JP2016074789A - Fluorine-containing diblock copolymer having polymerizable unsaturated group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorine-containing diblock copolymer having a polymerizable unsaturated group that uses as a monomer a fluorine-containing (meth)acrylic acid ester having low bioaccumulation potential, and has excellent water and oil repellency.SOLUTION: A fluorine-containing diblock copolymer having a polymerizable unsaturated group according to the present invention is produced by reacting a (meth)acrylic acid ester having an isocyanate group with a fluorine-containing diblock copolymer having a hydroxyl group comprising a non-fluorinated (meth)acrylic acid ester polymer block containing a non-fluorinated (meth)acrylic acid ester having a hydroxyl group as a constituent monomer and a fluorine-containing (meth)acrylic acid ester polymer block containing a fluorine-containing (meth)acrylic acid ester as a constituent monomer.SELECTED DRAWING: None

Description

  The present invention relates to a fluorine-containing diblock copolymer comprising a non-fluorine (meth) acrylic acid ester polymer block and a fluorine-containing (meth) acrylic acid ester polymer block. More specifically, the present invention relates to a fluorine-containing diblock copolymer having a polymerizable unsaturated group in the side chain of a non-fluorine (meth) acrylic acid ester polymer block.

Fluorine-containing (meth) acrylic esters such as CH ₂ = CHCO ₂ CH ₂ CH ₂ Rf or CH ₂ = C (CH ₃ ) CO ₂ CH ₂ CH ₂ Rf are raw materials for surface treatment agents such as water and oil repellents. It is used in large quantities as a monomer. However, in recent years, the above monomer having a perfluoroalkyl group (Rf) having 8 or more carbon atoms is highly bioaccumulative, making its use difficult. In order to avoid this problem, it is recommended to use a fluorine-containing (meth) acrylic acid ester having a perfluoroalkyl group having 6 or less carbon atoms.

For example, Patent Document 1 discloses a fluorine-containing block copolymer using a (meth) acrylic acid ester having a C 1-6 perfluoroalkyl group as a monomer. Patent Document 2 discloses C _n F _{2n + 1} (CH ₂ CF ₂ ) _a (CF ₂ CF ₂ ) _b (CH ₂ CH ₂ ) _c as an acrylate ester having a C 1-6 perfluoroalkyl group. OCOCH = CH ₂ is disclosed.

JP 2010-235784 A Japanese Patent No. 4673604

  However, the fluorine-containing block copolymer disclosed in Patent Document 1 has insufficient water and oil repellency. Moreover, although it is described that the fluorine-containing (meth) acrylic acid ester disclosed in Patent Document 2 can be used as a water / oil repellent synthetic monomer, the fluorine-containing (meth) acrylic acid ester is used. There was no report on the fluorine-containing block copolymer.

  Therefore, in order to solve the above-mentioned problems, the object of the present invention is to use a polymerizable unsaturated unsaturated monomer that uses a fluorine-containing (meth) acrylic acid ester having a low bioaccumulation property and has a good water / oil repellency. The object is to provide a fluorine-containing diblock copolymer having a group.

In order to achieve the above object, the fluorine-containing diblock copolymer having a polymerizable unsaturated group according to the present invention is a non-fluorine (meth) acrylic containing a non-fluorine (meth) acrylic acid ester having a hydroxyl group as a constituent monomer. Acid ester polymer block and the following general formula (1)
(In General Formula (1), R ¹ is a hydrogen atom or a methyl group, a is an integer of 1 to 3, b is an integer of 1 to 2, n is an integer of 1 to 6, C _n F _{2n + 1} is _- (CF 2 _{CH 2) b} - is bonded to CH _{2 groups, - (CF 2 CF 2)} a - group _- (CF 2 _{CH 2) b} - binding to CF ₂ groups And a fluorine-containing diblock copolymer having a hydroxyl group comprising a fluorine-containing (meth) acrylic acid ester-based polymer block having a fluorine-containing (meth) acrylic acid ester as a constituent monomer. It is produced by reacting a (meth) acrylic acid ester having a group.

The fluorine-containing diblock copolymer having a hydroxyl group is represented by the following general formula (2).
(In General Formula (2), R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and one of R ² and R ³ may contain one carboxyl group. R ⁴ is a linear alkyl group having 1 to 18 carbon atoms).
It is preferable to be produced by living radical polymerization in the presence of a trithiocarbonate represented by

  The number average molecular weight of the fluorine-containing diblock copolymer having a hydroxyl group is preferably 5,000 to 100,000.

  The fluorine-containing diblock copolymer having a polymerizable unsaturated group according to the present invention can form a water- and oil-repellent coating film on a substrate by being cured under appropriate conditions. It can be used as a surface modifier for a resin substrate.

It is a figure which shows the GPC curve of the polymer obtained at the 1st process and the 2nd process of Example 1-1. It is a figure which shows the GPC curve of the polymer obtained at the 1st process of Example 1-3, and the 2nd process. It is a figure which shows the GPC curve of the polymer obtained at the 1st process of the comparative example 1-1, and the 2nd process. It is a figure which shows the evaluation result of the magic ink resilience in Example 3-1 and Comparative Example 3-1. It is a figure which shows the evaluation result of the magic ink repellent property in Example 4-1 and Comparative Example 4-1. It is a figure which shows the evaluation result of the magic ink resilience in Example 5-1 and Comparative Example 5-1. It is a figure which shows the evaluation result of the magic ink repellent property in Example 6-1 and Example 6-2.

(Fluorine-containing diblock copolymer having a polymerizable unsaturated group)
The fluorine-containing diblock copolymer having a polymerizable unsaturated group according to the present invention includes a non-fluorine (meth) acrylate polymer block containing a non-fluorine (meth) acrylate having a hydroxyl group as a constituent monomer; The following general formula (1)
A fluorine-containing diblock copolymer having a hydroxyl group consisting of a fluorine-containing (meth) acrylic acid ester polymer block having a fluorine-containing (meth) acrylic acid ester represented by ) Manufactured by reacting acrylic ester. In Formula (1), R ¹ is a hydrogen atom or a methyl group, a is an integer of 1 to 3, b is an integer of 1 to 2, and n is an integer of 1 to 6. _{Also, -C n F 2n + 1 - (} CF 2 CH 2) b - is bonded to CH ₂ of, _- (CF 2 _{CF 2) a} - is _- (CF 2 _{CH 2) b} - binding to CF ₂ of doing.

  In the present specification, the phrase “(meth) acrylic acid ester” is used as a concept including both an acrylic acid ester and a methacrylic acid ester. Further, the phrase “non-fluorine” attached to a compound or a solvent is used to clarify that it is not “fluorine-containing”, that is, does not contain a fluorine atom in the molecule.

  The non-fluorine (meth) acrylic acid ester polymer block is formed by polymerizing a monomer containing a non-fluorine (meth) acrylic acid ester having a hydroxyl group. Examples of the non-fluorine (meth) acrylic acid ester having a hydroxyl group include (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid-2-hydroxypropyl, (Meth) acrylic acid-4-hydroxybutyl, (meth) acrylic acid-2-hydroxybutyl, polyethylene glycol mono (meth) acrylic acid ester, propylene glycol mono (meth) acrylic acid ester, 1,4-cyclohexanedimethanol mono ( Examples include (meth) acrylic acid esters, 1,3-dihydroxyadamantane mono (meth) acrylic acid esters, and the like.

  The non-fluorine (meth) acrylic acid ester polymer block may contain a non-fluorine (meth) acrylic acid ester copolymerizable with a non-fluorine (meth) acrylic acid ester having a hydroxyl group as a constituent monomer. Examples of such non-fluorine (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic. N-butyl acid, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth) acrylic N-octyl acid, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-octadecyl (meth) acrylate, Benzyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, (meth ) Dicyclopentanyl acrylate, dicyclopentenyl (meth) acrylate, and the like.

The fluorine-containing (meth) acrylic acid ester polymer block is formed by polymerizing the fluorine-containing (meth) acrylic acid ester represented by the general formula (1). As the fluorine-containing (meth) acrylic acid ester represented by the general formula (1), specifically,
3,3,4,4,5,5,7,7,8,8,8-undecafluorooctyl acrylate,
3,3,4,4,5,5,7,7,8,8,9,9,10,10,10-pentadecafluorodecyl acrylate,
3,3,4,4,5,5,6,6,7,7,9,9,10,10,10-pentadecafluorodecyl acrylate,
3,3,4,4,5,5,7,7,9,9,10,10,10-tridecafluorodecyl acrylate,
3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-nonadecafluorododecyl acrylate,
3,3,4,4,5,5,6,6,7,7,9,9,11,11,12,12,12-heptadecafluorododecyl acrylate,
3,3,4,4,5,5,7,7,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl acrylate,
3,3,4,4,5,5,6,6,7,7,9,9,11,11,12,12,13,13,14,14,14-heneicosafluorotetradecyl acrylate,
3,3,4,4,5,5,7,7,8,8,8-undecafluorooctyl methacrylate,
3,3,4,4,5,5,7,7,8,8,9,9,10,10,10-pentadecafluorodecyl methacrylate,
3,3,4,4,5,5,6,6,7,7,9,9,10,10,10-pentadecafluorodecyl methacrylate,
3,3,4,4,5,5,7,7,9,9,10,10,10-tridecafluorodecyl methacrylate,
3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-nonadecafluorododecyl methacrylate,
3,3,4,4,5,5,6,6,7,7,9,9,11,11,12,12,12-heptadecafluorododecyl methacrylate,
3,3,4,4,5,5,7,7,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl methacrylate,
3,3,4,4,5,5,6,6,7,7,9,9,11,11,12,12,13,13,14,14,14-heneicosafluorotetradecyl methacrylate Can be mentioned. Among them, in particular, 3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-nonadecafluorododecyl acrylate or 3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-nonadecafluorododecyl methacrylate is preferred.

  The fluorine-containing diblock copolymer having a hydroxyl group is composed of 10 to 99% by weight of a non-fluorine (meth) acrylate polymer block and 1 to 90% by weight of a fluorine (meth) acrylate polymer block. It is preferable to become. More preferably, the non-fluorine (meth) acrylic acid ester polymer block is 20 to 95% by weight, and the fluorine-containing (meth) acrylic acid ester polymer block is 5 to 80% by weight. If the fluorine-containing (meth) acrylic acid ester polymer block is less than 1% by weight, the water- and oil-repellent effect of the fluorine-containing diblock copolymer having a polymerizable unsaturated group may not be sufficiently exhibited. On the other hand, when the fluorine-containing (meth) acrylic acid ester polymer block exceeds 90% by weight, the fluorine-containing diblock copolymer having a polymerizable unsaturated group with respect to the non-fluorine polyfunctional unsaturated monomer and the non-fluorine solvent. There is a tendency for the solubility of the to decrease. Further, the water / oil repellent effect is not improved any more, which is uneconomical.

  The number average molecular weight of the fluorine-containing diblock copolymer having a hydroxyl group is 5,000 to 100,000. When the number average molecular weight is less than 5,000, the chain length of the fluorine-containing (meth) acrylic acid ester polymer block is shortened, and the surface modification effect or the water / oil repellency is lowered. On the other hand, when the number average molecular weight exceeds 100,000, the solubility of the fluorine-containing diblock copolymer having a polymerizable unsaturated group in a non-fluorine polyfunctional unsaturated monomer and a non-fluorine solvent tends to decrease. .

  The fluorine content of the fluorine-containing diblock copolymer having a hydroxyl group is 2 to 50% by weight, preferably 2 to 30% by weight, and more preferably 5 to 30% by weight. When the fluorine content is less than 2% by weight, the surface modification effect of the fluorine-containing diblock copolymer having a polymerizable unsaturated group is insufficient. On the other hand, even if the fluorine content exceeds 50% by weight, the surface modification effect is not improved and it is uneconomical.

(Method for producing fluorine-containing diblock copolymer having a polymerizable unsaturated group)
The fluorine-containing diblock copolymer having a polymerizable unsaturated group is produced by reacting a fluorine-containing diblock copolymer having a hydroxyl group with a (meth) acrylic acid ester having an isocyanate group. Examples of the (meth) acrylic acid ester having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 3- (meth) acryloyloxypropyl isocyanate, 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate. Etc.

  When producing a fluorine-containing diblock copolymer having a polymerizable unsaturated group, the isocyanate group of the (meth) acrylic acid ester having an isocyanate group and the hydroxyl group contained in the fluorine-containing diblock copolymer having a hydroxyl group The molar equivalent ratio (—NCO / —OH) is preferably 0.2 to 1.2. More preferably, it is 0.5-1.2. When the molar equivalent ratio is less than 0.2, the polymerizability of the fluorine-containing diblock copolymer having a polymerizable unsaturated group is lowered. On the other hand, if the molar equivalent ratio exceeds 1.2, a (meth) acrylic acid ester having an unreacted isocyanate group is generated, which is uneconomical.

  The reaction between the fluorine-containing diblock copolymer having a hydroxyl group and the (meth) acrylic acid ester having an isocyanate group is preferably performed in the presence of a urethanization catalyst. As the urethanization catalyst, an organic tin compound, an organic titanium compound, an organic zirconium compound, or an organic amine compound can be used. Further, an organic amine compound and an organic tin compound may be used in combination.

  Examples of the organotin compound used as a urethanization catalyst include dibutyltin dilaurate, bis (2-ethylhexanoate) tin, dibutyltinbis (2,4-pentanedionate), and the like.

  Examples of the organic titanium compound include titanium diisopropoxybis (ethyl acetoacetate).

  Examples of the organic zirconium compound include zirconium dibutoxybis (ethyl acetoacetate), zirconium tetra (acetylacetonate), and the like.

  Examples of organic amine compounds include N-methylmorpholine, N-ethylmorpholine, triethylenediamine, bis (dimethylaminoethyl) ether, 1,4-diazabicyclo (2,2,2) octane, pentamethyldiethylenetriamine, N, N-dimethyl. Cyclohexylamine, N-methyldicyclohexylamine, N, N, N, N-tetramethylpropylenediamine, N, N, N, N-tetramethylhexamethylenediamine, N-methylmorpholine, N-ethylmorpholine, N, N- Examples include dimethylethanolamine, N, N-diethylethanolamine, 1,8-diazabicyclo [5,4,0] -7-undecene and the like. Further, an organic acid salt of 1,8-diazabicyclo [5,4,0] -7-undecene can also be used. As the organic acid salt of 1,8-diazabicyclo [5,4,0] -7-undecene, for example, formate of 1,8-diazabicyclo [5,4,0] -7-undecene, 2-ethylhexanoic acid Examples thereof include salts, phenol salts, octylates, p-toluenesulfonates and orthophthalates.

  The reaction between the fluorine-containing diblock copolymer having a hydroxyl group and the (meth) acrylic acid ester having an isocyanate group can be carried out in an organic solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and toluene. it can.

  A fluorine-containing diblock copolymer having a polymerizable unsaturated group, after producing a fluorine-containing diblock copolymer having a hydroxyl group, has a urethanization catalyst and an isocyanate group in the solution containing the copolymer (meta ) It can manufacture by adding an acrylic ester and an organic solvent suitably as needed.

  The urethanization catalyst is used in an amount of 0.000001 to 0.01 mole equivalent to the hydroxyl group to be isocyanated. The hydroxyl group to be isocyanate is a hydroxyl group of a fluorine-containing diblock copolymer having a hydroxyl group.

  The production of the fluorine-containing diblock copolymer having a polymerizable unsaturated group is preferably performed in the presence of a polymerization inhibitor in order to suppress polymerization of the unsaturated group. As the polymerization inhibitor, for example, 4-methoxyphenol, 2,6-di-t-butyl-4-methylphenol and the like can be used. The polymerization inhibitor is used in the range of 1 to 5,000 ppm with respect to the fluorine-containing diblock copolymer having a hydroxyl group.

  Moreover, reaction with the fluorine-containing diblock copolymer which has a hydroxyl group, and the (meth) acrylic acid ester which has an isocyanate group can be performed at 0-100 degreeC. In order to suppress the polymerization reaction of the fluorine-containing diblock copolymer having a polymerizable unsaturated group, it is more preferably performed at 0 to 60 ° C.

(Method for producing fluorine-containing diblock copolymer having a hydroxyl group)
The fluorine-containing diblock copolymer having a hydroxyl group can be produced by controlled living radical polymerization. Representative methods of controlled living radical polymerization include reversible addition-fragmentation chain transfer polymerization (RAFT polymerization), atom transfer radical polymerization (ATRP) and nitroxide-mediated radical polymerization (NMP).

  In addition, since ATRP uses a metal catalyst such as a copper catalyst, a step of removing the metal catalyst may be required after the polymerization step. NMP requires a relatively high polymerization temperature. On the other hand, RAFT polymerization is suitable for the production of a fluorine-containing diblock copolymer having a hydroxyl group because there is no restriction on the production process and the polymerization control is easy.

  The fluorine-containing diblock copolymer having a hydroxyl group is preferably produced by either the following method (A) or method (B).

  (A) The method includes a first step and a second step. Hereinafter, the first step is referred to as “(A) method first step”, and the second step is referred to as “(A) method second step”.

  (A) Method 1st process superposes | polymerizes the monomer containing the non-fluorine (meth) acrylic acid ester which has a hydroxyl group in trithio carbonate ester and radical polymerization initiator presence, and is the non-fluorine (meth) acrylic acid ester which has a hydroxyl group. This is a process for producing a polymer.

In the second step (A), in the presence of a polymer of a non-fluorine (meth) acrylic acid ester having a hydroxyl group obtained in the first step (A), the following general formula (1)
Is a step of polymerizing a fluorine-containing (meth) acrylic acid ester represented by: In Formula (1), R ¹ is a hydrogen atom or a methyl group, a is an integer of 1 to 3, b is an integer of 1 to 2, and n is an integer of 1 to 6. _{Also, -C n F 2n + 1 - (} CF 2 CH 2) b - is bonded to CH ₂ of, _- (CF 2 _{CF 2) a} - is _- (CF 2 _{CH 2) b} - binding to CF ₂ of doing.

  In the first step (A), the above-mentioned non-fluorine (meth) acrylic acid ester having a hydroxyl group can be used as a monomer. In addition to the non-fluorine (meth) acrylic acid ester having a hydroxyl group, a non-fluorine (meth) acrylic acid ester copolymerizable with a non-fluorine (meth) acrylic acid ester having a hydroxyl group may be used as the monomer used for the polymerization. Good. As the copolymerizable non-fluorine (meth) acrylic acid ester, those described above can be used.

(A) In the first step of the method, trithiocarbonate is used as a RAFT agent. The trithiocarbonate is not particularly limited, but from the viewpoint of polymerization rate and polymerization yield, those represented by the following general formula (2) can be preferably used in the present invention.

In formula (2), R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and one of R ² and R ³ may contain one carboxyl group. Preferred examples of R ² and R ³ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a 2-carboxyethyl group. R ⁴ is a linear alkyl group having 1 to 18 carbon atoms. Considering the hydrolysis resistance of the trithiocarbonate, R ⁴ is preferably a linear alkyl group having 6 to 18 carbon atoms.

  Specific examples of the trithiocarbonate include 2-cyano-2-propyldodecyltrithiocarbonate, 4-cyano-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid, cyanomethyldodecyltrithiocarbonate, and the like. It is done.

A guideline of the amount of trithiocarbonate used can be obtained by the following equation.
W (RAFT) = W (A) × M (RAFT) / MW (PA)
here,
W (RAFT): Amount of trithiocarbonate used (g)
W (A): Total amount of non-fluorine (meth) acrylic acid ester (g)
M (RAFT): Molecular weight of trithiocarbonate (g / mol)
MW (PA): target molecular weight of non-fluorine (meth) acrylic acid ester polymer having a hydroxyl group (g / mol)
It is.

  The amount of trithiocarbonate used is preferably 0.1 to 10% by weight based on the total amount of non-fluorinated (meth) acrylic acid ester. In addition, the total usage-amount of non-fluorine (meth) acrylic acid ester is the monomer whole quantity containing the non-fluorine (meth) acrylic acid ester which has a hydroxyl group.

  (A) The polymerization solvent used in the first step of the method is appropriately selected in consideration of the solubility of the non-fluorine (meth) acrylic acid ester having a hydroxyl group and the solubility of the resulting polymer. As the polymerization solvent, for example, a fluorine-containing solvent, a non-fluorine solvent, or a mixture of a non-fluorine solvent and a fluorine-containing solvent is used. Among these, a non-fluorine solvent is more preferable. Examples of the non-fluorine solvent include methyl ethyl ketone, acetone, methyl isobutyl ketone, ethyl acetate, toluene, xylene and the like.

  It is preferable that the usage-amount of a solvent is 0-300 weight% with respect to the monomer whole quantity containing the non-fluorine (meth) acrylic acid ester which has a hydroxyl group. More preferably, it is 0 to 200% by weight. If it exceeds 300% by weight, the polymerization rate becomes slow, which is not practical.

  Polymerization of the monomer containing a non-fluorine (meth) acrylic acid ester having a hydroxyl group is preferably performed at 0 to 150 ° C, more preferably at 40 to 100 ° C. If it is less than 0 degreeC, sufficient polymerization rate may not be achieved but it may lead to the fall of a polymerization yield. On the other hand, when it exceeds 150 ° C., an inactive non-fluorine (meth) acrylic acid ester homopolymer having no hydroxyl group at the polymer end tends to be easily formed.

  The radical polymerization initiator used in the first step of the method (A) is not particularly limited as long as the polymerization reaction can proceed smoothly without any particular problem, but an azo radical polymerization initiator is preferably used. Specific examples of the azo radical polymerization initiator suitably used in the present invention include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 1,1 '-Azobis (cyclohexanecarbonitrile), 4,4-azobis (4-cyanovaleric acid) and the like.

  The radical polymerization initiator is preferably used in an amount of 5 to 35 mol% with respect to the trithiocarbonate. More preferably, it is 10-30 mol%. If it is less than 5 mol%, the polymerization yield may be reduced. On the other hand, if it exceeds 35 mol%, an inactive, non-fluorine (meth) acrylate homopolymer having a hydroxyl group that does not contain a trithiocarbonate fragment at the polymer end tends to be easily formed.

  (A) The material of the polymerization reaction vessel used in the first step of the method is not particularly limited as long as no trouble occurs in carrying out the polymerization reaction, such as decomposition of the trithiocarbonate or termination of the polymerization reaction, but borosilicate glass Or stainless steel is preferable. As a polymerization reaction vessel made of borosilicate glass that can be used in the present invention, a commercially available borosilicate glass vessel may be used. Does the trithiocarbonate decompose during the polymerization reaction and the polymerization reaction stops? If there are concerns about problems such as failure to achieve a stable high polymerization yield, a borosilicate tempered glass container is recommended. Borosilicate tempered glass is produced by air-cooling or chemical strengthening borosilicate glass.

  Specific examples of the borosilicate tempered glass container include a Hiper Glass (registered trademark) cylinder manufactured by Pressure Glass Industrial Co., Ltd. For example, HPG-10, HPG-96, TEM-U1000N, TEM-V-100, TEM-V-200, TEM-V-300, TEM-V-500, TEM-4-B1-2L, TEM-4- B1-4L (all manufactured by Pressure Glass Industry Co., Ltd.) can be mentioned.

  In the second step (A), the fluorine-containing (meth) acrylic acid ester represented by the general formula (1) is used as a monomer. Specific compounds described above can be used.

(A) Method 2nd process can be specifically performed by the method of the following method I or II.
Method I: A method in which a fluorine-containing (meth) acrylic acid ester and, if necessary, a polymerization solvent and a radical polymerization initiator are added to the polymerization solution obtained in the first step of method (A) for polymerization;
Method II: After isolating the non-fluorine (meth) acrylic acid ester polymer having a hydroxyl group obtained in the first step of method (A), the isolated polymer was subjected to fluorine-containing (meth) acrylic acid ester, Method of polymerizing by adding polymerization solvent and radical polymerization initiator

  (A) The polymerization solvent used in the second step of the method is a non-fluorine (meth) acrylic ester polymer having a hydroxyl group obtained in the first step of the (A) method and the dissolution of the fluorine-containing (meth) acrylic ester. In consideration of the characteristics, it is appropriately selected. As the polymerization solvent, for example, a fluorine-containing solvent, a non-fluorine solvent, or a mixture of a fluorine-containing solvent and a non-fluorine solvent is used. Examples of the fluorine-containing solvent include 1,3-bis (trifluoromethyl) benzene. Examples of the non-fluorine solvent include methyl ethyl ketone, acetone, methyl isobutyl ketone, ethyl acetate, toluene, xylene and the like.

  The amount of the solvent used is a non-fluorine (meth) acrylic acid ester polymer having a hydroxyl group obtained in the first step (A) and a fluorine-containing (meth) acrylic newly added in the second step (A). It is preferably 50 to 200% by weight based on the total weight of the acid ester. If it is less than 50% by weight, the viscosity of the reaction solution increases as the polymerization proceeds, and stirring and mixing may become difficult. On the other hand, if it exceeds 200% by weight, the polymerization rate becomes slow, which is not practical.

  The polymerization of the fluorine-containing (meth) acrylic acid ester is preferably performed at 0 to 150 ° C, more preferably at 40 to 100 ° C. If it is less than 0 degreeC, sufficient polymerization rate may not be achieved but it may lead to the fall of a polymerization yield. On the other hand, when it exceeds 150 ° C., a homopolymer of fluorine-containing (meth) acrylic acid ester tends to be easily produced as a by-product.

  Examples of the radical polymerization initiator used in the second step (A) include the same radical polymerization initiators used in the first step (A).

  The radical polymerization initiator is used in an amount of 5 to 35 mol% with respect to the trithiocarbonate fragment contained in the non-fluorine (meth) acrylic acid ester polymer having a hydroxyl group obtained in the first step of the method (A). More preferably, it is 10-30 mol%. If it is less than 5 mol%, the polymerization yield may be reduced. On the other hand, when it exceeds 35 mol%, a homopolymer of fluorine-containing (meth) acrylic acid ester tends to be easily produced as a by-product.

  Examples of the material of the polymerization reaction vessel used in the (A) method second step include the same materials as the polymerization reaction vessel used in the (A) method first step.

  Next, the method (B) will be described. (B) The method includes a first step and a second step. Hereinafter, the first step is referred to as “(B) method first step”, and the second step is referred to as “(B) method second step”.

(B) Method 1st process superposes | polymerizes the fluorine-containing (meth) acrylic acid ester represented by the said General formula (1) in presence of a trithiocarbonate and a radical polymerization initiator, and fluorine-containing (meth) acrylic acid ester This is a process for producing the polymer. In Formula (1), R ¹ is a hydrogen atom or a methyl group, a is an integer of 1 to 3, b is an integer of 1 to 2, and n is an integer of 1 to 6. _{Also, -C n F 2n + 1 - (} CF 2 CH 2) b - is bonded to CH ₂ of, _- (CF 2 _{CF 2) a} - is _- (CF 2 _{CH 2) b} - binding to CF ₂ of doing.

  The (B) method second step is a step of polymerizing a non-fluorine (meth) acrylic acid ester having a hydroxyl group in the presence of the fluorine-containing (meth) acrylic acid ester polymer obtained in the (B) method first step. It is.

  In the first step (B), the fluorine-containing (meth) acrylic acid ester represented by the general formula (1) is used as a monomer. Specific compounds described above can be used.

  (B) In the first step of the method, trithiocarbonate is used as a RAFT agent. The trithiocarbonate is not particularly limited, but from the viewpoint of the polymerization rate and the polymerization yield, those represented by the general formula (2) can be preferably used in the present invention.

A guideline of the amount of trithiocarbonate used can be obtained by the following equation.
W (RAFT) = W (FA) × M (RAFT) / MW (PFA)
here,
W (RAFT): Amount of trithiocarbonate used (g)
W (FA): Fluorine-containing (meth) acrylic ester usage (g)
M (RAFT): Molecular weight of trithiocarbonate (g / mol)
MW (PFA): Target molecular weight (g / mol) of fluorine-containing (meth) acrylic acid ester polymer
It is.

  The amount of trithiocarbonate used is preferably 0.1 to 10% by weight based on the fluorine-containing (meth) acrylic acid ester.

  The polymerization of the fluorine-containing (meth) acrylic acid ester can be carried out in the absence of a solvent (in the form of a block) or in a suitable organic solvent. As the polymerization solvent, for example, a fluorine-containing solvent or a mixed solvent of a fluorine-containing solvent and a non-fluorine solvent is used. Examples of the fluorine-containing solvent include 1,3-bis (trifluoromethyl) benzene. Examples of the non-fluorine solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, toluene, xylene and the like.

  It is preferable that the usage-amount of a solvent is 0 to 300 weight% with respect to fluorine-containing (meth) acrylic acid ester. More preferably, it is 0 to 200% by weight. If it exceeds 300% by weight, the polymerization rate becomes slow, which is not practical.

  Further, the polymerization of the fluorine-containing (meth) acrylic acid ester is preferably performed at 0 to 150 ° C, more preferably at 40 to 100 ° C. If it is less than 0 degreeC, sufficient polymerization rate may not be achieved but it may lead to the fall of a polymerization yield. On the other hand, if it exceeds 150 ° C., an inactive fluorine-containing (meth) acrylic acid ester homopolymer which does not contain a trithiocarbonate ester fragment at the polymer end tends to be easily formed.

  (B) The radical polymerization initiator used in the first step of the method is not particularly limited as long as the polymerization reaction can proceed smoothly without any particular problem, but an azo radical polymerization initiator is preferably used. Specific examples of the azo radical polymerization initiator suitably used in the present invention include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 1,1 '-Azobis (cyclohexanecarbonitrile), 4,4-azobis (4-cyanovaleric acid) and the like.

  The radical polymerization initiator is preferably used in an amount of 5 to 35 mol% with respect to the trithiocarbonate. More preferably, it is 10-30 mol%. If it is less than 5 mol%, the polymerization yield may be reduced. On the other hand, if it exceeds 35 mol%, an inactive fluorine-containing (meth) acrylate homopolymer which does not contain a trithiocarbonate ester fragment at the polymer end tends to be easily formed.

  (B) The material of the polymerization reaction vessel used in the first step of the method is not particularly limited as long as no trouble occurs in carrying out the polymerization reaction, such as decomposition of trithiocarbonate or termination of the polymerization reaction, but borosilicate glass Or stainless steel is preferable. As a polymerization reaction vessel made of borosilicate glass that can be used in the present invention, a commercially available borosilicate glass vessel may be used. Does the trithiocarbonate decompose during the polymerization reaction and the polymerization reaction stops? If there are concerns about problems such as failure to achieve a stable high polymerization yield, a borosilicate tempered glass container is recommended. Borosilicate tempered glass is produced by air-cooling or chemical strengthening borosilicate glass.

  Specific examples of the borosilicate tempered glass container include a Hiper Glass (registered trademark) cylinder manufactured by Pressure Glass Industrial Co., Ltd. For example, HPG-10, HPG-96, TEM-U1000N, TEM-V-100, TEM-V-200, TEM-V-300, TEM-V-500, TEM-4-B1-2L, TEM-4- B1-4L (all manufactured by Pressure Glass Industry Co., Ltd.) can be mentioned.

  In addition, the polymerization of the fluorine-containing (meth) acrylic acid ester in the first step of the method (B) may be easily and efficiently performed by using a borosilicate reinforced glass container. The cause is not clear, but it is presumed that the surface of the container probably has a structure chemically or physically inert with respect to the trithiocarbonate. Therefore, the first step of the method (B) is preferably performed in a borosilicate reinforced glass container or a stainless steel container.

  In the second step (B), the above-mentioned non-fluorine (meth) acrylic acid ester having a hydroxyl group can be used as a monomer. In addition to the non-fluorine (meth) acrylic acid ester having a hydroxyl group, a non-fluorine (meth) acrylic acid ester copolymerizable with a non-fluorine (meth) acrylic acid ester having a hydroxyl group may be used as the monomer used for the polymerization. Good. As the copolymerizable non-fluorine (meth) acrylic acid ester, those described above can be used.

(B) Method 2nd process can be specifically performed by the method of the following method I or II.
Method I: Polymerization is carried out by adding a monomer containing a non-fluorine (meth) acrylic acid ester having a hydroxyl group and, if necessary, a polymerization solvent and a radical polymerization initiator to the polymerization solution obtained in the first step of method (B). Method
Method II: After isolating the polymer of fluorine-containing (meth) acrylic acid ester obtained in the first step of method (B), non-fluorine (meth) acrylic acid ester having a hydroxyl group is added to the isolated polymer. Method of polymerizing by adding monomer, polymerization solvent and radical polymerization initiator

  (B) The polymerization solvent used in the second step of the method is the dissolution of the fluorine-containing (meth) acrylic acid ester polymer obtained in the first step of the (B) method and the non-fluorine (meth) acrylic acid ester having a hydroxyl group. In consideration of the characteristics, it is appropriately selected. As the polymerization solvent, for example, a fluorine-containing solvent, a non-fluorine solvent, or a mixture of a fluorine-containing solvent and a non-fluorine solvent is used. Examples of the fluorine-containing solvent include 1,3-bis (trifluoromethyl) benzene. Examples of the non-fluorine solvent include methyl ethyl ketone, acetone, methyl isobutyl ketone, ethyl acetate, toluene, xylene and the like.

  The amount of the solvent used is 50 with respect to the total weight of the fluorine-containing (meth) acrylic acid ester polymer obtained in the first step (B) and the monomer newly added in the second step (B). It is preferable that it is -200 weight%. If it is less than 50% by weight, the viscosity of the reaction solution increases as the polymerization proceeds, and stirring and mixing may become difficult. On the other hand, if it exceeds 200% by weight, the polymerization rate becomes slow, which is not practical.

  Polymerization of the monomer containing a non-fluorine (meth) acrylic acid ester having a hydroxyl group is preferably performed at 0 to 150 ° C, more preferably at 40 to 100 ° C. If it is less than 0 degreeC, sufficient polymerization rate may not be achieved but it may lead to the fall of a polymerization yield. On the other hand, when it exceeds 150 ° C., a homopolymer of non-fluorine (meth) acrylic acid ester having a hydroxyl group tends to be easily produced as a by-product.

  Examples of the radical polymerization initiator used in the second step (B) include the same radical polymerization initiators used in the first step (B).

  The radical polymerization initiator is used in an amount of 5 to 35 mol% with respect to the trithiocarbonate ester fragment contained in the polymer of the fluorine-containing (meth) acrylic acid ester obtained in the first step of the method (B). More preferably, it is 10-30 mol%. If it is less than 5 mol%, the polymerization yield may be reduced. On the other hand, when it is more than 35 mol%, a homopolymer of non-fluorine (meth) acrylic acid ester having a hydroxyl group tends to be easily produced as a by-product.

  (B) As a material of the polymerization reaction vessel used in the second step of the method, the same material as the polymerization reaction vessel used in the first step of the (B) method may be mentioned.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples.

(1) Raw materials Abbreviations of the raw materials used are shown below.
AIBN: 2,2′-azobis (isobutyronitrile) [manufactured by Wako Pure Chemical Industries, Ltd.]
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) [manufactured by Wako Pure Chemical Industries, Ltd.]
MEK: Methyl ethyl ketone CPDTC: 2-cyano-2-propyldodecyl trithiocarbonate (manufactured by Aldrich)
FAAC6: 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate FAAC10 (2H): 3,3,4,4,5,5 6,6,7,7,9,9,10,10,11,11,12,12,12-nonadecafluorododecyl acrylate MMA: methyl methacrylate [manufactured by Wako Pure Chemical Industries, Ltd.]
HEA: 2-hydroxyethyl acrylate [Wako Pure Chemical Industries]
AOI: 2-acryloyloxyethyl isocyanate (manufactured by Wako Pure Chemical Industries, Ltd.)
BHT: 2,6-di-t-butyl-4-methylphenol [Wako Pure Chemical Industries, Ltd.]
DEG: Diethylene glycol (Wako Pure Chemical Industries, Ltd.)
DBTDL: Dibutyltin dilaurate (Wako Pure Chemical Industries, Ltd.)
MQ: 4-methoxyphenol [Wako Pure Chemical Industries, Ltd.]

(2) Measurement method and evaluation method The measurement method and evaluation method are shown below.
〔composition〕
The composition of the fluorine-containing diblock copolymer having a hydroxyl group was calculated by ¹ H-NMR.
Apparatus: JEOL: JNM-LA300 (manufactured by JEOL Ltd.)
Solvent: chloroform-d or acetone-d6
Chemical shift: TMS standard [Molecular weight]
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the fluorine-containing diblock copolymer having a hydroxyl group were calculated in terms of polystyrene using GPC.
Column: Shodex (registered trademark) KF-807 (manufactured by Showa Denko) 4 measuring temperature: 40 ° C
Sample injection volume: 100 μl
Outflow rate: 1 ml / min
Eluent: Tetrahydrofuran [Molecular weight distribution]
Whether the molecular weight distribution of the fluorine-containing diblock copolymer having a hydroxyl group is unimodal or multimodal was determined by a GPC curve.
(Polymerization rate)
The final polymerization rate of the fluorine-containing diblock copolymer having a hydroxyl group was calculated by the following formula.
Polymerization rate = Solid content concentration of polymerization solution (actual value) / Solid content concentration of polymerization solution assuming 100% polymerization rate (calculated value)
[Modification rate]
The ratio (modification rate) of the hydroxyl group in the fluorine-containing diblock copolymer having a hydroxyl group converted to a polymerizable unsaturated group was calculated by ¹ H-NMR. A specific calculation method will be described later.
[Contact angle]
The contact angles for water and n-hexadecane were measured by DropMaster DM500 (manufactured by Kyowa Interface Science Co., Ltd.).
[Magic ink repellency]
A line was drawn on the surface of the resin film with a black oil-based pen Himackey (registered trademark, manufactured by Zebra Corporation), and the coating condition of the magic ink was visually observed.

(Example 1-1)
(First step: copolymerization of MMA and HEA)
Magnet Glass Stirrer, MMA 1.2g, HEA 0.30g, CPDTC 42mg, AIBN 4.0mg and MEK 1.0g in a 96ml Hiper Glass (registered trademark) cylinder (HPG-96: Pressure Glass Industrial Co., Ltd.) Was charged. The cylinder was immersed in liquid nitrogen to freeze the contents, and then degassed with an oil rotary vacuum pump for 5 minutes. After closing the needle valve, the cylinder was immersed in an oil bath at 85 ° C. for 16 hours, and a polymerization reaction was performed to obtain a solution containing a copolymer of MMA and HEA. The GPC curve of the polymer obtained in the first step of Example 1-1 is shown by the broken line in FIG.

(Second step: polymerization of FAAC10 (2H))
After the first step, 3.5 g of FAAC10 (2H), 3.0 mg of V-65, and 3.0 g of MEK were added into the cylinder. The cylinder was immersed in liquid nitrogen to freeze the contents, and then degassed with an oil rotary vacuum pump for 5 minutes. After closing the needle valve, the cylinder was immersed in an oil bath at 60 ° C. for 16 hours, and a polymerization reaction was performed to obtain a solution containing a fluorine-containing diblock copolymer having a hydroxyl group. From the solid content concentration of the contents, it was found that the final polymerization rate including the first step was 94%.
A part of the obtained polymerization solution was dropped into n-hexane, and a reprecipitation operation was performed. Then, the fluorine-containing diblock copolymer which has a hydroxyl group was obtained by making it dry at 60 degreeC under pressure reduction. Table 1 shows the composition, molecular weight, polydispersity PDI (Mw / Mn), and molecular weight distribution of the obtained copolymer. The GPC curve of the polymer obtained in the second step of Example 1-1 is shown by the solid line in FIG.

(Third step: Reaction of fluorine-containing diblock copolymer having a hydroxyl group with AOI)
After completion of the second step, 0.36 g of AOI, 10 mg of DBTDL, 5 mg of BHT, and 6.5 g of MEK were added into the cylinder. After degassing the inside of the cylinder, the cylinder was immersed in an oil bath at 60 ° C. for 4 hours to perform AOI modification to obtain a solution containing a fluorine-containing diblock copolymer having a polymerizable unsaturated group. Table 1 shows the modification rate of hydroxyl groups by AOI.
Denaturation rate = (a × y) / (b × x)
a = 3-position cis proton (6.44 ppm) peak integrated value of modified acryloyl group (CH ₂ ═CHC (═O) —) b = α-position CH ₃ group proton of modified MMA (0.7 to 1.1 ppm) ) Peak integral value / 3
x = side chain 1-position CH ₂ proton (4.10 ppm) peak integrated value of HEA before denaturation / 2
y = α-position CH ₃ group proton (0.7 to 1.1 ppm) peak integrated value of MMA before modification / 3

(Example 1-2)
(First step: copolymerization of MMA and HEA)
A solution containing a copolymer of MMA and HEA was obtained in the same manner as in the first step of Example 1-1 except that MMA was changed to 3.2 g and MEK was changed to 2.5 g.

(Second step: polymerization of FAAC10 (2H))
A solution containing a fluorine-containing diblock copolymer having a hydroxyl group was obtained in the same manner as in the second step of Example 1-1 except that FAAC10 (2H) was changed to 1.5 g and MEK was changed to 2.0 g. It was. The final polymerization rate including the first step was 94%.

(Third step: Reaction of fluorine-containing diblock copolymer having a hydroxyl group with AOI)
A fluorine-containing diblock copolymer having a polymerizable unsaturated group was obtained in the same manner as in Example 1-1 except that BHT was changed to 15 mg, MEK was changed to 6.0 g, and MQ 20 mg was further added. .

(Example 1-3)
(First step: copolymerization of MMA and HEA)
A solution containing a copolymer of MMA and HEA was obtained in the same manner as in the first step of Example 1-2 except that MMA was changed to 2.8 g and HEA was changed to 0.70 g. The GPC curve of the polymer obtained in the first step of Example 1-3 is shown by a broken line in FIG.

(Second step: polymerization of FAAC10 (2H))
A solution containing a fluorine-containing diblock copolymer having a hydroxyl group was obtained in the same manner as in the second step of Example 1-2. The final polymerization rate including the first step was 98%. The GPC curve of the polymer obtained in the second step of Example 1-3 is shown by the solid line in FIG.

(Third step: Reaction of fluorine-containing diblock copolymer having a hydroxyl group with AOI)
Fluorine-containing 2-block copolymer having a polymerizable unsaturated group in the same manner as in Example 1-2, except that AOI was changed to 0.85 g, the reaction temperature was changed to 20 ° C., and the reaction time was changed to 2 hours. Coalescence was obtained.

(Example 1-4)
(First step: copolymerization of MMA and HEA)
A solution containing a copolymer of MMA and HEA was obtained in the same manner as in the first step of Example 1-1 except that MMA was changed to 3.4 g, HEA was changed to 0.85 g, and MEK was changed to 3.5 g. It was.

(Second step: polymerization of FAAC10 (2H))
A solution containing a fluorine-containing diblock copolymer having a hydroxyl group was obtained in the same manner as in the second step of Example 1-1 except that FAAC10 (2H) was changed to 0.75 g and MEK was changed to 1.5 g. It was. The final polymerization rate including the first step was 99%.

(Third step: Reaction of fluorine-containing diblock copolymer having a hydroxyl group with AOI)
A fluorine-containing diblock copolymer having a polymerizable unsaturated group was obtained in the same manner as in Example 1-3, except that AOI was changed to 1.03 g and MEK was changed to 5.5 g.

(Example 1-5)
(First step: copolymerization of MMA and HEA)
A solution containing a copolymer of MMA and HEA was obtained in the same manner as in Example 1-1 except that MMA was changed to 3.7 g, HEA was changed to 0.90 g, and MEK was changed to 3.8 g. It was.

(Second step: polymerization of FAAC10 (2H))
A solution containing a fluorine-containing diblock copolymer having a hydroxyl group was obtained in the same manner as in the second step of Example 1-1 except that FAAC10 (2H) was changed to 0.40 g and MEK was changed to 1.2 g. It was. The final polymerization rate including the first step was 99%.

(Third step: Reaction of fluorine-containing diblock copolymer having a hydroxyl group with AOI)
A fluorine-containing diblock copolymer having a polymerizable unsaturated group was obtained in the same manner as in Example 1-4 except that AOI was changed to 1.10 g.

(Comparative Example 1-1)
(First step: copolymerization of MMA and HEA)
A solution containing a copolymer of MMA and HEA was obtained in the same manner as in the first step of Example 1-3. The GPC curve of the polymer obtained in the first step of Comparative Example 1-1 is shown by the broken line in FIG.

(Second step: polymerization of FAAC6)
A solution containing a fluorine-containing diblock copolymer having a hydroxyl group was obtained in the same manner as in the second step of Example 1-3 except that FAAC6 was used instead of FAAC10 (2H). The final polymerization rate including the first step was 99%. The GPC curve of the polymer obtained in the second step of Comparative Example 1-1 is shown by the solid line in FIG.

(Third step: Reaction of fluorine-containing diblock copolymer having a hydroxyl group with AOI)
In the same manner as in Example 1-3, a fluorine-containing diblock copolymer having a polymerizable unsaturated group was obtained.

(Example 2-1)
100 parts by weight of polypropylene glycol diacrylate (Fancrill (registered trademark) FA-P240A (manufactured by Hitachi Chemical Co., Ltd.)), 10 parts by weight of trimethylolpropane triacrylate (manufactured by Aldrich), 1-hydroxycyclohexyl phenyl ketone (Aldrich) 2 parts by weight and 56 parts by weight of MEK were mixed to prepare an ultraviolet curable resin composition solution A having a solid content of 66% by weight.
The fluorine-containing diblock copolymer having a polymerizable unsaturated group obtained in Example 1-1 (solid content: about 36% by weight) was added to 100 parts by weight of the ultraviolet curable resin composition solution A (solid content: 66% by weight). ) 1.83 parts by weight of the solution was added to obtain an ultraviolet curable resin composition solution. The ultraviolet curable resin composition solution was uniformly applied to a 76 mm × 26 mm × 1.0 mm glass slide and left in an oven at 60 ° C. for 5 minutes to remove the solvent. Thereafter, ultraviolet rays (200 mJ / cm ² ) were irradiated with an ultraviolet irradiation device under a nitrogen atmosphere to cure the resin composition (the thickness of the resin coating film was about 100 μm). Table 2 shows the static contact angle and the dynamic contact angle on the surface of the resin film.

(Example 2-2 to Example 2-5, Comparative Example 2-1)
The fluorine-containing diblock copolymer solution having a polymerizable unsaturated group obtained in Example 1-2 to Example 1-5 and Comparative Example 1-1 was added to the ultraviolet curable resin composition solution A, respectively. Except for the above, an ultraviolet curable resin composition solution was obtained in the same manner as in Example 2-1. The obtained ultraviolet curable resin composition solution was cured in the same manner as in Example 2-1. Table 2 shows the static contact angle and the dynamic contact angle on the surface of the resin film.

(Comparative Example 2-2)
Without adding the fluorine-containing diblock copolymer solution having a polymerizable unsaturated group, only the ultraviolet curable resin composition solution A was cured in the same manner as in Example 2-1. Table 2 shows the static contact angle and the dynamic contact angle on the surface of the resin film.

(Example 3-1)
(Preparation of polyfunctional acrylic ester DEG / BEI)
A magnetic stirrer, 7.18 g of Karenz (registered trademark) BEI (manufactured by Showa Denko KK), 1.59 g of DEG, 12 mg of DBTDL, and 12 mg of MQ were charged into a Schlenk tube made of borosilicate glass having an internal volume of 50 ml. After degassing the Schlenk tube, it was immersed in an oil bath at 40 ° C. for 6 hours. After completion of the reaction, a part of the product was extracted and the presence or absence of an isocyanate group was confirmed by an infrared absorption spectrometer. Since 2,280 cm ⁻¹ absorption due to the isocyanate group was not observed, it was confirmed that the reaction was completed and the following polyfunctional acrylic ester DEG / BEI was produced.
100 parts by weight of polyfunctional acrylic ester DEG / BEI, 2 parts by weight of 2-hydroxycyclohexyl phenyl ketone and 204 parts by weight of MEK were mixed to prepare an ultraviolet curable resin composition solution B having a solid content of 33% by weight.
The fluorine-containing diblock copolymer having a polymerizable unsaturated group obtained in Example 1-3 (solid content: about 36% by weight) was added to 100 parts by weight of the ultraviolet curable resin composition solution B (solid content: 33% by weight). ) 0.92 parts by weight of the solution was added to obtain an ultraviolet curable resin composition solution. The ultraviolet curable resin composition solution was uniformly applied to a 76 mm × 26 mm × 1.0 mm glass slide and left in an oven at 60 ° C. for 5 minutes to remove the solvent. Thereafter, ultraviolet rays (200 mJ / cm ² ) were irradiated with an ultraviolet irradiation device under a nitrogen atmosphere to cure the resin composition (the thickness of the resin coating film was about 100 μm). Table 3 shows the static contact angle and the dynamic contact angle on the surface of the resin film. Moreover, the evaluation result of magic ink flipping property is shown on the right side of FIG.

(Comparative Example 3-1)
Without adding the fluorine-containing diblock copolymer solution having a polymerizable unsaturated group, only the ultraviolet curable resin composition solution B was cured in the same manner as in Example 3-1. Table 3 shows the static contact angle and the dynamic contact angle on the surface of the resin film. Further, the evaluation result of the magic ink repelling property is shown on the left side of FIG.

(Example 4-1)
Urethane acrylate UV curable resin beam set (registered trademark) 575CB (Arakawa Chemical Industries, Ltd.) 100 parts by weight, MEK 150 parts by weight, and fluorine-containing 2 having a polymerizable unsaturated group obtained in Example 1-3 A block copolymer (solid content of about 3.6% by weight diluted with MEK) solution 0.28 parts by weight (active ingredient addition amount 0.01 parts by weight) is mixed to obtain an ultraviolet curable resin composition solution. It was. This ultraviolet curable resin composition solution was uniformly applied to a 76 mm × 26 mm × 1.0 mm glass slide and left in an oven at 60 ° C. for 5 minutes to remove the solvent. Thereafter, ultraviolet rays (180 mJ / cm ² ) were irradiated with an ultraviolet irradiation device in a nitrogen atmosphere to cure the resin composition (the thickness of the resin coating film was about 100 μm). Table 4 shows the static contact angle and the dynamic contact angle on the surface of the resin film. Further, the evaluation result of the magic ink repellent property is shown on the right side of FIG.

(Comparative Example 4-1)
Without adding a fluorine-containing diblock copolymer solution having a polymerizable unsaturated group, 100 parts by weight of urethane acrylate-based UV curable resin beam set (registered trademark) 575CB and 150 parts by weight of MEK are mixed to obtain an ultraviolet curable resin composition. A solution was obtained. This ultraviolet curable resin composition solution was cured in the same manner as in Example 4-1. Table 4 shows the static contact angle and the dynamic contact angle on the surface of the resin film. Further, the evaluation result of the magic ink repelling property is shown on the left of FIG.

(Example 5-1)
Urethane acrylate-based UV curable resin Hitaloid (registered trademark) 7909-1 (manufactured by Hitachi Chemical Co., Ltd., solid content 80% by weight) 125 parts by weight, 2-hydroxycyclohexyl phenyl ketone 2 parts by weight, MEK 123 parts by weight, and Example 1 -3 fluorinated diblock copolymer having a polymerizable unsaturated group obtained in -3 (solid content diluted to 3.6% by weight with MEK) 2.8 parts by weight (active ingredient addition amount 0.10) Part by weight) and UV cured. Thereafter, ultraviolet rays (180 mJ / cm ² ) were irradiated with an ultraviolet irradiation device in a nitrogen atmosphere to obtain a mold resin composition solution. This ultraviolet curable resin composition solution was uniformly applied to a 76 mm × 26 mm × 1.0 mm slide glass, and left in an oven at 60 ° C. for 5 minutes to remove the solvent, and the resin composition was cured (resin coating film Thickness of about 100 μm). Table 5 shows the static contact angle and the dynamic contact angle on the surface of the resin film. Moreover, the evaluation result of magic ink flipping property is shown on the right side of FIG.

(Comparative Example 5-1)
Without adding a fluorine-containing diblock copolymer solution having a polymerizable unsaturated group, urethane acrylate-based UV curable resin Hitaloid (registered trademark) 7909-1125 parts by weight, 2-hydroxycyclohexyl phenyl ketone 2 parts by weight, and MEK 123 parts by weight Parts were mixed to prepare an ultraviolet curable resin composition solution. This ultraviolet curable resin composition solution was cured in the same manner as in Example 5-1. Table 5 shows the static contact angle and the dynamic contact angle on the surface of the resin film. Moreover, the evaluation result of magic ink flipping property is shown on the left of FIG.

(Example 6-1)
Urethane acrylate UV curable resin Hitaroid (registered trademark) 7909-1125 parts by weight, 2-hydroxycyclohexyl phenyl ketone 2 parts by weight, MEK 40 parts by weight, and the polymerizable unsaturated group obtained in Example 1-3. Fluorine diblock copolymer (solid content of about 3.6% by weight diluted with MEK) 2.78 parts by weight (active ingredient addition amount 0.10 parts by weight) is mixed, and UV curable resin composition solution Got. Using a bar coater, this ultraviolet curable resin composition solution was applied to a corona-treated PET film (thickness 50 μm) and left in an oven at 60 ° C. for 5 minutes to remove the solvent. Thereafter, ultraviolet rays (180 mJ / cm ² ) were irradiated with an ultraviolet irradiation device in a nitrogen atmosphere to cure the resin composition (the thickness of the resin coating film was about 20 μm). The evaluation result of the magic ink flipping property is shown on the left of FIG.

(Example 6-2)
Urethane acrylate UV curable resin beam set (registered trademark) 575 CB 100 parts by weight, MEK 67 parts by weight, and fluorine-containing diblock copolymer having a polymerizable unsaturated group obtained in Example 1-3 (solid content of about 3 0.69 parts by weight (diluted with MEK to 6% by weight)) was mixed with 0.694 parts by weight (active ingredient addition amount 0.025 parts by weight) to obtain an ultraviolet curable resin composition solution. Using a bar coater, this ultraviolet curable resin composition solution was applied to a corona-treated PET film (thickness 50 μm) and left in an oven at 60 ° C. for 5 minutes to remove the solvent. Thereafter, ultraviolet rays (180 mJ / cm ² ) were irradiated with an ultraviolet irradiation device in a nitrogen atmosphere to cure the resin composition (the thickness of the resin coating film was about 20 μm). The evaluation result of the magic ink flipping property is shown on the right side of FIG.

  In Examples 2-1 to 2-5 and Comparative Example 2-2, a small amount of the fluorine-containing diblock copolymer having a polymerizable unsaturated group according to the present invention is added to the ultraviolet curable resin, so that It is data which shows that favorable water and oil repellency can be provided to the resin coating film surface. Comparative Example 2-1 is a case where FAAC6 is used as a monomer constituting the fluorine-containing (meth) acrylic acid ester polymer block, and the fluorine content is 17% by weight, which is substantially the same as Example 2-3. Nevertheless, the data shows that the water and oil repellency is insufficient.

  Examples 3-1 and 4-1 and 5-1 and Comparative Examples 3-1 and 4-1 and 5-1 are UV-cured fluorine-containing diblock copolymers having a polymerizable unsaturated group according to the present invention. This data shows that by adding a small amount to the mold resin, water and oil repellency and antifouling property against magic ink can be imparted to the surface of the cured resin coating film.

  In Examples 6-1 and 6-2, a small amount of the fluorine-containing diblock copolymer having a polymerizable unsaturated group according to the present invention is added to the ultraviolet curable resin so that the surface of the cured resin coating film has magic. It is data which shows that the antifouling property with respect to ink can be provided.

  As described above, the fluorine-containing diblock copolymer having a polymerizable unsaturated group according to the present invention can form a water- and oil-repellent coating and an antifouling coating on a substrate by curing with ultraviolet rays or the like. it can. In particular, even when the fluorine content of the fluorine-containing diblock copolymer having a polymerizable unsaturated group is 20% by weight or less, good water and oil repellency can be imparted. In addition, by adding a small amount (1% by weight or less) to an ultraviolet curable resin containing polyfunctional unsaturated compounds (urethane acrylate, epoxy acrylate, polyester acrylate, etc.) as a main component, the coating film surface after UV curing is good. Water and oil repellency and antifouling properties can be imparted.

Claims (3)

A non-fluorine (meth) acrylate polymer block containing a non-fluorine (meth) acrylate having a hydroxyl group as a constituent monomer, and the following general formula (1)
(In General Formula (1), R ¹ is a hydrogen atom or a methyl group, a is an integer of 1 to 3, b is an integer of 1 to 2, n is an integer of 1 to 6, C _n F _{2n + 1} is _- (CF 2 _{CH 2) b} - is bonded to CH _{2 groups, - (CF 2 CF 2)} a - group _- (CF 2 _{CH 2) b} - binding to CF ₂ groups doing.)
A fluorine-containing diblock copolymer having a hydroxyl group consisting of a fluorine-containing (meth) acrylic acid ester polymer block having a fluorine-containing (meth) acrylic acid ester represented by ) A fluorine-containing diblock copolymer having a polymerizable unsaturated group, which is produced by reacting an acrylic ester. The fluorine-containing diblock copolymer having a hydroxyl group is represented by the following general formula (2)
(In General Formula (2), R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and one of R ² and R ³ may contain one carboxyl group. R ⁴ is a linear alkyl group having 1 to 18 carbon atoms.)
The fluorine-containing diblock copolymer having a polymerizable unsaturated group according to claim 1, which is produced by living radical polymerization in the presence of a trithiocarbonate represented by the formula:   The fluorine-containing diblock having a polymerizable unsaturated group according to claim 1 or 2, wherein the fluorine-containing diblock copolymer having a hydroxyl group has a number average molecular weight of 5,000 to 100,000. Copolymer.