JP2019085450A - Fluorine-containing polymer and curable composition - Google Patents

Abstract

To provide a fluorine-containing polymer capable of obtaining a cured product having high heat resistance and hardness and excellent adhesiveness with a base material and a curable composition.SOLUTION: There is provided a fluorine-containing polymer having a unit based on the following monomer A and a unit based on the following monomer B. Monomer A: a monomer having a carbon ring or a ring structure having a carbon-carbon double bond in a heterocycle and a perfluoroalkyl group or a group having an ethereal oxygen atom between carbon atoms in the perfluoroalkyl group (provided that a monomer having a protected crosslinkable group or an active hydrogen-containing group is excluded). Monomer B: a monomer having a protected crosslinkable group.SELECTED DRAWING: None

Description

  The present invention relates to a fluorine-containing polymer and a curable composition.

  The use of the fluorine-containing polymer includes, for example, a water and oil repellent and a release agent. When the water- and oil-repellent agent, the release agent, etc. are required to have adhesion to a substrate, heat resistance, etc., a curable composition containing a fluorine-containing polymer having a protected crosslinkable group may be used. .

  The fluorinated polymer having a protected crosslinkable group includes a unit based on a monomer having a (meth) acryloyl group and a perfluoroalkyl group, and a unit based on a monomer having a (meth) acryloyl group and a blocked isocyanate group The fluorine-containing polymer is proposed (patent documents 1 and 2).

International Publication No. 2015/064360 Unexamined-Japanese-Patent No. 2017-039318

However, the fluorine-containing polymers described in Patent Documents 1 and 2 are mainly composed of units formed by polymerization of a monomer having a (meth) acryloyl group, and therefore, are easily depolymerized by heating. Therefore, the heat resistance of the cured product obtained by crosslinking the fluorine-containing polymer is insufficient.
In addition, in order to allow the crosslinking reaction of the fluorine-containing polymer to sufficiently proceed and obtain a cured product having sufficient hardness, the blocking agent is dissociated from the blocked isocyanate group by heat treatment at about 200 ° C. to sufficiently perform the crosslinking reaction. It is necessary to advance. However, since the fluoropolymers described in Patent Documents 1 and 2 depolymerize during heat treatment, the hardness of a cured product obtained by crosslinking the fluoropolymer is low.

  The present invention provides a fluorine-containing polymer and a curable composition which can obtain a cured product which is high in heat resistance and hardness and excellent in adhesion to a substrate.

ただし、Ｒ^ｆ１は、ペルフルオロアルキル基又はペルフルオロアルキル基の炭素原子間にエーテル性酸素原子を有する基であり、Ｑ^１は、単結合又は２価の有機基であり、ｍは、０又は１であり、Ｒ^ｆ２は、ペルフルオロアルキル基又はペルフルオロアルキル基の炭素原子間にエーテル性酸素原子を有する基であり、Ｑ^２は、単結合又は２価の有機基であり、Ｒ^１及びＲ^２は、それぞれ独立に水素原子又はメチル基である。
＜３＞前記モノマーＢにおける保護された架橋性基が、ブロックドイソシアネート基である、前記＜１＞又は＜２＞の含フッ素ポリマー。
＜４＞下記モノマーＣに基づく単位をさらに有する、前記＜１＞〜＜３＞のいずれかの含フッ素ポリマー。
モノマーＣ：炭素環又は複素環中に炭素−炭素二重結合を有する環構造と、活性水素含有基とを有するモノマー。
＜５＞前記モノマーＣが、下式Ｃ−１で表されるモノマー又は下式Ｃ−２で表されるモノマーである、前記＜４＞の含フッ素ポリマー。

ただし、Ｑ^３は、単結合又は２価の有機基であり、ｎは、０又は１であり、Ｑ^４は、単結合又は２価の有機基であり、Ｒ^３及びＲ^４は、それぞれ独立に水素原子又はメチル基である。
＜６＞（メタ）アクリロイル基を有するモノマーが重合して形成された単位の割合が、前記含フッ素ポリマーを構成する全単位のうち、５０質量％以下である、前記＜１＞〜＜５＞のいずれかの含フッ素ポリマー。
＜７＞前記＜１＞〜＜６＞のいずれかの含フッ素ポリマーを含む、硬化性組成物。
＜８＞撥水撥油剤組成物である、前記＜７＞の硬化性組成物。 The present invention has the following aspects.
The fluorine-containing polymer which has a unit based on the <1> following monomer A, and a unit based on the following monomer B.
Monomer A: a monomer having a ring structure having a carbon-carbon double bond in a carbon ring or a heterocycle and a group having an etheric oxygen atom between carbon atoms of a perfluoroalkyl group or a perfluoroalkyl group (provided that it is protected Excluding those having a crosslinkable group or an active hydrogen-containing group).
Monomer B: a monomer having a protected crosslinkable group.
<2> The fluorine-containing polymer of <1>, wherein the monomer A is a monomer represented by the following formula A-1 or a monomer represented by the following formula A-2.

However, R ^f1 is a group having an etheric oxygen atom between carbon atoms of a perfluoroalkyl group or a perfluoroalkyl group, Q ¹ is a single bond or a divalent organic group, and m is 0 or 1 R ^f2 is a group having an etheric oxygen atom between carbon atoms of a perfluoroalkyl group or a perfluoroalkyl group, Q ² is a single bond or a divalent organic group, and R ¹ and R ² are Each of them is independently a hydrogen atom or a methyl group.
The fluorine-containing polymer of said <1> or <2> whose protected crosslinkable group in <3> said monomer B is a blocked isocyanate group.
The fluorine-containing polymer in any one of said <1>-<3> which further has a unit based on the <4> following monomer C.
Monomer C: A monomer having a ring structure having a carbon-carbon double bond in a carbon ring or a heterocycle and an active hydrogen-containing group.
<5> The fluorine-containing polymer of <4>, wherein the monomer C is a monomer represented by the following formula C-1 or a monomer represented by the following formula C-2.

However, Q ³ is a single bond or a divalent organic group, n is 0 or 1, Q ⁴ is a single bond or a divalent organic group, and R ³ and R ⁴ are each independently Is a hydrogen atom or a methyl group.
The ratio of a unit formed by polymerizing a monomer having a <6> (meth) acryloyl group is 50% by mass or less of all units constituting the fluoropolymer, in the above <1> to <5> Any of the fluorine-containing polymers.
The curable composition containing the fluorine-containing polymer in any one of <7> said <1>-<6>.
The curable composition of said <7> which is a <8> water / oil repellent composition.

According to the fluorine-containing polymer of the present invention, a cured product which is high in heat resistance and hardness and excellent in adhesion to a substrate can be obtained.
According to the curable composition of the present invention, it is possible to obtain a cured product which is high in heat resistance and hardness and excellent in adhesion to a substrate.

In the present specification, the monomer represented by formula A-1 is referred to as monomer A-1. The same applies to monomers represented by other formulas.
The following definitions of terms apply throughout the specification and claims.
The "unit" means an atomic group based on the monomer formed by radical polymerization of the monomer. The unit may be an atomic group directly formed by a polymerization reaction, or may be an atomic group in which a part of the atomic group is converted to another structure by treating a polymer.
The "monomer" is a compound having a polymerization reactive carbon-carbon double bond.
The "crosslinkable group" is a group capable of forming a crosslinked structure by reacting with each other or via a crosslinking agent.
The “protected crosslinkable group” is a group in which the crosslinkability is suppressed by chemically modifying the crosslinkable group, and is a group that can become a crosslinkable group by deprotection.
The "(meth) acryloyl group" is a generic term for acryloyl group and methacryloyl group.
"(Meth) acrylate" is a generic term for acrylate and methacrylate.
The “proportion of each unit” in the polymer is determined from the integral ratio of the peaks unique to each unit in the ¹ H-NMR spectrum of the polymer.
The "mass average molecular weight" of the polymer is a value in terms of standard polymethyl methacrylate determined by gel permeation chromatography.
"-" Which shows a numerical range means including the numerical value described before and after that as a lower limit and an upper limit.

<Fluorinated polymer>
The fluorine-containing polymer of the present invention (hereinafter referred to as "the present fluorine-containing polymer") is a unit based on the following monomer A (hereinafter referred to as the "monomer A unit") and a unit based on the following monomer B (hereinafter referred to as Also described as "monomer B unit".
The fluorine-containing polymer may further have a unit based on the following monomer C (hereinafter, also referred to as “monomer C unit”).
In the present fluorine-containing polymer, units based on other monomers other than monomer A, monomer B and monomer C (hereinafter also referred to as “other monomer units”) are within a range that does not impair the effects of the present invention. You may have further.

(Monomer A)
Monomer A is a monomer having a ring structure having a carbon-carbon double bond in a carbon ring or a heterocyclic ring, and a group having an etheric oxygen atom between carbon atoms of a perfluoroalkyl group or a perfluoroalkyl group (however, protected) Except for those having a crosslinkable group or an active hydrogen-containing group). When the present fluorine-containing polymer has a monomer A unit, it is possible to obtain a cured product having excellent properties derived from a fluorine atom (water and oil repellency, releasability, electrical properties, etc.) and high heat resistance. As the monomer A, one type may be used alone, or two or more types may be used in combination.

  The ring structure having a carbon-carbon double bond in the carbon ring or the heterocyclic ring includes cycloalkene having 4 to 10 carbon atoms, norbornene, 7-oxa norbornene, 7-thio norbornene, maleimide, acenaphthylene, 2 to 4 Ring structure having one or more carbon-carbon double bond in the fused ring consisting of cycloalkane ring, one carbon-carbon double bond in the fused ring consisting of a total of 2 to 4 of cycloalkane ring and norbornane ring The ring structure etc. which have a carbon-carbon double bond in a non-aromatic ring among condensed rings which consist of a total of 2 to 4 of the ring structure which has the above, a cycloalkane ring, and an aromatic ring etc. are mentioned.

  1-20 are preferable and, as for carbon number of a perfluoro alkyl group, 2-10 are more preferable. If the carbon number of the perfluoroalkyl group is at least the lower limit value of the above range, a cured product which is further excellent in properties derived from fluorine atoms (water and oil repellency, releasability, electrical properties, etc.) can be obtained. If the carbon number of the perfluoroalkyl group is not more than the upper limit value of the above range, the polymerization reactivity is not lowered, so that the synthesis of the present fluorine-containing polymer becomes easy and the solubility of the obtained present fluorine-containing polymer is not lowered. , It is easy to mix this fluorine-containing polymer with resin etc.

Examples of the group having an etheric oxygen atom between carbon atoms of a perfluoroalkyl group or a perfluoroalkyl group include the following groups.
− (CF ₂ ) _p CF ₃ ,
_{- (CF 2 CF (CF 3} )) q OCF 2 CF 2 CF 3,
_{- (OCF 2 CF 2) r} O (CF 2) s CF 3 and the like.
However, p is an integer of 0-19, q is an integer of 0-9, r is an integer of 0-9, and s is an integer of 0-19.

  As the monomer A, the monomer A-1 or the monomer A-2 is preferable in terms of easiness of synthesis and high solubility of the polymer in the solvent.

However, R ^f1 is a group having an etheric oxygen atom between carbon atoms of the aforementioned perfluoroalkyl group or perfluoroalkyl group, Q ¹ is a single bond or a divalent organic group, and m is 0 or R ^f2 is a group having an etheric oxygen atom between carbon atoms of the aforementioned perfluoroalkyl group or perfluoroalkyl group, and Q ² is a single bond or a divalent organic group, and R ¹ and R ² are Each R ² is independently a hydrogen atom or a methyl group.

As the divalent organic group in Q ¹ and Q ^2, an alkylene group having 1 to 6 carbon atoms, a group having an etheric oxygen atom or an ester bond between carbon atoms of an alkylene group having 2 to 6 carbon atoms, 1 carbon atom A group having an etheric oxygen atom or an ester bond at the end of an alkylene group of 6 to 6, a fluoroalkylene group having 1 to 6 carbon atoms having one or more hydrogen atoms, or a fluorocarbon having 2 to 6 carbon atoms having one or more hydrogen atoms A group having an etheric oxygen atom between carbon atoms of an alkylene group, a group having an etheric oxygen atom at the end of a fluoroalkylene group having 1 to 6 carbon atoms having one or more hydrogen atoms, an arylene group, a heteroarylene group, and the like Groups in which two or more of the groups listed above are combined, and the like.

  Examples of the monomer A-1 include the following monomers.

  Examples of the monomer A-2 include the following monomers.

(Monomer B)
The monomer B is a monomer having a protected crosslinkable group. When the present fluorine-containing polymer has a monomer B unit, a cured product having high hardness and excellent adhesion to a substrate can be obtained. As the monomer B, one type may be used alone, or two or more types may be used in combination.

The protected crosslinkable group includes blocked isocyanate group, tert-butoxycarbonyl group, benzyloxycarbonyl group, methoxymethyl group and the like, and the protective group can be removed by both heat and acid, and deprotection Blocked isocyanate groups are preferred because the subsequent isocyanate groups are excellent in crosslinking reactivity.
A blocked isocyanate group is a group obtained by blocking an isocyanate group with a blocking agent. Examples of the blocking agent include oxime, pyrazole and derivatives thereof.

  As the monomer B having a blocked isocyanate group, the monomer B-1 is preferable in terms of high availability and high hardness after crosslinking.

However, R ⁵ is a hydrogen atom, a halogen atom or a methyl group, and Q ⁵ is a group having an etheric oxygen atom between carbon atoms of an alkylene group having 1 to 6 carbon atoms or an alkylene group having 2 to 6 carbon atoms And Z is a monovalent organic group derived from a blocking agent.
As R ⁵ , a hydrogen atom or a methyl group is preferable, and a methyl group is more preferable.
As Z, a group represented by the following formula Z1, a group represented by the following formula Z2 or a group represented by the following formula Z3 is preferable.

However, * is a bond, R < ⁶ >, R < ⁷ >, R < ⁸ > and R < ⁹ > are a C1-C4 alkyl group each independently.
Examples of the monomer B-1 include the following monomers.

(Monomer C)
The monomer C is a monomer having a ring structure having a carbon-carbon double bond in a carbon ring or a heterocycle and an active hydrogen-containing group. When the present fluorine-containing polymer has a monomer C unit, a crosslinked structure is formed by the reaction of an active hydrogen-containing group and a crosslinkable group derived from the monomer B unit, so that a cured product having a still higher hardness can be obtained. it can. In addition, a cured product with higher heat resistance can be obtained. As the monomer C, one type may be used alone, or two or more types may be used in combination.

As a ring structure which has a carbon-carbon double bond in a carbocyclic ring or a heterocyclic ring, the thing similar to the ring structure in the monomer A is mentioned, A preferable form is also the same.
Examples of the active hydrogen-containing group include a hydroxyl group, a thiol group, an amino group, a pyrazole group, an imidazole group, a morpholino group, a pyrrolidinyl group, and a piperidyl group. From the viewpoint of crosslinking reactivity, hydroxyl group, thiol group or amino A group is preferred, and a hydroxyl group is more preferred.

  As the monomer C, the monomer C-1 or the monomer C-2 is preferable in terms of high polymerization reactivity and high heat resistance of the cured product.

However, Q ³ is a single bond or a divalent organic group, n is 0 or 1, Q ⁴ is a single bond or a divalent organic group, and R ³ and R ⁴ are each independently Is a hydrogen atom or a methyl group.
Examples of the divalent organic group in Q ³ and Q ⁴ include the same as the divalent organic group in Q ¹ and Q ² of the monomer A, and preferred embodiments are also the same.

  Examples of the monomer C-1 include the following monomers.

  Examples of the monomer C-2 include the following monomers.

  As another illustration of the monomer C, the following monomers are mentioned, for example.

(Other monomer)
As another monomer, a monomer having a ring structure having a carbon-carbon double bond in a carbon ring or a heterocycle (but excluding monomer A and monomer C), alkyl (meth) acrylate, alkyl vinyl ether, vinyl chloride And tetrafluoroethylene, trifluoroethylene, a perfluorovinyl ether which may have a functional group, and the like. The other monomers may be used alone or in combination of two or more.

(Percentage of each unit)
10-80 mol% is preferable among all the units which comprise this fluorine-containing polymer, and, as for the ratio of a monomer A unit, 20-60 mol% is more preferable. If the proportion of the monomer A unit is equal to or more than the lower limit of the above range, properties derived from fluorine atoms (water / oil repellency, releasability, electrical properties, etc.) are further excellent, and a cured product having even higher heat resistance is obtained. Can. If the proportion of the monomer A unit is equal to or less than the upper limit value of the above range, the effects of units other than the monomer A unit are unlikely to be impaired.

  10-50 mol% is preferable among all the units which comprise this fluorine-containing polymer, and, as for the ratio of a monomer B unit, 20-40 mol% is more preferable. If the proportion of the monomer B unit is equal to or more than the lower limit value of the above range, a cured product having higher hardness and further excellent adhesion to the substrate can be obtained. If the proportion of monomer B units is equal to or less than the upper limit value of the above range, the effects of units other than monomer B units are unlikely to be impaired.

  The proportion of monomer C units is preferably 0 to 60 mol%, and more preferably 20 to 60 mol%, of the total units constituting the present fluoropolymer. If the proportion of the monomer C unit is 20 mol% or more, a cured product having even higher heat resistance and hardness can be obtained. If the proportion of monomer C units is equal to or less than the upper limit value of the above range, the effects of units other than monomer C units are unlikely to be impaired.

  The proportion of the other monomer units is preferably 0 to 40 mol%, and more preferably 0 to 20 mol%, of all units constituting the present fluoropolymer. If the proportion of the other monomer units is equal to or less than the upper limit value of the above range, the effects of units other than the other monomer units are unlikely to be impaired.

  50 mass% or less is preferable among all the units which comprise this fluorine-containing polymer, and, as for the ratio of the unit formed by superposition | polymerization of the monomer which has a (meth) acryloyl group, 30 mass% or less is more preferable. If the ratio of the unit formed by polymerizing the monomer having a (meth) acryloyl group is not more than the upper limit value of the above range, a cured product with higher heat resistance and hardness can be obtained.

(Mechanism of action)
The fluorine-containing polymer described above has the monomer A unit, and thus is excellent in the characteristics derived from the fluorine atom (water / oil repellency, releasability, electrical characteristics, etc.).
Further, since the present fluorine-containing polymer has a monomer A unit, the proportion of units formed by polymerization of a monomer having a (meth) acryloyl group is smaller than that of a conventional fluorine-containing polymer. Therefore, it is hard to depolymerize by heating and a hardened | cured material with high heat resistance can be obtained.
Moreover, in this fluorine-containing polymer, since it has a monomer B unit, the hardened | cured material which is excellent in adhesiveness with a base material can be obtained.
And in this fluorine-containing polymer, since it has a monomer A unit and a monomer B unit, when heat processing is carried out, reaction of the crosslinkable group originating in a monomer B unit can fully be advanced, suppressing depolymerization. it can. Therefore, a cured product with high hardness can be obtained.

<Curable composition>
The curable composition of the present invention (hereinafter also referred to as "the present curable composition") contains the present fluorine-containing polymer.
The present curable composition may contain a crosslinking agent in that a cured product having higher heat resistance and hardness can be obtained.
The curable composition may contain a solvent.
The present fluorine-containing polymer may contain an additive, if necessary, as long as the effects of the present invention are not impaired.

(Crosslinking agent)
When the protected crosslinkable group in the monomer B unit of the fluorine-containing polymer is a blocked isocyanate group, as a crosslinking agent, a compound having an active hydrogen-containing group, a group capable of producing an active hydrogen-containing group by ring opening The compound etc. which it has are mentioned. A crosslinking agent may be used individually by 1 type, and may use 2 or more types together.

Examples of the compound having an active hydrogen-containing group include a monomer having an active hydrogen-containing group, a polymer having a monomer unit having an active hydrogen-containing group, and a polymer having an active hydrogen-containing group in a side chain or terminal.
As a monomer having an active hydrogen-containing group, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (4-benzoyl-3-hydroxyphenoxy) ethyl (meth) acrylate, Pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate , Dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrye , 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2,2-bis [4- {1- (meth) acryloxy-2-hydroxypropyl} phenyl] propane, 1-hexanethiol, 1-heptanethiol, 1 -Octanethiol, tert-octanethiol, 1-nonanethiol, 1-decanethiol, 1-undecanethiol, 1-dodecanethiol, 1-tetradecanethiol, 1-hexadecanethiol, 1-octadecanethiol, 1,4-butanedithiol 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 1,12-dodecane dithiol, 1,1 -Tetradecanedithiol, 1,16-hexadecanedithiol, 1,18-octadecanedithiol, 4,4-thiobisbenzenethiol, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate) Trimethylolpropane tris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3- (3-mercaptopropionate) Mercapto propionate), dipentaerythritol hexakis (3-mercapto propionate), etc. are mentioned.

  Polymers having an active hydrogen-containing group at the side chain or at the end include polyoxypropylene glycol, polyethylene glycol, polyoxypropylene sorbitol ether, epoxy resin obtained by copolymerizing bisphenol A and epichlorohydrin, bisphenol F and epichlorohydrin Epoxy resins copolymerized with phosphorus, epoxy resins copolymerized with novolak and epichlorohydrin, phenol resins, lignin extracts, polysaccharides, polyethyleneimines, aminoethylated (meth) acrylic resins, polysulfide resins, etc. may be mentioned.

An epoxy group, an oxetanyl group, etc. are mentioned as group which can produce | generate an active hydrogen containing group by ring-opening.
As a compound having a group capable of generating an active hydrogen-containing group by ring opening, a monomer having a group capable of generating an active hydrogen-containing group by ring opening, a monomer unit having a group capable of generating an active hydrogen-containing group by ring opening And the like.
Examples of the monomer having a group capable of generating an active hydrogen-containing group by ring opening include glycidyl (meth) acrylate, oxetanyl (meth) acrylate, 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, -Hydroxybutyl (meth) acrylate glycidyl ether, xylylene bis oxetane, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate, phenyl glycidyl ether, bisphenol A-diglycidyl ether, diglycidyl oxy Naphthalene etc. are mentioned.

(solvent)
As the solvent, a fluorine-containing compound (1H-tridecafluorohexane (manufactured by Asahi Glass Co., Ltd., Asahikaline (registered trademark) AC2000), 1,1,1,2,2,3,3,4,5,5,5) 6, 6-tridecafluorooctane (Asahi Glass Co., Ltd., Asahi Clean (registered trademark) AC6000), 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane (Asahi Glass Co., Ltd.) (Manufactured by Asahi Glass Co., Ltd., Asahi Glass Co., Ltd., Asahiklin (registered trademark) AK-225), 1,1,1,2,3,4,4,5,5,5 -Decafluoro-3-methoxy-2- (trifluoromethyl) pentane (manufactured by Asahi Glass Co., Ltd., Cytop (registered trademark) CT-solv 100 E), 1-methoxynonafluorobutane (3 M Made in Japan, Novec (registered trademark) 7100), 1-ethoxynonafluorobutane (manufactured by 3M Japan Ltd., Novec (registered trademark) 7200), 1,1,1,2,3,3-hexafluoro-4- (4) 1,1,2,3,3,3-Hexafluoropropoxy) Pentane (manufactured by 3M Japan, Novec (registered trademark) 7600), 2H, 3H-perfluoropentane (manufactured by Du Pont-Mitsui Fluorochemicals, Vertrel (registered trademark) ) XF), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octanol, 4,4,5,5,6,6, 7,7,8,8,9,9,9-tridecafluoro-1-nonanol, hexafluorobenzene, hexafluoro-2-propanol, 2,2,3,3,4,4,5,5 Octafluoro-1-pentanol, 1H, 1H, 7H-dodecafluoro-1-heptanol etc., non-fluorinated ketones (cyclopentanone, cyclohexanone, methyl amyl ketone, 2-butanone etc.) non-fluorinated esters (ethyl lactate, Methyl benzoate, ethyl benzoate, benzyl benzoate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol methyl ethyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene carbonate etc., non-fluorinated ether Diethylene glycol methyl ethyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethoxyethane, anisole, diglyme, triglyme etc. Be The solvents may be used alone or in combination of two or more.

(Additive)
Additives include surfactants, thixotropic agents, antifoaming agents, antioxidants, light stabilizers, antigelling agents, photosensitizers, resins, oligomers, carbon compounds, metal fine particles, metal oxide particles, A silane coupling agent, other organic compounds, etc. are mentioned.

(Mechanism of action)
Since the present curable composition described above contains the present fluorine-containing polymer, it is possible to obtain a cured product which is high in heat resistance and hardness and excellent in adhesion to a substrate.
As the application of the present curable composition, a water and oil repellent composition, a releasing agent composition, a composition for forming an insulating layer of an electronic device, a pixel for a display, a liquid repellent film such as a biochip and a microchemical chip, etc. A composition, an antifouling coating agent, a hard coating agent, a resin composition for imprinting, a composition for an optical material such as a lens array, and the like can be mentioned.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
Examples 1 to 5 are Examples, and Examples 6 to 8 are Comparative Examples.

<Physical properties and evaluation>
(Percentage of each unit)
The ¹ H-NMR spectrum of the polymer was measured using an FT-NMR apparatus (manufactured by JEOL Ltd., JNM-AL300). The proportion of each unit in the polymer was determined from the integral ratio of the peaks unique to each unit in the ¹ H-NMR spectrum of the polymer.

(Molecular weight and molecular weight distribution)
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer are standard polymethyl methacrylates of known molecular weight from chromatograms obtained by high-speed gel permeation chromatography (GPC) apparatus (HLC-8220, manufactured by Tosoh Corporation) It calculated | required using the calibration curve created using the sample. Molecular weight distribution (Mw / Mn) was determined from Mw and Mn.

(Adhesiveness)
JIS K 5600-5-6: 1999 "General test method for paints-Part 5: Mechanical properties of coating film-Section 6: Adhesion (cross-cut method)" (Corresponding International Standard ISO 2409: 1992) The adhesion of the cured film to the glass substrate was evaluated according to the following criteria.
Good: Peeling of the cured film is not observed.
Poor: Peeling of the cured film is observed.

(hardness)
According to JIS K 5600-5-4: 1999 "General test methods for paints-Part 5: Mechanical properties of coatings-Section 4: Scratch hardness (pencil method)" (Corresponding International Standard ISO 15184: 1996), The pencil hardness of the cured film was determined. The cured film having a pencil hardness of 3H or more has a sufficiently high hardness.

(Heat-resistant)
The thermal weight of the cured film peeled off from the glass substrate using a differential thermal thermogravimetry (TG-DTA) device (STA 7220 manufactured by Hitachi High-Tech Science Co., Ltd.) at a temperature of 10 ° C./min in a nitrogen atmosphere The temperature at which the reduction rate was 5% was determined.

(Water and oil repellency)
The contact angles of water and propylene glycol monomethyl ether acetate (PGMEA) on the surface of the cured film were measured with a fully automatic contact angle meter (DM-701, manufactured by Kyowa Interface Science Co., Ltd.). The liquid volume was 2.0 μL, and the contact angle after holding for 2000 milliseconds after dropping was measured. A cured film having a water contact angle of 100 degrees or more is excellent in water repellency. A cured film having a contact angle of 45 degrees or more of PGMEA is excellent in oil repellency.

<Raw material>
(monomer)
C6NB: 5-tridecafluorohexyl-2-norbornene,
C6 EtMI: N- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) maleimide,
C6 FMA: 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl methacrylate,
BM: 2- (O- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate (Karen MOI-BM (registered trademark), manufactured by Showa Denko KK),
HEMI: N- (2-hydroxyethyl) maleimide,
HMNB: 5-hydroxymethyl-2-norbornene,
HEMA: 2-hydroxyethyl methacrylate,
CyMI: N-cyclohexylmaleimide.

(solvent)
MEK: 2-butanone,
OFPO: 2,2,3,3,4,4,5,5-octafluoro-1-pentanol.
(Polymerization initiator)
V65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., V-65).

Synthesis Example 1
Charges of C6EtMI, BM and V65 shown in Table 1 were dissolved in 20 g of MEK and stirred at 50 ° C. for 24 hours under a nitrogen atmosphere. The reaction solution was added to 500 mL of hexane, and the precipitated solid was filtered with a polytetrafluoroethylene filter with a pore size of 3 μm to obtain a fluoropolymer. The proportions of the units of the fluoropolymer, Mw and Mw / Mn are shown in Table 2.

(Synthesis examples 2 to 8)
A fluorine-containing polymer was obtained in the same manner as in Synthesis Example 1 except that the types and amounts of monomers shown in Table 1 were changed. The proportions of the units of the fluoropolymer, Mw and Mw / Mn are shown in Table 2.

(Example 1)
0.1 g of the fluorine-containing polymer obtained in Synthesis Example 1, 0.1 g of the fluorine-containing polymer obtained in Synthesis Example 8 and 1.8 g of OFPO were placed in a glass vial and sufficiently stirred to obtain a uniform solution . The solution was filtered through a polytetrafluoroethylene filter with a nominal pore diameter of 0.20 μm to prepare a curable composition.

  A coating film of 1 μm thick of the curable composition was formed by spin coating on the surface of the cleaned 10 cm square glass substrate, and heated at 200 ° C. for 30 minutes using a hot plate to form a cured film. The cured film was evaluated for adhesion, hardness, heat resistance and water and oil repellency. The results are shown in Table 3.

(Examples 2 to 8)
A curable composition was prepared and a cured film was formed in the same manner as in Example 1 except that the type and amount of the fluorinated polymer shown in Table 3 were changed. The cured film was evaluated for adhesion, hardness, heat resistance and water and oil repellency. The results are shown in Table 3.

  The fluorine-containing polymer of the present invention comprises a water and oil repellent agent, a releasing agent, an insulating layer of an electronic device, a pixel for a display, a composition for forming a liquid repellent film such as a biochip and a microchemical chip, an antifouling coating agent and a hard coat It is useful as an agent, a resin composition for imprinting, a composition for optical materials such as a lens array, and the like.

Claims (8)

The fluorine-containing polymer which has a unit based on the following monomer A, and a unit based on the following monomer B.
Monomer A: a monomer having a ring structure having a carbon-carbon double bond in a carbon ring or a heterocycle and a group having an etheric oxygen atom between carbon atoms of a perfluoroalkyl group or a perfluoroalkyl group (provided that it is protected Excluding those having a crosslinkable group or an active hydrogen-containing group).
Monomer B: a monomer having a protected crosslinkable group. The fluorine-containing polymer according to claim 1, wherein the monomer A is a monomer represented by the following formula A-1 or a monomer represented by the following formula A-2.

However,
R ^f1 is a group having an etheric oxygen atom between carbon atoms of a perfluoroalkyl group or a perfluoroalkyl group,
Q ¹ is a single bond or a divalent organic group,
m is 0 or 1;
R ^f2 is a group having an etheric oxygen atom between carbon atoms of a perfluoroalkyl group or a perfluoroalkyl group,
Q ² is a single bond or a divalent organic group,
R ¹ and R ² are each independently a hydrogen atom or a methyl group.   The fluoropolymer according to claim 1 or 2, wherein the protected crosslinkable group in the monomer B is a blocked isocyanate group. The fluoropolymer according to any one of claims 1 to 3, further comprising a unit based on the following monomer C.
Monomer C: A monomer having a ring structure having a carbon-carbon double bond in a carbon ring or a heterocycle and an active hydrogen-containing group. The fluorine-containing polymer according to claim 4, wherein the monomer C is a monomer represented by the following formula C-1 or a monomer represented by the following formula C-2.

However,
Q ³ is a single bond or a divalent organic group,
n is 0 or 1 and
Q ⁴ is a single bond or a divalent organic group,
R ³ and R ⁴ are each independently a hydrogen atom or a methyl group.   The proportion of a unit formed by polymerizing a monomer having a (meth) acryloyl group is 50% by mass or less among all the units constituting the fluorine-containing polymer. The fluorine-containing polymer as described.   The curable composition containing the fluorine-containing polymer as described in any one of Claims 1-6.   The curable composition according to claim 7, which is a water and oil repellent composition.