future.

  In view of the circumstances as described above, an object of the present invention is to provide a fluorine-containing block copolymer that ensures slipperiness and water / oil repellency and is excellent in usability and durability.

In order to achieve the above object, the fluorine-containing block copolymer according to one embodiment of the present invention is composed of (A) a fluorine-containing segment and (B) a non-fluorine segment.
The (A) fluorine-containing monomer constituting the fluorine-containing segment is a fluorine-containing monomer having a C6 perfluoroalkyl group represented by the formula (1).
The non-fluorine-based monomer constituting the non-fluorine segment (B) includes (b-1) (meth) acrylic acid alkyl ester monomer, (b-2) (meth) acrylic acid monomer, including.

…（１）
（式（１）中、Ｒ^１は、水素原子、メチル基、フッ素原子又は塩素原子を示し、ｎは１〜１８の整数である。）

… (1)
(In the formula (1), R ¹ represents a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom, and n is an integer of 1 to 18.)

  According to this constitution, since the fluorine-containing monomer represented by the formula (1) has a perfluoroalkyl group having 6 carbon atoms, the fluorine-containing block copolymer is excellent in slipperiness and repellency. It becomes possible to impart water repellency. Further, (B) the non-fluorine-based monomer constituting the non-fluorine segment is (b-1) (meth) acrylic acid alkyl ester monomer and (b-2) (meth) acrylic acid monomer. By containing, the slipperiness, water and oil repellency, and usability of the fluorine-containing block copolymer can be improved.

  The fluorine-containing block copolymer may contain 10 to 55% by weight of the fluorine-containing monomer.

  According to this structure, it is possible to further improve the slidability, the water / oil repellency, and the feeling of use of the fluorine-containing block copolymer.

  The non-fluorine-based monomer constituting the non-fluorine segment (B) may further include (b-3) a hydroxyl group-containing (meth) acrylic acid alkyl ester monomer.

  According to this structure, it is possible to further improve the slidability, the water / oil repellency, and the feeling of use of the fluorine-containing block copolymer.

  A fluorine-containing block copolymer composition according to one aspect of the present invention contains the above-mentioned (X) fluorine-containing block copolymer and (Y) a tertiary amine. In the fluorine-containing block copolymer (X), the molar ratio of the component (b-2) to the component (Y) is 0.9 to 1.1.

  With this configuration, the fluorine-containing block copolymer composition can be further improved in slipperiness, water and oil repellency, and usability.

  It is possible to provide a fluorine-containing block copolymer and a fluorine-containing block copolymer composition which have excellent slipperiness and water / oil repellency and are excellent in usability and durability.

  An embodiment of the present invention will be described below. In the present invention, “A to B” indicating a numerical range means “A or more and B or less” unless otherwise specified. Moreover, "(meth) acrylic acid" is a concept including both methacrylic acid and acrylic acid.

<(X) Fluorine-containing block copolymer>
The (X) fluorine-containing block copolymer according to the present embodiment is composed of (A) a fluorine-containing segment and (B) a non-fluorine segment.

  Hereinafter, the (A) fluorine-containing segment and the (B) non-fluorine segment will be described in detail.

[(A) Fluorine-containing segment]
The (A) fluorine-containing segment is formed only of a monomer containing a fluorine atom (fluorine-containing monomer). The above-mentioned fluorine-containing monomer is a fluorine-containing monomer (C6 fluorine monomer) having a perfluoroalkyl group having 6 carbon atoms and is represented by the formula (1).

…（１）

… (1)

In formula (1), R ¹ represents a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom, and n is an integer of 1 to 18.

  The fluorine-containing monomer represented by the formula (1) has a perfluoroalkyl group having 6 carbon atoms. This makes it possible to impart excellent water repellency and oil repellency and slipperiness to the fluorine-containing block copolymer (X). Furthermore, the amount of fluorine is smaller than that of a fluorine-containing monomer having a perfluoroalkyl group having 8 carbon atoms (C8 fluorine monomer), and the compatibility with a synthetic resin having a small amount of fluorine is good.

Examples of the fluorine-containing monomer represented by the formula (1) include CH ₂ ═CHCOO (CH ₂ ) ₂ (CF ₂ ) ₅ CF ₃ and CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₂ ( _{CF 2) 5 CF 3, CH} 2 = C (F) COO (CH 2) 2 (CF 2) 5 CF 3, CH 2 = C (Cl) COO (CH 2) 2 (CF 2) 5 CF 3, CH _{2 = CHCOO (CH 2) 18} (CF 2) 5 CF 3, CH 2 = C (CH 3) COO (CH 2) 18 (CF 2) 5 CF 3 , and the like.

  The content of the fluorine-containing monomer represented by the formula (1) is not particularly limited. As the content, for example, 10 to 55% of the fluorine-containing monomer represented by the formula (1) may be contained in 100% by weight of the (X) fluorine-containing block copolymer. As a result, the slidability, water and oil repellency, and usability of the (X) fluorine-containing block copolymer can be further improved.

[(B) Non-fluorine segment]
The non-fluorine segment (B) is formed of a fluorine-free monomer (non-fluorine-based monomer).

  The non-fluorine-based monomer is not limited to a specific type as long as it is a radical-polymerizable monomer containing no fluorine.

  Here, a non-fluorine-based monomer that can obtain a sufficient polymerization conversion rate, ensures compatibility with the curable resin component, and does not impair the water repellency of the cured molded product is represented by the formula (2). There are non-fluorine-based monomers.

…（２）

… (2)

In formula (2), R ² represents an alkyl group having 1 to 22 carbon atoms or a substituted alkyl group, a cycloalkyl group having 3 to 15 carbon atoms or a substituted cycloalkyl group, a phenyl group, a substituted phenyl group, and R ³ Represents a hydrogen atom or a methyl group.

  Specific examples of the non-fluorine-based monomer represented by the formula (2) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid. t-butyl, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate, ( Hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylamide, (meth) acrylic acid amide N, N-dimethyl, N-methylol (meth) acrylamide, N- (meth ) Acryloylmorpholine, (meth) acrylic acid, (meth) acrylonitrile, vinyl acetate, Styrene, methoxy styrene, N- methylmaleimide, N- ethylmaleimide, N- phenylmaleimide, diisopropyl fumarate, di-t- butyl, dicyclohexyl fumarate, dibenzyl fumarate, dimethyl, and the like itaconic acid.

  The non-fluorine-based monomer that constitutes the non-fluorine segment (B) includes (b-1) (meth) acrylic acid alkyl ester monomer and (b-2) (meth) acrylic acid monomer. Including. This can improve the slidability, water and oil repellency, and usability of the (X) fluorine-containing block copolymer.

  Examples of the (b-1) (meth) acrylic acid alkyl ester monomer include methyl methacrylate, stearyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like.

  The (meth) acrylic acid monomer (b-2) is not limited to a specific type as long as it has a skeleton of acrylic acid, but acrylic acid or methacrylic acid is preferable.

  The non-fluorine-based monomer that constitutes the non-fluorine segment (B) may include (b-3) a hydroxyl group-containing (meth) acrylic acid alkyl ester monomer. Thereby, the slidability, water / oil repellency, and usability of the (X) fluorine-containing block copolymer can be further improved.

  (B-3) Examples of the (meth) acrylic acid alkyl ester monomer having a hydroxyl group include 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

<Production Method of (X) Fluorine-Containing Block Copolymer>
The method for producing the above (X) fluorine-containing block copolymer is not particularly limited, and a known method for synthesizing a block copolymer can be used.

  The polymerization initiator used in the polymerization reaction is not particularly limited, but polymeric peroxide may be used. Polymeric peroxide is a compound having two or more peroxy bonds in one molecule.

  As the polymeric peroxide, various polymeric peroxides described in JP-B-5-59942 may be used alone or in combination of two or more. In particular, it is preferable to use the polymeric peroxides represented by formulas (3) to (5).

…（３）

… (3)

In formula (3), R ³ − represents a substituent represented by “alkyl-C (═O) OO—”, and R ⁴ — represents a substituent represented by “—CO-alkyl”. n is an integer of 1 to 10 and m is an integer of 2 to 20. Alkyl is a hydrocarbon group having 1 to 18 carbon atoms.

…（４）

… (4)

In formula (4), R ⁵ − represents a substituent represented by “alkyl-C (═O) OO—”, and R ⁶ — represents a substituent represented by “—CO-alkyl”. n is an integer of 1-10. Alkyl is a hydrocarbon group having 1 to 18 carbon atoms.

…（５）

… (5)

Wherein (5), ^{R 7} - represents a substituent represented by "alkyl-C (= O) OO-", ^{R 8} - represents a substituent represented by "-CO-alkyl". n is an integer of 1-10. Alkyl is a hydrocarbon group having 1 to 18 carbon atoms.

<Method for producing fluorine-containing block copolymer composition>
By adding the tertiary amine (Y) to the fluorine-containing block copolymer (X), amine treatment is carried out to obtain a fluorine-containing block copolymer composition.
It is preferable to use triethylamine as the (Y) tertiary amine. As a result, the slidability, water / oil repellency and usability of the fluorine-containing block copolymer composition can be further improved.

  In the fluorine-containing block copolymer (X), the molar ratio ((Y) / (b-2)) of the component (b-2) and the component (Y) is preferably 0.9 to 1.1. . Within this range, the slidability, water / oil repellency and usability of the fluorine-containing block copolymer composition can be further improved.

  Hereinafter, embodiments of the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the scope of these Examples.

<Production of fluorinated copolymer>
The types and compounding ratios of the monomers of the dispersions containing the (X) fluorine-containing block copolymer produced in Examples 1-1 to 1-8 and 2-1 to 2-3 are as shown in Table 1. is there.
Table 2 shows the types and compounding ratios of the monomers of the dispersions containing the fluorocopolymers produced in Comparative Examples 1-1 to 1-12.

[Example 1-1]
A 5 liter four-necked flask equipped with a thermometer, a stirrer and a reflux condenser was charged with 78 parts by weight of isopropyl alcohol (IPA) and heated to 70 ° C. while blowing nitrogen gas. Then, in this, as (b-1) (meth) acrylic acid alkyl ester, 33 parts by weight of methyl methacrylate (MMA), 32 parts by weight of butyl methacrylate (BMA), and (b-2) as (meth) acrylic acid A mixed solution composed of 5 parts by weight of acrylic acid (AA) and a mixed solution composed of 38 parts by weight of IPA and 17 parts by weight of polymeric peroxide (formula (3), n = 10) were simultaneously charged over 2 hours, The polymerization reaction was further performed for 5 hours. As a result, a dispersion liquid of the polymer constituting the non-fluorine segment (B) was obtained.

Subsequently, as the fluorine-containing monomer _{CH 2 = CHCOO (CH 2)} 2 (CF 2) 5 CF 3 (FA (C6)) of 30 parts by weight expressed as in the IPA36 parts and formula (1) The mixed solution was charged over 0.5 hour and a polymerization reaction was performed for 2 hours. After that, the temperature was further raised to 80 ° C. and a polymerization reaction was performed for 2.5 hours, and then the solution was cooled to 40 ° C. or lower to obtain a dispersion liquid containing the (X) fluorine-containing block copolymer.

[Examples 1-2 to 1-8]
Examples 1-2 to 1-8 are performed by performing the same operation as in Example 1-1, except that each of the monomers used is changed to the monomer and the blending amount shown in Table 1. X) A dispersion liquid containing a fluorine-containing block copolymer was obtained.
In Example 1-2, methacrylic acid (MAA) was used instead of AA as (b-2).
In Example 1-3, 2-ethylhexyl methacrylate (EHMA) was used instead of BMA as (b-1).
In Example 1-4～1-6, respectively _CH 2 ₌ C _{(CH 3)} instead of (A) as _{FA (C6) COO (CH 2} ) 2 (CF 2) 5 CF 3 (FMA (C6)) _{, CH 2 = C (Cl)} COO (CH 2) 2 (CF 2) 5 CF 3 ((Cl) FA (C6)), CH 2 = CHCOO (CH 2) 18 (CF 2) 5 CF 3 (FA ( C18) (C6)) was used.

[Examples 2-1 to 2-3]
Regarding each of the monomers used, Example 1 was repeated except that 2-hydroxyethyl methacrylate (HEMA) was used as (b-3) in (B) and the monomers and the compounding amounts shown in Table 1 were changed. By performing the same operation as in -1, the dispersions containing the (X) fluorine-containing block copolymer according to Examples 2-1 to 2-3 were obtained.
In Example 2-2, EHMA was used instead of BMA as (b-1). In Example 2-2, FMA (C6) was used as (A) instead of FA (C6).
In Example 2-3, MAA was used instead of AA as (b-2). Moreover, in Example 2-3, (Cl) FA (C6) was used instead of FA (C6) as (A).

[Comparative Example 1-1]
A 5 liter four-necked flask equipped with a thermometer, a stirrer and a reflux condenser was charged with 36 parts by weight of IPA and heated to 70 ° C. while blowing nitrogen gas. Subsequently, in this, MMA 33 parts by weight as (b-1) (meth) acrylic acid alkyl ester, BMA 32 parts by weight, AA 5 parts by weight as (b-2) (meth) acrylic acid and represented by the formula (1). A mixed solution of 30 parts by weight of FA (C6) as a fluorine-containing monomer and a mixed solution of 38 parts by weight of IPA and 4 parts by weight of t-butylperoxypivalate were simultaneously charged over 2 hours, and further 3 The polymerization reaction was carried out for 5 hours. After that, the temperature was further raised to 80 ° C. and a polymerization reaction was performed for 2.5 hours, and then the solution was cooled to 40 ° C. or lower to obtain a dispersion liquid containing a fluorine-containing random copolymer.

[Comparative Examples 1-2 to 1-4]
By performing the same operation as in Comparative Example 1-1, except that the respective monomers used were changed to the monomers and the blending amounts shown in Table 2, the contents of Comparative Examples 1-2 to 1-4 were included. A dispersion liquid containing a fluorine random copolymer was obtained.
In Comparative Example 1-2, MAA was used instead of AA as (b-2).
In Comparative Example 1-3, EHMA was used instead of BMA as (b-1).
In Comparative Example 1-4, HEMA was used as (b-3) in (B).

[Comparative Examples 1-5 to 1-12]
Comparative Examples 1-5 to 1-12 are performed by performing the same operation as in Example 1-1, except that each of the used monomers is changed to the monomer and the blending amount shown in Table 2. X) A dispersion liquid containing a fluorine-containing block copolymer was obtained.
In Comparative Examples 1-4, 1-5, 1-8 to 1-12, HEMA was used as (b-3) in (B).
In Comparative Example 1-7, MAA was used instead of AA as (b-2).
In Comparative Example 1-6, EHMA was used instead of BMA as (b-1).
In Comparative Examples 1-6 and 1-8 was used instead of _CH 2 = CHCOO of FA (C6) as _{(A) (CH 2) 2} (CF 2) 3 CF 3 (FA (C4)).
In Comparative Examples 1-7 and 1-9 was used instead of _CH 2 = CHCOO of (A) as _{FA (C6) (CH 2)} 2 (CF 2) 7 CF 3 (FA (C8)).

<Production of fluorinated copolymer composition>
The composition of the fluorine-containing block copolymer composition produced in Examples 3-1 to 3-8 and 4-1 to 4-3 and the compounding ratio thereof, and the molar ratio of (b-2) and (Y) were as follows. As shown in Table 3.
The composition of the fluorine-containing copolymer composition produced in Comparative Examples 2-1 to 2-15, the compounding ratio thereof, and the molar ratio of (b-2) and (Y) are as shown in Table 4.

[Example 3-1]
A fluorine-containing block copolymer composition was obtained by adding 90 parts by weight of IPA and 7 parts by weight of triethylamine to the dispersion liquid containing the (X) fluorine-containing block copolymer obtained in Example 1-1 and performing amine treatment. Obtained.

[Examples 3-2 to 3-8, 4-1 to 4-3]
In Examples 3-2 to 3-8 and 4-1 to 4-3, the composition of the fluorine-containing block copolymer composition shown in Table 3 and its compounding ratio, and the moles of (b-2) and (Y). Except for the ratio, it was prepared in the same manner as in Example 3-1.
In addition, in Examples 3-2 to 3-8 and 4-1 to 4-3, the (X) fluorine-containing block obtained in Examples 1-2 to 1-8 and 2-1 to 2-3, respectively. A polymer was used.

[Comparative Example 2-1]
A fluorine-containing random copolymer composition was obtained by adding 90 parts by weight of IPA and 7 parts by weight of triethylamine to the dispersion containing the fluorine-containing random copolymer obtained in Comparative Example 1-1 and performing amine treatment.

[Comparative Examples 2-2 to 2-15]
In Comparative Examples 2-2 to 2-15, Comparative Example 1-1 except for the composition of the fluorocopolymer composition and the compounding ratio thereof and the molar ratio of (b-2) and (Y) shown in Table 3. It was manufactured by the same method as.
In Comparative Examples 2-2 to 2-11, the fluorine-containing copolymers obtained in Comparative Examples 1-2 to 1-11 were used, respectively.
In Comparative Examples 2-12 to 2-15, the (X) fluorine-containing block copolymer obtained in Comparative Example 1-12 was used.
In Comparative Example 2-14, tetrabutylammonium hydroxide (TBAH) was used as the (Y) tertiary amine.
In Comparative Example 2-15, tetrabutylphosphonium hydroxide (TBPH) was used instead of the (Y) tertiary amine.

<Evaluation method>
[Sample preparation]
Using a glass substrate having a thickness of 2 mm, the dispersion containing the fluorocopolymer was applied by a bar coater so that the film thickness after drying was 20 μm, and then dried by heating at 120 ° C. for 1 hour. The obtained sample plate was used to carry out tests for slipperiness, water / oil repellency, and usability.

[Sliding property (dynamic friction coefficient)]
A dynamic friction coefficient was measured by using a surface property measuring machine (Tribogear manufactured by Shinto Kagaku Co., Ltd.) and a steel ball as a friction element by a method according to ASTM D1894.

[Water and oil repellency (static contact angle)]
Using a contact angle measuring device (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), the static contact angles of water and n-hexadecane were measured by a method (droplet method) based on JIS R 3257. The static contact angle was measured before and after the abrasion treatment described below.
(Abrasion treatment)
The sample plate is set horizontally, and a reciprocating abrasion tester (Tribogear manufactured by Shinto Kagaku Co., Ltd.) is used to attach a nonwoven fabric ("Bencot S" manufactured by Asahi Kasei Fibers Corporation, 1.7 N / cm ² ) Was repeatedly rubbed 5000 times.

[Usage (finger touch test)]
The feeling of use was evaluated by 10 expert panelists for sensory evaluation according to the following evaluation criteria, and the average thereof was taken as the result.
1: Very bad 2: Poor 3: Normal 4: Good 5: Very good

<Evaluation criteria>
Those satisfying all of the following standard values were regarded as good.
Sliding property: Dynamic friction coefficient less than 0.15 Water repellency: Static contact angle is 100 ° or more before abrasion treatment and 90 ° or more after abrasion treatment Oil repellency: Static contact angle is 60 ° or more before abrasion treatment and 50 ° after abrasion treatment Above usability: 4 or more

<Evaluation result>
Table 3 shows the evaluation results of the fluorine-containing block copolymer compositions according to Examples 3-1 to 3-8 and 4-1 to 4-3.

  As shown in Table 3, all of the (X) fluorine-containing block copolymers according to Examples 3-1 to 3-8 and 4-1 to 4-3 have good slidability, water and oil repellency, and use. You can see that you have a feeling. Furthermore, in Examples 4-1 to 4-3 in which 2-hydroxyethyl methacrylate was used as the (meth) acrylic acid alkyl ester having a hydroxyl group (b-3), slipperiness, water and oil repellency, and usability were improved. It has improved.

  Next, Table 4 shows the evaluation results of the fluorine-containing copolymer compositions according to Comparative Examples 2-1 to 2-15.

As shown in Table 4, in Comparative Examples 2-1 to 2-4, although the fluorine-containing random copolymers using the same kind of monomer as those in Examples were used, the standard values in terms of slipperiness and water / oil repellency were obtained. Did not meet.
In Comparative Example 2-5 containing no (b-2), the reference values were not satisfied in terms of slipperiness and water / oil repellency.
(A) In Comparative Examples 2-6 to 2-9 in which FA (C4) or FA (C8) was used for the fluorine-containing segment, the water and oil repellency was lowered, and Comparative Example 2-6 in which FA (C4) was used. In Nos. 2 and 8, the slipperiness was further reduced.

  In Comparative Examples 2-10 and 2-11, the (X) fluorine-containing block copolymer containing the same type of monomer as that in the Example is used, but Comparative Example 2-10 shows the (A) fluorine-containing segment. The content exceeded 55% by weight, and the water and oil repellency and the feeling of use did not meet the criteria. Further, in Comparative Example 2-11, the content of the fluorine-containing monomer was less than 10% by weight, and the slidability, the water / oil repellency, and the feeling of use did not satisfy the standard values.

In Comparative Example 2-12 in which the molar ratio of (b-2) and (Y) was less than 0.9, the water and oil repellency and the feeling of use did not satisfy the standard values.
In Comparative Example 2-13 in which the molar ratio of (b-2) and (Y) exceeded 1.1, the standard values were not satisfied in all of the slipperiness, the water / oil repellency, and the feeling of use.

In Comparative Example 2-14 in which TBAH was used as the (Y) tertiary amine, the reference values were not satisfied in all of the slipperiness, the water / oil repellency, and the feeling of use.
In Comparative Example 2-15 containing (Y) phosphonium (TBPH) instead of the tertiary amine, all of the slipperiness, the water / oil repellency, and the feeling of use did not satisfy the standard values.

  Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and it goes without saying that various modifications can be made without departing from the scope of the present invention.

Claims (2)

(A) a fluorine-containing segment, and (B) a non-fluorine and segments, Ru is composed of (X) a fluorine-containing block copolymer,
(Y) triethylamine,
Including,
The (A) fluorine-containing monomer constituting the fluorine-containing segment is a fluorine-containing monomer having a perfluoroalkyl group having 6 carbon atoms represented by the formula (1),
The non-fluorine-based monomer forming the non-fluorine segment (B) includes (b-1) (meth) acrylic acid alkyl ester monomer, (b-2) (meth) acrylic acid monomer, only including,
The (X) fluorine-containing block copolymer contains 10 to 55% by weight of the fluorine-containing monomer,
A fluorine-containing block copolymer composition in which the molar ratio of the component (b-2) and the component (Y) is 0.9 to 1.1 .

(1)
(In the formula (1), R ¹ represents a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom, and n is an integer of 1 to 18.) The fluorine-containing block copolymer composition according to claim 1 , wherein
The non-fluorine-based monomer that constitutes the non-fluorine segment (B) further includes (b-3) a (meth) acrylic acid alkyl ester monomer having a hydroxyl group. A fluorine-containing block copolymer composition .