Photocurable composition containing fluorine-based polymer

文档序号：1661331 发布日期：2019-12-27 浏览：30次中文

阅读说明：本技术 含有氟系聚合物的光硬化性组合物 (Photocurable composition containing fluorine-based polymer ) 是由田仲拓郎安藤达也于 2018-05-17 设计创作，主要内容包括：本发明提供一种透明性、耐磨耗性优异,可有效用作眼镜、太阳眼镜等的光学构件或可携式电子设备的显示器的保护涂敷剂的光硬化性组合物。一种光硬化性组合物,含有氟系聚合物(A)、氨基甲酸酯(甲基)丙烯酸酯(B)及光聚合引发剂(C),氟系聚合物(A)为包含：源自在分子内具有一个加成聚合性官能基的氟倍半硅氧烷的构成单元A-1、源自加成聚合性单体的在侧链含有具有聚合性不饱和键的基团的构成单元A-2的聚合物,所述构成单元A-1源自下述式(1)所表示的氟倍半硅氧烷。(式中,Rf1～Rf7分别独立地表示任意的亚甲基可经氧取代的碳数1～20的氟烷基；至少一个氢经氟或三氟甲基取代的碳数6～20的氟芳基；或者芳基中的至少一个氢经氟或三氟甲基取代的碳数7～20的氟芳基烷基,A1表示加成聚合性官能基)。<Image he="406" wi="700" file="DDA0002273051580000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention provides a photo-curing composition which has excellent transparency and abrasion resistance and can be effectively used as an optical member of glasses, sunglasses and the like or a protective coating agent of a display of a portable electronic device. A photocurable composition comprising a fluorine-containing polymer (A), a urethane (meth) acrylate (B) and a photopolymerization initiator (C), wherein the fluorine-containing polymer is polymerizedThe substance (A) comprises: a polymer which is derived from a constituent unit A-1 of a fluorosilsesquioxane having one addition polymerizable functional group in the molecule and a constituent unit A-2 of an addition polymerizable monomer having a group having a polymerizable unsaturated bond in a side chain, wherein the constituent unit A-1 is derived from a fluorosilsesquioxane represented by the following formula (1). (wherein Rf 1-Rf 7 independently represent fluoroalkyl groups having 1-20 carbon atoms in which any methylene group may be substituted by oxygen; fluoroaryl groups having 6-20 carbon atoms in which at least one hydrogen is substituted by fluorine or trifluoromethyl; fluoroarylalkyl groups having 7-20 carbon atoms in which at least one hydrogen is substituted by fluorine or trifluoromethyl; and A1 represents an addition polymerizable functional group).)

1. A photocurable composition comprising a fluorine-containing polymer (A), a urethane (meth) acrylate (B) and a photopolymerization initiator (C),

the fluorine-containing polymer (A) comprises: a polymer comprising a constituent unit A-1 derived from a fluorosilsesquioxane having one addition polymerizable functional group in the molecule represented by the formula (1) and a constituent unit A-2 derived from an addition polymerizable monomer and having a group having a polymerizable unsaturated bond in the side chain,

[ solution 1]

(in the formula, R_f ¹～R_f ⁷Independently represent fluoroalkyl groups having 1 to 20 carbon atoms in which any methylene group may be substituted by oxygen; at least one fluorine aryl group with 6-20 carbon atoms, wherein hydrogen is substituted by fluorine or trifluoromethyl; or a fluoroarylalkyl group having 7 to 20 carbon atoms, wherein at least one hydrogen in the aryl group is substituted by fluorine or trifluoromethyl, A¹Represents an addition polymerizable functional group).

2. The photohardening composition according to claim 1, wherein R in formula (1)_f ¹～R_f ⁷Each independently selected from the group consisting of 3,3, 3-trifluoropropyl, 3,3,4,4, 4-pentafluorobutyl, 3,3,4,4,5,5,6,6, 6-nonafluorohexyl, tridecafluoro-1, 1,2, 2-tetrahydrooctyl, heptadecafluoro-1, 1,2, 2-tetrahydrodecyl, heneicosyl-1, 1,2, 2-tetrahydrododecyl, pentacosyl-1, 1,2, 2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, and α, α, α -trifluoromethylphenyl.

3. The photohardening composition according to claim 1, wherein R in formula (1)_f ¹～R_f ⁷Each independently selected from the group consisting of 3,3, 3-trifluoropropyl, 3,3,4,4,5,5,6,6, 6-nonafluorohexyl, and tridecafluoro-1, 1,2, 2-tetrahydrooctyl.

4. The photocurable composition according to claim 1, wherein the group having a polymerizable unsaturated bond of the constituent unit a-2 is a (meth) acrylic group bonded to a main chain via a urethane bond.

5. The photocurable composition according to any one of claims 1 to 4, wherein the fluorine-based polymer (A) is a polymer further comprising a constituent unit A-3 derived from an organopolysiloxane having an addition polymerizable functional group represented by the following formula (2),

[ solution 2]

(wherein n is an integer of 1 to 1,000; R¹And R²Each independently is methyl, phenyl or 3,3, 3-trifluoropropyl; r³And R⁴Each independently is methyl or phenyl; r⁵Selected from the group consisting of methyl, ethyl, propyl, butyl, isobutyl, phenyl, 3,3, 3-trifluoropropyl, 3,3,4,4, 4-pentafluorobutyl, 3,3,4,4,5,5,6,6, 6-nonafluorohexyl, tridecafluoro-1, 1,2, 2-tetrahydrooctyl, heptadecafluoro-1, 1,2, 2-tetrahydrodecyl, heneicosano-1, 1,2, 2-tetrahydrododecyl, pentacosano-1, 1,2, 2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, and α, α, α -trifluoromethylphenyl; a. the²Is an addition polymerizable functional group).

6. The photohardening composition according to claim 5, wherein R in the formula (2)¹、R²、R³And R⁴Are each simultaneously methyl, A²Is (meth) acrylic acid group.

7. The photocurable composition according to any one of claims 1 to 6, further comprising inorganic fine particles (D).

8. The photocurable composition according to claim 7, wherein said inorganic fine particles (D) are surface-modified colloidal silica.

9. The photocurable composition according to any one of claims 1 to 8, wherein the urethane (meth) acrylate (B) is a 6-functional urethane (meth) acrylate having a viscosity of 20,000 mPas or less at 40 ℃.

10. The photocurable composition according to claim 9, wherein the urethane (meth) acrylate (B) is contained in an amount of 50 to 98 wt% based on 100 wt% of the total solid content.

11. A cured film obtained by curing the photocurable composition according to any one of claims 1-10.

12. A cured film obtained by curing a photocurable composition comprising a fluorine-containing polymer (A), a 6-functional urethane (meth) acrylate (B) having a viscosity of 20,000 mPas or less at 40 ℃, a photopolymerization initiator (C), and inorganic fine particles (D),

the photocurable composition has a delta haze of 3 or less in evaluation method 1,

the fluorine-containing polymer (A) comprises: a polymer derived from a constituent unit A-1 of a fluorosilsesquioxane having one addition polymerizable functional group in the molecule represented by formula (1), a constituent unit A-2 derived from an addition polymerizable monomer and having a group having a polymerizable unsaturated bond in the side chain, and a constituent unit A-3 derived from an organopolysiloxane having an addition polymerizable functional group represented by formula (2),

in the formula (1), R_f ¹～R_f ⁷Each independently selected from the group consisting of 3,3, 3-trifluoropropyl, 3,3,4,4,5,5,6,6, 6-nonafluorohexyl, and tridecafluoro-1, 1,2, 2-tetrahydrooctyl; a. the¹In order to add a polymerizable functional group to the polymer,

the group having a polymerizable unsaturated bond of A-2 is a (meth) acrylic group bonded to the main chain via a urethane bond,

in the formula (2), n is an integer of 1 to 1,000, R¹、R²、R³And R⁴Are each simultaneously methyl, R⁵Is butyl, A²Is a (meth) acrylic group;

[ solution 3]

[ solution 4]

[ evaluation method 1]

Forming a cured film having a thickness of 5 μm containing the photocurable composition on a polyethylene terephthalate (PET) film substrate having a thickness of 100 μm;

the cured film-attached polyethylene terephthalate was measured for haze (%), according to american society for testing and materials D1044, and after taber abrasion test was performed in a state where a load of 1kg (9.8N) was applied, haze (%) was measured, according to american society for testing and materials D1044, the difference Δ haze (%) was determined;

Δ haze (%) - (haze (%) before taber abrasion test) after taber abrasion test in a state where a load of 1kg (9.8N) was applied.

13. A laminate comprising the hardened film of claim 11 or 12.

14. An optical member comprising the cured film according to claim 11 or 12 or the laminate according to claim 13.

Technical Field

The present invention relates to a photocurable composition containing a fluorine-containing polymer. The present invention also relates to a cured film obtained from the photocurable composition containing a fluoropolymer.

Background

Conventionally, various surface modifying agents have been studied, which form a coating film on the surface of various substrates to provide protection, water repellency, oil repellency, insulation, non-adhesiveness, stain resistance, and the like to the substrates. As a method, for example, there is a method of improving water repellency by applying a coating material containing a fluororesin, a silicone resin, or the like to a substrate.

For example, patent document 1 proposes a coating film containing a silicone-containing fluorine-based copolymer or a composition containing the silicone-containing fluorine-based copolymer, in which the number of Si atoms and the number of F atoms present on the surface of the coating film are in a certain ratio as measured by X-ray photoelectron spectroscopy (XPS).

Patent document 2 discloses the following: an addition copolymer containing, as essential components, a constituent unit derived from a fluorosilsesquioxane having one addition polymerizable functional group in the molecule, a constituent unit derived from an organopolysiloxane having an addition polymerizable functional group, and a constituent unit derived from an addition polymerizable monomer having a group having a polymerizable unsaturated bond in a side chain has excellent water repellency and oil repellency, and is effectively used as a surface modifier.

Further, patent document 3 proposes an active energy ray-curable composition containing a fluorine-containing polymerizable resin containing a polymer obtained as follows: a polymer obtained by copolymerizing a polymerizable unsaturated monomer having a fluorinated alkyl group having 4-6 carbon atoms, a polymerizable unsaturated monomer having a silicone group, and a polymerizable unsaturated monomer having a reactive functional group as essential monomer components is reacted with a compound containing a functional group reactive with the reactive functional group and a polymerizable unsaturated group.

Disclosure of Invention

Problems to be solved by the invention

The cured film obtained from the active energy ray-curable composition proposed in patent document 2 has characteristics of repelling contamination by a universal pen or the like and having good wiping properties.

In recent years, with the miniaturization and thinning of electronic devices, there has been an increasing demand for coating materials for protecting displays thereof, and particularly, for more comfortable use of displays of portable electronic devices such as smart phones and tablet panels, which are often used outdoors, it has been required to protect the displays from contamination or damage at a high level. Further, optical members such as spectacles and sunglasses have been increasingly thinned and improved in performance, and further demands for transparency and abrasion resistance have been made on protective materials.

Accordingly, an object of the present invention is to provide a resin composition and a coating material for a coating layer which can be used for displays of portable electronic devices such as smart phones and tablet, optical members such as glasses and sunglasses, has high transparency, can be sufficiently protected from contamination or damage, and has high abrasion resistance.

Means for solving the problems

The present inventors have made extensive studies from the above-mentioned viewpoints and as a result, have found that a cured film obtained by curing a composition containing a specific fluorine-based polymer (a) and a urethane (meth) acrylate (B) in combination has excellent transparency and abrasion resistance, and have completed the present invention.

That is, the embodiment of the present invention includes the following configurations.

[1] A photocurable composition comprising a fluorine-containing polymer (A), a urethane (meth) acrylate (B) and a photopolymerization initiator (C),

[ solution 1]

[2]According to [1]The photo-curable composition, wherein R in the formula (1)_f ¹～R_f ⁷Each independently selected from the group consisting of 3,3, 3-trifluoroPropyl, 3,4,4, 4-pentafluorobutyl, 3,4,4,5,5,6,6, 6-nonafluorohexyl, tridecafluoro-1, 1,2, 2-tetrahydrooctyl, heptadecafluoro-1, 1,2, 2-tetrahydrodecyl, heneicosyl-1, 1,2, 2-tetrahydrododecyl, pentacosyl-1, 1,2, 2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, and α, α, α -trifluoromethylphenyl.

[3]According to [1]The photo-curable composition, wherein R in the formula (1)_f ¹～R_f ⁷Each independently selected from the group consisting of 3,3, 3-trifluoropropyl, 3,3,4,4,5,5,6,6, 6-nonafluorohexyl, and tridecafluoro-1, 1,2, 2-tetrahydrooctyl.

[4] The photocurable composition according to any one of [1] to [3], wherein the group having a polymerizable unsaturated bond of the constituent unit A-2 is a (meth) acrylic group bonded to the main chain via a urethane bond.

[5] The photocurable composition according to any one of [1] to [4], wherein the fluorine-based polymer (A) is a polymer further comprising a constituent unit A-3 derived from an organopolysiloxane having an addition polymerizable functional group represented by the following formula (2).

[ solution 2]

[6]According to [5]]The photo-curable composition, wherein R in the formula (2)¹、R²、R³And R⁴Are each simultaneously methyl, A²Is (meth) acrylic acid group.

[7] The photocurable composition according to any one of [1] to [6], further comprising inorganic fine particles (D).

[8] The photocurable composition according to [7], wherein the inorganic fine particles (D) are colloidal silica having a modified surface.

[9] The photocurable composition according to any one of [1] to [8], wherein the urethane (meth) acrylate (B) is a 6-functional urethane (meth) acrylate having a viscosity of 20,000 mPas or less at 40 ℃.

[10] The photocurable composition according to [9], wherein the urethane (meth) acrylate (B) is contained in an amount of 50 to 98 wt% based on 100 wt% of the total solid content.

[11] A cured film obtained by curing the photocurable composition according to any one of [1] to [10 ].

[12] A cured film obtained by curing a photocurable composition comprising a fluorine-containing polymer (A), a 6-functional urethane (meth) acrylate (B) having a viscosity of 20,000 mPas or less at 40 ℃, a photopolymerization initiator (C), and inorganic fine particles (D),

the photocurable composition has a Δ haze of 3 or less in evaluation method 1.

The fluorine-containing polymer (A) comprises: a polymer derived from a constituent unit A-1 of a fluorosilsesquioxane having one addition polymerizable functional group in the molecule represented by formula (1), a constituent unit A-2 derived from an addition polymerizable monomer and having a group having a polymerizable unsaturated bond in the side chain, and a constituent unit A-3 derived from an organopolysiloxane having an addition polymerizable functional group represented by formula (2),

in the formula (1), R_f ¹～R_f ⁷Each independently is 3,3, 3-trifluoropropyl, 3,3,4,4,5,5,6,6, 6-nonafluorohexyl, or tridecafluoro-1, 1,2, 2-tetrahydrooctyl; a. the¹In order to add a polymerizable functional group to the polymer,

the group having a polymerizable unsaturated bond of A-2 is a (meth) acrylic group bonded to the main chain via a urethane bond,

in the formula (2), n is an integer of 1 to 1,000, R¹、R²、R³And R⁴Are each simultaneously methyl, R⁵Is butyl, A²Is (meth) acrylic acid group.

[ solution 3]

[ solution 4]

[ evaluation method 1]

A cured film having a thickness of 5 μm comprising the photocurable composition was formed on a polyethylene terephthalate (PET) film substrate having a thickness of 100 μm.

The haze (%) of the cured film-attached PET was measured according to American Society for Testing and Materials (ASTM) D1044, and the difference Δ haze (%) was determined by measuring the haze (%) of the cured film-attached PET in accordance with ASTM D1044 after a Taber abrasion test was performed under a load of 1kg (9.8N).

Delta haze (%) (haze (%) after taber abrasion test under a load of 1kg (9.8N) applied thereto) (haze (%) before taber abrasion test)

[13] A laminate comprising the cured film according to [11] or [12 ].

[14] An optical member comprising the cured film according to [11] or [12], or the laminate according to [13 ].

ADVANTAGEOUS EFFECTS OF INVENTION

The cured film obtained from the photocurable composition containing a fluoropolymer according to the present invention has excellent transparency and abrasion resistance.

Detailed Description

The following is a detailed description of the embodiments of the present invention, but the following description is an example (representative example) of the embodiments of the present invention, and the present invention is not limited to these contents at all. In addition, the embodiments of the present invention can be combined as appropriate.

In the present invention, addition-polymerizable means addition-polymerizable, addition-polymerizable monomer means addition-polymerizable monomer, and addition-polymerizable functional group means addition-polymerizable functional group.

A photocurable composition according to an embodiment of the present invention (hereinafter also referred to as a composition of the present invention) includes a fluorine-based polymer (a) (hereinafter also referred to as a polymer a or a component (a)), a urethane (meth) acrylate (B) (hereinafter also referred to as a component (B)), and a photopolymerization initiator (C) (hereinafter also referred to as a component (C)), and the fluorine-based polymer (a) includes: a polymer which is derived from a constituent unit A-1 of a fluorosilsesquioxane having one addition polymerizable functional group in the molecule and a constituent unit A-2 of an addition polymerizable monomer having a group having a polymerizable unsaturated bond in a side chain, wherein the constituent unit A-1 is derived from a fluorosilsesquioxane represented by the following formula (1). The term "derived" means a polymerized residue when each monomer constitutes the fluorine-containing polymer (A).

[ solution 5]

When "the mole fraction (%) of the constituent unit a-1 in the fluorinated polymer (a)" is "a", and "the mole fraction (%) of the constituent unit a-2 in the polymer" is "b", and "the mole fraction (%) of the constituent unit a-3 in the polymer, which will be described later," is "c", and "the mole fraction (%) of the constituent unit D (constituent units other than the constituent units a-1 to a-3) in the polymer, which will be described later," is "D", 0 < a < 100, 0 < b < 100, 0 < c < 100, 0 < D < 100, and a + b + c + D < 100 are satisfied, respectively.

The fluorine-based polymer (a) of the present invention is preferably obtained, for example, by: the polymer is obtained by copolymerizing an addition polymerizable monomer (α) having a fluorine atom and an addition polymerizable monomer having a functional group into which a group having a polymerizable unsaturated bond can be introduced, and introducing the group having a polymerizable unsaturated bond into the precursor through the functional group.

< fluoropolymer (A) >

Description of constituent Unit A-1

< Fluorosilsesquioxane (α) >, having an addition polymerizable functional group in the molecule

The molecular structure of the fluorine silsesquioxane has a silsesquioxane skeleton. The silsesquioxane is [ (R-SiO)_1.5)_n]The general term of the polysiloxane (R is an optional substituent). The structure of the silsesquioxane is generally classified into a random structure, a ladder structure, a cage structure according to its Si-O-Si skeleton. Further, the cage structure is classified as T₈Type, T₁₀Type, T₁₂Type, etc. Wherein the fluorosilsesquioxane used in the present invention has T₈Type [ (R-SiO)_1.5)₈]The cage structure of (1).

The fluorosilsesquioxane is characterized by having one addition polymerizable functional group. Namely, silsesquioxane [ (R-SiO)_1.5)_n]One of R in (2) is an addition polymerizable functional group.

Examples of the addition polymerizable functional group include a group having a radical polymerizable functional group of a terminal olefin type or an internal olefin type; a group having a cationically polymerizable functional group such as vinyl ether and propenyl ether; and groups having an anionic polymerizable functional group such as a vinylcarboxyl group and a cyanoacryloyl group, and preferably a radical polymerizable functional group is exemplified.

The radical polymerizable functional group is not particularly limited as long as it is a group that undergoes radical polymerization, and includes, for example, a methacryloyl group, an acryloyl group, an allyl group, a styryl group, an α -methylstyrene group, a vinyl ether, a vinyl ester, an acrylamide, a methacrylamide, an N-vinylamide, a maleate, a fumarate, an N-substituted maleimide, and the like, and among them, a group having a (meth) acrylic group or a styryl group is preferable. Here, the (meth) acrylic group is a general term for the acrylic group and the methacrylic group, and means an acrylic group and/or a methacrylic group. The same applies hereinafter.

Examples of the radical polymerizable functional group having a (meth) acrylic group include groups represented by the following formula (3).

In the formula (3), Y¹Represents an alkylene group having 2 to 10 carbon atoms, preferably an alkylene group having 2 to 6 carbon atoms, and more preferably an alkylene group (propylene group) having 3 carbon atoms. In addition, R⁶Represents hydrogen, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably hydrogen or an alkyl group having 1 to 3 carbon atoms, and more preferably hydrogen or methyl. Here, the alkyl group having 1 to 5 carbon atoms may be either linear or branched.

Examples of the radical polymerizable functional group having a styryl group include groups represented by the following formula (5). In the formula (5), Y²Represents a single bond or an alkylene group having 1 to 10 carbon atoms, preferably a single bond or an alkylene group having 1 to 6 carbon atoms, more preferably a single bond or an alkylene group having 1 or 2 carbon atoms, and particularly preferably a single bond or an alkylene group (ethylene group) having 2 carbon atoms. In addition, the vinyl group is bonded to any one of the carbons of the benzene ring, preferably to Y²But is on the para-carbon.

[ solution 6]

In the fluorosilsesquioxane, R other than the addition polymerizable functional group is fluoroalkyl, fluoroarylalkyl, and/or fluoroaryl.

The fluoroalkyl group may be linear or branched. The carbon number of the fluoroalkyl group is 1 to 20, preferably 3 to 14. Further, any methylene group of the fluoroalkyl group may be substituted with oxygen. Here, the methylene group contains-CH₂-, -CFH-or-CF₂-. That is, "any methylene group may be substituted with oxygen" means-CH₂-, -CFH-or-CF₂-may be substituted by-O-. Wherein, in the fluoroalkyl group, two oxygens do not undergo a bond (-O-). That is, the fluoroalkyl group may have an ether bond. In addition, in a preferred fluoroalkyl group, a methylene group adjacent to Si is not substituted with oxygen, and the end opposite to Si is CF₃. Further, compared with-CH₂-or-CFH-substituted by oxygen, preferably-CF₂-substituted by oxygen. Preferred examples of the fluoroalkyl group include: 3,3, 3-trifluoropropyl group, 3,3,4,4, 4-pentafluorobutyl group, 3,3,4,4,5,5,6,6, 6-nonafluorohexyl group, tridecafluoro-1, 1,2, 2-tetrahydrooctyl group, heptadecafluoro-1, 1,2, 2-tetrahydrododecyl group, heneicosano-1, 1,2, 2-tetrahydrododecyl group, pentacosano-1, 1,2, 2-tetrahydrotetradecyl group, (3-heptafluoroisopropoxy) propyl group and the like. Among them, a perfluoroalkylethyl group can be preferably exemplified, and a group via-CH may be also exemplified₂-CH₂A fluoroalkyl group bonded thereto, which may also be through-CH₂-a fluoroalkyl group bonded thereto.

The fluoroarylalkyl group is an alkyl group containing an aryl group containing fluorine, and the number of carbon atoms is preferably 7 to 20, more preferably 7 to 10. The fluorine contained is preferably one in which one or two or more hydrogens of the aryl group are substituted with fluorine or trifluoromethyl. Examples of the aryl moiety include heteroaryl groups in addition to phenyl groups and naphthyl groups, and examples of the alkyl moiety include methyl groups, ethyl groups, and propyl groups.

The fluoroaryl group is a group in which one or two or more hydrogens of an aryl group are substituted with fluorine or a trifluoromethyl group, and the number of carbons is preferably 6 to 20, more preferably 6. Examples of the aryl group include heteroaryl groups in addition to phenyl groups and naphthyl groups. Specifically, a fluorophenyl group such as a pentafluorophenyl group or a trifluoromethylphenyl group is exemplified.

Among the fluoroalkyl groups, fluoroarylalkyl groups, or fluoroaryl groups contained in the fluorosilsesquioxane, preferred groups are fluoroalkyl groups, and more preferred is a perfluoroalkylethyl group.

As mentioned above, the fluorosilsesquioxanes have T₈A structure of type (II) having one addition polymerizable functional group, and R_f ¹～R_f ⁷Each independently has a fluoroalkyl group, a fluoroarylalkyl group, and/or a fluoroaryl group, and the fluorosilsesquioxane is represented by the following structural formula (1).

[ solution 7]

In the formula (1), A¹For addition polymerization to form functional groups, preferably the free-radically polymerizable functional groups, R_f ¹～R_f ⁷Independently represent fluoroalkyl groups having 1 to 20 carbon atoms in which any methylene group may be substituted with oxygen; at least one fluorine aryl group with 6-20 carbon atoms, wherein hydrogen is substituted by fluorine or trifluoromethyl; or a fluoroarylalkyl group having 7 to 20 carbon atoms wherein at least one hydrogen in the aryl group is substituted with fluorine or trifluoromethyl, R_f ¹～R_f ⁷May be different groups or may be the same group.

R in the formula (1)_f ¹～R_f ⁷Preferably, R is independently selected from the group consisting of 3,3, 3-trifluoropropyl, 3,3,4,4, 4-pentafluorobutyl, 3,3,4,4,5,5,6,6, 6-nonafluorohexyl, tridecafluoro-1, 1,2, 2-tetrahydrooctyl, heptadecafluoro-1, 1,2, 2-tetrahydrodecyl, heneicosano-1, 1,2, 2-tetrahydrododecyl, pentacosano-1, 1,2, 2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, and α, α, α -trifluoromethylphenyl_f ¹～R_f ⁷More preferably, each is independently selected from the group consisting of 3,3, 3-trifluoropropyl, 3,3,4,4,5,5,6,6, 6-nonafluorohexyl, and tridecafluoro-1, 1,2, 2-tetrahydrooctyl.

The fluorosilsesquioxane (. alpha.) having one addition polymerizable functional group in the molecule can be synthesized, for example, with reference to Japanese patent laid-open No. 2004-123698.

Description of constituent Unit A-2

< addition polymerizable monomer having functional group capable of introducing group having polymerizable unsaturated bond >

As described above, with respect to the polymer (a) having a group having a polymerizable unsaturated bond in a side chain, a polymer having a functional group into which a group having a polymerizable unsaturated bond can be introduced can be obtained as a precursor. Examples of the functional group capable of introducing a group having a polymerizable unsaturated bond include a group having an active hydrogen and a monovalent functional group containing a cyclic ether. The active hydrogen is hydrogen which is present in a hydrogen atom in a molecule of an organic compound and is bonded to an atom having an electronegativity of not less than carbon (for example, a nitrogen atom, a sulfur atom, and an oxygen atom). Therefore, a preferred precursor for obtaining the polymer (a) is a precursor which contains a polymer having a group having active hydrogen, and the polymer used in the composition of the present invention is preferably obtained together with the organopolysiloxane (γ) having an addition polymerizable functional group described later, using as essential components the fluorosilsesquioxane (α) having one addition polymerizable functional group in the molecule, and the addition polymerizable monomer (∈) containing a monovalent functional group having an active hydrogen group or a cyclic ether.

Examples of the group having active hydrogen include-OH, -SH, -COOH, -NH and-NH₂、-CONH₂、-NHCONH-、-NHCOO-、Na⁺[CH(COOC₂H₅)]、-CH₂NO₂、-OOH、-SiOH、-B(OH)₂and-SH, etc., are preferably carboxyl, amino, hydroxyl, and more preferably hydroxyl. The addition polymerizable monomer (e) containing a group having an active hydrogen may be a compound containing a group having an active hydrogen and an addition polymerizable double bond in the molecule, and may be any of a vinyl compound, a vinylidene compound, and a vinylidene compound containing a group having an active hydrogen. Acrylic acid derivatives or styrene derivatives containing groups having active hydrogen are preferred.

Examples of the monovalent functional group containing a cyclic ether include glycidyl groups, epoxycyclohexyl groups, and oxetanyl groups.

As addition polymerizable monomers containing a group having an active hydrogen, there can be mentioned monomers disclosed in Japanese patent laid-open No. Hei 9-208681, Japanese patent laid-open No. 2002-348344 and Japanese patent laid-open No. 2006-158961.

Specifically, the following monomers can be mentioned.

Examples of the carboxyl group-containing vinyl monomer include: (meth) acrylic acid, maleic acid (anhydride), monoalkyl maleate, fumaric acid, monoalkyl fumarate, crotonic acid, itaconic acid, monoalkyl itaconate, glycol monoether of itaconic acid, citraconic acid, monoalkyl citraconate, hexadecyl (meth) acrylate, cinnamic acid, and the like.

As the hydroxyl group-containing vinyl monomer, a hydroxyl group-containing monofunctional vinyl monomer, a hydroxyl group-containing polyfunctional vinyl monomer, and the like can be used. As the monofunctional vinyl monomer having a hydroxyl group, a vinyl monomer having one vinyl group can be used, and examples thereof include: hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, HEMA, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotonol, 1-buten-3-ol, 2-buten-1, 4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether (2-acryloyloxyethanol), 16-hydroxyhexadecane methacrylate, sucrose allyl ether, and the like. As the hydroxyl group-containing polyfunctional vinyl monomer, a vinyl monomer having a plurality of vinyl groups can be used, and examples thereof include: glycerol di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, diglycerin tri (meth) acrylate, sorbitan tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tetraglycerol penta (meth) acrylate, glycerol di (meth) allyl ether, trimethylolpropane di (meth) allyl ether, pentaerythritol tri (meth) allyl ether, diglycerol tri (meth) allyl ether, sorbitan tri (meth) allyl ether, dipentaerythritol penta (meth) allyl ether, tetraglycerol penta (meth) allyl ether, and the like.

Examples of the amino group-containing vinyl monomer include: aminoethyl (meth) acrylate, aminoisopropyl (meth) acrylate, aminobutyl (meth) acrylate, aminohexyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, crotylamine, aminostyrene, methyl alpha-acetamidoacrylate, N-allylphenylenediamine, 16-methacryloylhexadecylamine, and the like.

In addition, examples of the addition polymerizable monomer of the (meth) acrylic acid derivative having a monovalent functional group containing a cyclic ether include: epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate; alicyclic epoxy group-containing (meth) acrylates such as methyl 3, 4-epoxycyclohexyl (meth) acrylate; oxetanyl group-containing (meth) acrylates such as 3-ethyl-3- (meth) acryloyloxymethyloxetane; dioxolane-containing (meth) acrylates such as 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1, 3-dioxolane, and the like.

Description of constituent Unit A-3

< organopolysiloxane (. gamma.) > -having addition polymerizable functional group

In the present invention, it is preferable that the fluorine-containing polymer (a) further contains a constituent unit a-3 derived from an organopolysiloxane (γ) having an addition-polymerizable functional group represented by the following formula (2).

[ solution 8]

In the formula (2), n is an integer of 1-1,000; r¹And R²Each independently is methyl, phenyl or 3,3, 3-trifluoropropyl; r³And R⁴Each independently is methyl or phenyl; r⁵Is methyl, ethyl, propyl, butyl, isobutyl, phenyl, 3,3, 3-trifluoropropyl, 3,3,4,4, 4-pentafluorobutyl, 3,3,4,4,5,5,6,6, 6-nonafluorohexyl, tridecafluoro-1, 1,2, 2-tetrahydrooctyl, heptadecafluoro-1, 1,2, 2-tetrahydrodecyl, heneicosano-1, 1,2, 2-tetrahydrododecyl, pentacosano-11,2, 2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, or α, α, α -trifluoromethylphenyl; a. the²Is an addition polymerizable functional group.

In the formula (2), A is preferably A²Is a radical polymerizable functional group, more preferably A²Contains a (meth) acrylic group or a styryl group, and is more preferably A²Is any one of the following formulae (3), (4) and (5).

In addition, from the viewpoint of lubricity, R in formula (2) is more preferable¹、R²、R³And R⁴Are each simultaneously methyl, A²Is (meth) acrylic acid group. In addition, R⁵Preferably a butyl group. n is preferably 50 to 100.

[ solution 9]

In the formula (3), Y¹R represents an alkylene group having 2 to 10 carbon atoms⁶Represents hydrogen, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms, wherein R in the formula (4)⁷Represents hydrogen, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms, X₁Represents an alkylene group having 2 to 20 carbon atoms, Y is-OCH₂CH₂-、-OCH(CH₃)CH₂-, or-OCH₂CH(CH₃) P is an integer of 0 to 3, and in formula (5), Y²Represents a single bond or an alkylene group having 1 to 10 carbon atoms. Here, the alkyl group having 1 to 5 carbon atoms may be either linear or branched.

In the present invention, in the formula (3), Y¹Preferably C2-C6 alkylene, R⁶Preferably hydrogen or methyl, in formula (4), X₁Is preferably-CH₂CH₂CH₂-, Y is preferably-OCH₂CH₂-, p is preferably 0 or 1, R⁷Preferably hydrogen or methyl, in formula (5), Y²Preferably a single bond or an alkylene group having 1 or 2 carbon atoms. In addition, a combination of preferable embodiments of the respective organic groups is included in the present invention.

Examples of the organopolysiloxane (γ) that can be preferably used in the present invention include selamela (silane) FM0711 (manufactured by JNC), selamela (silane) FM0721 (manufactured by JNC), selamela (silane) FM0725 (manufactured by JNC), selamela (silane) TM0701 (manufactured by JNC), and selamela (silane) TM0701 070 0701T (manufactured by JNC).

Description of constituent Unit A-4

< optional addition polymerizable monomer (. delta.) >)

In the precursor of the fluorine-based polymer (a) used in the present invention, in addition to the addition polymerizable monomer (α), the addition polymerizable monomer (e) and the addition polymerizable monomer (γ), the addition polymerizable monomer (δ) other than the monomer (α), the monomer (β) and the monomer (γ) may be used in combination at an arbitrary ratio as needed, in order to control compatibility with a resin, leveling property, content of a group having a polymerizable unsaturated bond in a copolymer, and the like.

Examples of the addition polymerizable monomer (δ) not containing a group having an active hydrogen include a (meth) acrylic compound having one addition polymerizable double bond and not containing a group having an active hydrogen, and a styrene compound having one addition polymerizable double bond and not containing a group having an active hydrogen. Specific examples of the (meth) acrylic compound include: alkyl (meth) acrylates such as methyl (meth) acrylate, MMA, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate; aryl (meth) acrylates such as phenyl (meth) acrylate and toluyl (meth) acrylate; arylalkyl (meth) acrylates such as benzyl (meth) acrylate; alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, and 3-methoxybutyl (meth) acrylate; ethylene oxide adducts of (meth) acrylic acid, and the like.

Further, examples of the (meth) acrylic compound having one addition polymerizable double bond and not containing a group having an active hydrogen include (meth) acrylic compounds having a silsesquioxane skeleton. Specific examples of the (meth) acrylic compound having a silsesquioxane skeleton include: 3- (3,5,7,9,11,13, 15-heptaethylpentacyclic [9.5.1.1 ]^3,9.1⁵ ^,15.1^7,13]Octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13, 15-heptaisobutylpentacyclo [9.5.1.1^3,9.1^5,15.1^7,13]Octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13, 15-heptaisooctyl pentacyclic [9.5.1.1 ]^3,9.1^5,15.1^7,13]Octa-siloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13, 15-heptacyclopentyl pentacyclic [9.5.1.1 ]^3,9.1^5,15.1^7,13]Octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13, 15-heptaphenylpentacyclo [9.5.1.1 [ ]^3,9.1^5,15.1^7,13]Octa-siloxane-1-yl) propyl (meth) acrylate, 3- [ (3,5,7,9,11,13, 15-heptaethyl pentacyclo [9.5.1.1 [ ]^3,9.1^5,15.1^7,13]Octasiloxane-1-yloxy) dimethylsilyl]Propyl (meth) acrylate, 3- [ (3,5,7,9,11,13, 15-heptaisobutylpentacyclo [9.5.1.1 ]^3,9.1^5, ¹⁵.1^7,13]Octasiloxane-1-yloxy) dimethylsilyl]Propyl (meth) acrylate, 3- [ (3,5,7,9,11,13, 15-heptaisooctyl-pentacyclic [9.5.1.1 ]^3,9.1^5,15.1^7,13]Octasiloxane-1-yloxy) dimethylsilyl]Propyl (meth) acrylate, 3- [ (3,5,7,9,11,13, 15-heptacyclopentyl-pentacyclo [9.5.1.1 ]^3,9.1^5,15.1^7,13]Octasiloxane-1-yloxy) dimethylsilyl]Propyl (meth) acrylate, 3- [ (3,5,7,9,11,13, 15-heptaphenylpentacyclo [9.5.1.1 ]^3, ⁹.1^5,15.1^7,13]Octasiloxane-1-yloxy) dimethylsilyl]Propyl (meth) acrylate, and the like.

Specific examples of the styrene compound having one addition polymerizable double bond and not containing a group having an active hydrogen include: styrene, vinyl toluene, alpha-methyl styrene, p-chlorostyrene, and the like.

Examples of the styrene compound having one addition polymerizable double bond and not containing a group having an active hydrogen include a styrene compound containing silsesquioxane. The silsesquioxane-containing styrene derivative comprises the following components: 1- (4-Vinylphenyl) -3,5,7,9,11,13, 15-heptaethylpentacyclo [9.5.1.1 ]^3,9.1^5,15.1^7,13]Octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13, 15-heptaisobutylpentacyclic [9.5.1.1 ]^3,9.1^5,15.1^7,13]Octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13, 15-heptaisooctylpentacyclo [9.5.1.1^3,9.1^5,15.1^7,13]Octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13, 15-heptacyclopentylpentacyclo [9.5.1.1^3,9.1^5,15.1^7,13]Octasiloxane, and 1- (4-vinylphenyl) -3,5,7,9,11,13, 15-heptaphenylpentacyclo [9.5.1.1 ]^3,9.1^5,15.1^7,13]Octasiloxanes (T) having 4-vinylphenyl group such as octasiloxane₈Type silsesquioxanes); and 3- (3,5,7,9,11,13, 15-heptaethylpentacyclo [9.5.1.1 ]^3,9.1^5,15.1^7,13]Octasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9,11,13, 15-heptaisobutylpentacyclo [9.5.1.1^3,9.1^5,15.1^7,13]Octasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9,11,13, 15-heptaisooctyl pentacyclic [9.5.1.1 ]^3,9.1^5,15.1^7,13]Octasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9,11,13, 15-heptacyclopentylpentacyclo [9.5.1.1 [ ]^3,9.1^5,15.1^7,13]Octasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9,11,13, 15-heptaphenylpentacyclo [9.5.1.1 ]^3,9.1^5,15.1^7,13]Octasiloxane-1-yl) ethylstyrene, 3- ((3,5,7,9,11,13, 15-heptaethylpentacyclo [9.5.1.1 ]^3,9.1^5,15.1^7,13]Octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3- ((3,5,7,9,11,13, 15-heptaisobutylpentacyclo [9.5.1.1^3,9.1^5,15.1^7,13]Octasiloxane-1-ylOxy) dimethylsilyl) ethylstyrene, 3- ((3,5,7,9,11,13, 15-heptaisooctyl-pentacyclo [9.5.1.1^3,9.1^5,15.1^7,13]Octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3- ((3,5,7,9,11,13, 15-heptacyclopentylpentacyclo [9.5.1.1 [)^3,9.1^5,15.1^7,13]Octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, and 3- ((3,5,7,9,11,13, 15-heptaphenylpentacyclo [9.5.1.1 [)^3,9.1^5,15.1^7,13]Octasiloxane (T) having 4-vinylphenylethyl group such as octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene₈Type silsesquioxane), and the like.

Further, as an arbitrary addition polymerizable monomer, a macromonomer having a main chain derived from styrene, (meth) acrylate, siloxane, and alkylene oxide, for example, ethylene oxide, propylene oxide, and the like, and having one polymerizable double bond can be exemplified.

Examples of the addition polymerizable monomer (δ) also include compounds having two addition polymerizable double bonds.

Examples of the compound having two addition polymerizable double bonds include: 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, bis [ (meth) acryloyloxyethoxy ] bisphenol A, bis [ (meth) acryloyloxyethoxy ] tetrabromobisphenol A, bis [ (meth) acryloyloxypolyethoxy ] bisphenol A, 1, 3-bis (hydroxyethyl) 5, 5-dimethylhydantoin, 3-methylpentanediol di (meth) acrylate, propylene glycol, Di (meth) acrylate monomers such as di (meth) acrylate of hydroxypivalate neopentyl glycol compound and bis [ (meth) acryloyloxypropyl ] tetramethyldisiloxane, and divinylbenzene.

Furthermore, macromonomers having a main chain derived from styrene, (meth) acrylate, siloxane, and alkylene oxide, for example, ethylene oxide, propylene oxide, and the like, and having two polymerizable double bonds can also be exemplified.

Examples of the addition polymerizable monomer (δ) also include compounds having three or more addition polymerizable double bonds. Examples of the compound having three or more addition polymerizable double bonds include: trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, tris (2-hydroxyethyl isocyanate) tri (meth) acrylate, tris (diethylene glycol) trimer tri (meth) acrylate, 3,7, 14-tris [ (((meth) acryloyloxypropyl) dimethylsiloxane)]-1,3,5,7,9,11, 14-heptaethyltricyclo [7.3.3.1^5,11]Heptasiloxane, 3,7, 14-tris [ (((meth) acryloxypropyl) dimethylsiloxane)]1,3,5,7,9,11, 14-heptaisobutyltricyclo [7.3.3.1^5,11]Heptasiloxane, 3,7, 14-tris [ (((meth) acryloxypropyl) dimethylsiloxane)]-1,3,5,7,9,11, 14-heptaisooctyltricyclo [7.3.3.1^5,11]Heptasiloxane, 3,7, 14-tris [ (((meth) acryloxypropyl) dimethylsiloxane)]-1,3,5,7,9,11, 14-heptacyclopentyltricyclo [7.3.3.1⁵ ^,11]Heptasiloxane, 3,7, 14-tris [ (((meth) acryloxypropyl) dimethylsiloxane)]-1,3,5,7,9,11, 14-heptaphenyltricyclo [7.3.3.1^5,11]Heptasiloxane, octa (3- (meth) acryloxypropyldimethylsiloxane) octasilsesquioxane and octa (3- (meth) acryloxypropyl) octasilsesquioxane.

Furthermore, a macromonomer having a main chain derived from styrene, (meth) acrylate, siloxane, and alkylene oxide, for example, ethylene oxide, propylene oxide, and the like, and having three or more polymerizable double bonds can also be exemplified.

Examples of the addition polymerizable monomer (δ) also include fluorine-containing compounds. The fluorine-containing compound may be a compound having a fluorine atom-containing group and an addition polymerizable double bond in the molecule, and may be any of a vinyl compound, a vinylidene compound, and a vinylidene compound having a fluorine atom. Acrylic acid derivatives or styrene derivatives having a fluorine atom are preferable.

Typical examples of the addition polymerizable monomer having a fluorine atom include: fluoroalkyl (meth) acrylate, fluorostyrene, and fluoropolyether compounds.

As such addition polymerizable monomers having a fluorine atom, there are exemplified monomers disclosed in Japanese patent laid-open No. Hei 10-251352, Japanese patent laid-open No. 2004-043671, Japanese patent laid-open No. 2004-155847, Japanese patent laid-open No. 2005-029743, Japanese patent laid-open No. 2006-117742, Japanese patent laid-open No. 2006-299016, and Japanese patent laid-open No. 2005-350560.

Specifically, the following monomers can be mentioned.

Examples of fluoroalkyl (meth) acrylates include: 2,2, 2-trifluoroethyl (meth) acrylate, 2,2,3, 3-tetrafluoro-n-propyl (meth) acrylate, 2,2,3, 3-tetrafluoro-tert-pentyl (meth) acrylate, 2,2,3,4,4, 4-hexafluorobutyl (meth) acrylate, 2,2,3,4, 4-hexafluoro-tert-hexyl (meth) acrylate, 2,3,4,5,5, 5-hexafluoro-2, 4-bis (trifluoromethyl) pentyl (meth) acrylate, 2,2,3,3,4, 4-hexafluorobutyl (meth) acrylate, 2,2,2',2',2' -hexafluoroisopropyl (meth) acrylate, 2,2,3,3,4,4, 4-heptafluorobutyl (meth) acrylate, 2,2,3,3,4,4,5, 5-octafluoropentyl (meth) acrylate, 2,3,3,4,4,5,5, 5-nonafluoropentyl (meth) acrylate, 2,3,3,4,4,5,5,6,6,7, 7-dodecafluoroheptyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8, 8-dodecafluorooctyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8, 8-tridecafluorooctyl (meth) acrylate, 2,3,3,4,4,5, 6,6,7, 7-tridecafluoroheptyl (meth) acrylate, 3,3,4,4,5, 6,6,7,7,7, 8,8,9,9,10, 10-hexadecafluorodecanyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, 10-heptadecafluorodecyl (meth) acrylate, 3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11, 11-octadecylfluoroundecyl (meth) acrylate, 3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11, 11-nonadecafluoroundecyl (meth) acrylate, 3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12, 12-icosyldodecafluorododecyl (meth) acrylate, and the like.

Examples of fluorostyrenes include: and fluoroalkyl styrenes such as p-trifluoromethylstyrene, p-heptafluoropropylstyrene, and p-pentafluoroethylstyrene.

Specific examples of the fluoropolyether compound include: 1H, 1H-perfluoro-3, 6-dioxaheptyl (meth) acrylate, 1H-perfluoro-3, 6-dioxaoctyl (meth) acrylate, 1H-perfluoro-3, 6-dioxadecyl (meth) acrylate, 1H-perfluoro-3, 6, 9-trioxadecyl (meth) acrylate, 1H-perfluoro-3, 6, 9-trioxaundecyl (meth) acrylate, 1H-perfluoro-3, 6, 9-trioxatridecyl (meth) acrylate, 1H-perfluoro-3, 6,9, 12-tetraoxatridecyl (meth) acrylate, 6,9, 12-tetraoxatetradecyl (meth) acrylate, 1H-perfluoro-3, 6,9, 12-tetraoxahexadecyl (meth) acrylate, 1H-perfluoro-3, 6,9,12, 15-pentaoxahexadecyl (meth) acrylate, 1H-perfluoro-3, 6,9,12, 15-pentaoxaheptadecyl (meth) acrylate, 1H-perfluoro-3, 6,9,12, 15-pentaoxanonadecyl (meth) acrylate, 1H-perfluoro-3, 6,9,12,15, 18-hexaoxaeicosyl (meth) acrylate, 1H-perfluoro-3, 6,9,12,15, 18-hexaoxadidodecyl (meth) acrylate, 1H, 1H-perfluoro-3, 6,9,12,15,18, 21-heptaoxaeicosyl (meth) acrylate, 1H-perfluoro-3, 6,9,12,15,18, 21-heptaoxapentacosyl (meth) acrylate, and the like.

In addition, such an addition polymerizable monomer having a fluorine atom can also be synthesized by reacting a fluorine compound having a hydroxyl group with an acid halide having an addition polymerizable functional group.

Examples of the fluorine compound having a hydroxyl group include (HO) C (CF)₃)₂CH₃、(HO)C(CF₃)₂CH₂CH₃Having the formula (HO) C (CF)₃)₂CH₂O-CH₂A compound of the group (HO) C (CF)₃)₂CH₂CH₂O-CH₃And the like.

In addition, it is commercially available from Yiforlo Research Corporation (Exfluor Research Corporation) and thus is also commercially available for use.

Further, the fluorine compound having a hydroxyl group can be synthesized and used, and a synthetic method is described in Japanese patent laid-open No. Hei 10-147639.

Examples of the addition polymerizable monomer (δ) also include compounds having a hydrophilic group. Examples thereof include oxyalkylene group-containing monomers such as methoxypolyethylene glycol mono (meth) acrylate.

The addition polymerizable monomer (δ) may be used alone or in combination of two or more. When a plurality of kinds are used in combination, the composition ratio can be appropriately adjusted in accordance with the characteristics of the target polymer.

< precursor of fluorine-based polymer (A) >)

The precursor of the fluorine-based polymer (a) (hereinafter also referred to as polymer (a)) used in the present invention is an addition copolymer containing, as essential components, a constituent unit (constituent unit a-1) derived from a fluorosilsesquioxane (α) having one addition polymerizable functional group in the molecule, and a constituent unit (constituent unit a-2') derived from an addition polymerizable monomer having a functional group into which a group having a polymerizable unsaturated bond can be introduced, preferably an addition polymerizable monomer (∈) containing a group having an active hydrogen, and may be a sequential copolymer such as a block copolymer, or may be a random copolymer, preferably a random copolymer. The fluorine-based polymer (a) may have a crosslinked structure or may be a graft copolymer.

The molar ratio of the constituent unit A-1 to the constituent unit A-2' in the precursor of the polymer (A) used in the present invention is arbitrary as long as it is (a): (b) about 0.001: 99.999 to about 99.999: 0.001 is needed. In the case where the constituent unit A-3 is contained, the molar ratio of the constituent unit A-1 to the constituent unit A-2' and the constituent unit A-3 is arbitrary as long as it is (a): (b) about 0.001: 99.999 to about 99.999: 0.001, (b): (c) about 0.001: 99.999 to about 99.999: 0.001, (a): (c) about 0.001: 99.999 to about 99.999: 0.001 is needed.

The proportion of the constituent unit a-2' contained in the polymer (a) used in the present invention is not particularly limited as long as it is within the range of the above-mentioned (b), and in order to achieve the binding property of the polymer used in the present invention to the binder resin to be formulated when used as a coating agent, the polymer may contain a group having a polymerizable unsaturated bond to such an extent that preferable reactivity with the binder resin monomer can be obtained.

As described later, when the composition of the present invention is used as a surface modifier, the surface modifier is preferably a mixture of (a): (b) about 1: 99 to about 99: when the constituent unit a-3 is contained, the monomer (a): (b) about 1: 99 to about 99: 1. (b): (c) about 1: 99 to about 99: 1. (a): (c) about 1: 99 to about 99: 1.

when the fluorine-containing polymer (a) used in the present invention further contains an optional constituent unit (D), the molar ratios of the constituent unit a-1, the constituent unit a-2 (or the constituent unit a-2') and the constituent unit a-3 contained in the fluorine-containing polymer (a) or a precursor thereof are also the same.

The weight average molecular weight of the fluorine-containing polymer (A) varies depending on the content of the constituent unit A-2, etc., but is about 1000 to 100 ten thousand on a basis. On the other hand, the molecular weight distribution (Mw/Mn) of the fluorine-containing polymer (A) is about 1.01 to 3.0.

When a precursor of the fluorine-based polymer (a) is obtained by using a plurality of monomers as, for example, a fluorosilsesquioxane (α) having one addition polymerizable functional group in the molecule, an addition polymerizable monomer (e) having a group having an active hydrogen, an organopolysiloxane (γ) having an addition polymerizable functional group, or an optional addition polymerizable monomer (δ), the ratio of each monomer may be appropriately determined depending on the characteristics of the target copolymer. In view of simplicity and versatility, radical copolymerization is preferable.

The addition polymerization can be performed using a polymerization initiator.

Examples of the polymerization initiator used include: azo compounds such as 2,2' -azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), 2' -azobis (2-butyronitrile), dimethyl-2, 2' -azobisisobutyrate, and 1,1' -azobis (cyclohexane-1-carbonitrile); peroxides such as benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxyneodecanoate and the like; and dithiocarbamates such as tetraethylthiuram disulfide; and the like, a radical polymerization initiator.

Examples of the polymerization reaction include living radical polymerization and living energy ray polymerization.

With respect to living radical polymerization, polymerization is carried out by atom transfer radical; reversible addition fragmentation chain transfer; iodine transfer polymerization; polymerization with an initiation-transfer-termination agent (iniferter) is typical, and can be carried out using the polymerization initiators described in the following cited documents a to C.

Citation A: futilely treating cattail pool, just repairing Yuancheng, published in 8 months and 10 days 1999, and published by NTS.

Citation B: free RADICAL POLYMERIZATION HANDBOOK (HANDBOOK OF RADICAL POLYMERIZATION), K. Matzisha FSK, T.P. Davis editor (K.Matyjaszewski, T.P.Davis, Eds.), John Wiley and Sons, Canada 2002

Citation document C: japanese patent laid-open No. 2005-105265

The active energy ray polymerization can be carried out using a compound described in cited document D as an active energy ray polymerization initiator.

Citation D: the photopolymer workshop, compiled listing of photosensitive materials, published by extension in 3.31.1996.

In the present invention, the active energy ray is an energy ray that can decompose a compound that generates an active species to generate an active species. Examples of such an active energy ray include: light energy rays such as visible rays, ultraviolet rays, infrared rays, X rays, alpha rays, beta rays, gamma rays, and electron beams.

Specific examples of the active energy ray polymerization initiator to be used are not particularly limited as long as they are compounds that generate radicals by irradiation with ultraviolet rays or visible rays. The compounds which can be used as the active energy ray polymerization initiator are: benzophenone, Michler's ketone, 4' -bis (diethylamino) benzophenone, xanthone (xanthone), thioxanthone (thioxanthone), isopropylxanthone, 2, 4-diethylthioxanthone2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4' -isopropylphenylacetone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2-diethoxy acetophenone, 2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl ] ethanone]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4,4 '-bis (tert-butylperoxycarbonyl) benzophenone, 3,4,4' -tris (tert-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2- (4 '-methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (3',4 '-dimethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (2',4' -Dimethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (2' -methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4' -pentyloxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 4- [ p-N, N-bis (ethoxycarbonylmethyl)]-2, 6-bis (trichloromethyl) -s-triazine, 1, 3-bis (trichloromethyl) -5- (2' -chlorophenyl) -s-triazine, 1, 3-bis (trichloromethyl) -5- (4' -methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3' -carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (4-ethoxycarbonylphenyl) -1,2' -biimidazole, 2' -bis (2, 4-dichlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2, 4-dibromophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2,4, 6-trichlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3, 6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenylketone, bis (. eta. eta.⁵-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium and the like. These compounds may be used alone, and two or more thereof may be used in combination. Preferred examples thereof include 3,3',4,4' -tetrakis (t-butylperoxycarbonyl) benzophenone, 3',4,4' -tetrakis (t-hexylperoxycarbonyl) benzophenone, and 3,3' -bis (methoxylperoxycarbonyl)Alkylcarbonyl) -4,4' -bis (tert-butylperoxycarbonyl) benzophenone, 3,4' -bis (methoxycarbonyl) -4,3' -bis (tert-butylperoxycarbonyl) benzophenone, 4' -bis (methoxycarbonyl) -3,3' -bis (tert-butylperoxycarbonyl) benzophenone, and the like.

The amount of the polymerization initiator used in the addition polymerization may be set to about 0.01 to 10 mol% with respect to the total number of moles of the monomers.

In addition, a chain transfer agent may be used in the addition polymerization. By using a chain transfer agent, the molecular weight can be appropriately controlled. Examples of the chain transfer agent include: thiols such as thio- β -naphthol, thiophenol, butyl mercaptan, ethyl thioglycolate, mercaptoethanol, thioglycolate, isopropyl mercaptan, t-butyl mercaptan, dodecyl mercaptan, thiomalic acid, pentaerythritol tetrakis (3-mercaptopropionate), and pentaerythritol tetrakis (3-thioglycolate); disulfide ethers such as diphenyl disulfide, diethyl dimercaptoacetate, and diethyl disulfide; further, the method also includes: toluene, methyl isobutyrate, carbon tetrachloride, cumene, diethyl ketone, chloroform, ethylbenzene, butyl chloride, sec-butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, chloropropene, methyl chloroform, tert-butyl benzene, butyl alcohol, isobutyl alcohol, acetic acid, ethyl acetate, acetone, dioxane, tetrachloroethane, chlorobenzene, methylcyclohexane, tert-butyl alcohol, benzene, and the like. In particular, thioglycolates reduce the molecular weight of the polymer and make the molecular weight distribution uniform.

The chain transfer agent may be used alone or in combination of two or more.

The specific production method of the fluorine-containing polymer (a) may be the same as the production method of a general addition polymer, and for example, the following methods can be used: solution polymerization method, emulsion polymerization method, suspension polymerization method, bulk-suspension polymerization method, polymerization method using supercritical CO₂The polymerization method of (1).

In the case of using the solution polymerization method, for example, the addition polymerization reaction can be carried out by dissolving a fluorosilsesquioxane (α) having one addition polymerizable functional group in the molecule, an addition polymerizable monomer (∈) having a group having an active hydrogen, an organopolysiloxane (γ) having an addition polymerizable functional group which can be used as needed, an optional addition polymerizable monomer (δ), a polymerization initiator, a chain transfer agent, and the like in an appropriate solvent and heating or irradiating with an active energy ray.

Examples of the solvent used in the polymerization reaction include: hydrocarbon solvents (benzene, toluene, etc.), ether solvents (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbon solvents (dichloromethane, chloroform, chlorobenzene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, butanol, t-butanol, etc.), nitrile solvents (acetonitrile, propionitrile, benzonitrile, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), carbonate solvents (ethylene carbonate, propylene carbonate, etc.), amide solvents (N, N-dimethylformamide, N-dimethylacetamide), hydrochlorofluorocarbon solvents (HCFC-141b, HCFC-225), Hydrofluorocarbon (HFCs) solvents (HFCs having 2 to 4,5, and 6 or more carbon atoms), perfluorocarbon solvents (perfluoropentane, acetone, ethyl acetate, and the like), and mixtures thereof, Perfluorohexane), alicyclic hydrofluorocarbon solvents (fluorocyclopentane and fluorocyclobutane), oxygen-containing fluorine solvents (fluoroether, fluoropolyether, fluoroketone and fluoroalcohol), aromatic fluorine solvents (α, α, α -trifluorotoluene and hexafluorobenzene), and water. These may be used alone or in combination of two or more.

The amount of the solvent used may be such that the monomer concentration becomes about 10 to 80% by weight.

The reaction temperature is not particularly limited, and may be about 0 to 200 ℃ as a standard, and preferably about room temperature to about 150 ℃. The polymerization reaction may be carried out under reduced pressure, normal pressure or increased pressure depending on the kind of the monomer or the kind of the solvent.

The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. The reason for this is that: the resultant radicals are inhibited from being deactivated by contact with oxygen and the polymerization rate is reduced, thereby obtaining a polymer having a suitably controlled molecular weight. Further, the polymerization reaction is preferably carried out under reduced pressure in a polymerization system in which dissolved oxygen is removed (after removing dissolved oxygen under reduced pressure, the polymerization reaction can be carried out under reduced pressure as it is).

The polymer obtained in the solution can be purified or isolated by a conventional method, and can be used for coating film formation or the like in the state of the solution.

In the case of purifying the fluorine-containing polymer (a), a purification method by a reprecipitation operation is preferable. The purification process was carried out in the following manner. First, a polymerization reaction solution containing a polymer and an unreacted monomer is added to a so-called precipitant, which is a solvent that does not dissolve the polymer but dissolves the unreacted monomer, to precipitate only the polymer. The amount of the precipitant used is preferably 20 to 50 times based on the weight of the polymerization reaction solution. The preferred precipitant is a solvent which is compatible with the solvent used in the polymerization, dissolves only the unreacted monomer without dissolving the polymer at all, and has a relatively low boiling point. Examples of preferred precipitants are lower alcohols and aliphatic hydrocarbons. Particularly preferred precipitants are methanol, ethanol, 2-propanol, hexane and heptane. These may be used alone or in combination of two or more. In the case of mixed use, sold as a modified alcohol, Solmix AP-1, Solmix A-11 and the like are commercially available from Nippon alcohol. In addition, in order to further improve the removal efficiency of the unreacted monomer, the number of repetition of the reprecipitation operation may be increased. By the method, only the polymer can be precipitated in the poor solvent, and the unreacted monomer can be easily separated from the polymer by a filtration operation.

< fluoropolymer (A) > < used in the present invention

As described above, the group having a polymerizable unsaturated bond can be introduced by reacting a precursor of the fluorine-based polymer with: the compound has, in the same molecule, a functional group reactive with a functional group (group having an active hydrogen) of the constituent unit (E) into which a group having a polymerizable unsaturated bond can be introduced, and a group having a polymerizable unsaturated bond.

Examples of the compound having a functional group reactive with a group having an active hydrogen and a group having a polymerizable unsaturated bond in the same molecule include: an isocyanate compound having a polymerizable unsaturated bond, an acid halide compound having a polymerizable unsaturated bond, a carboxylic acid ester compound having a polymerizable unsaturated bond, and an epoxy compound. The group having a polymerizable unsaturated bond is preferably a radical polymerizable group, and examples thereof include: (meth) acrylic, allyl, styryl, and the like.

As the isocyanate compound having a (meth) acrylic group, a compound having the following structure can be used.

[ solution 10]

In the formula, R⁸、R⁹Each independently hydrogen OR methyl, B is oxygen, C1-C3 alkylene OR-OR¹⁰-；R¹⁰Represents an alkylene group having 2 to 12 carbon atoms, an oxyalkylene group having 2 to 12 carbon atoms, or an arylene group having 6 to 12 carbon atoms.

As the isocyanate compound having a styryl group, a compound having the following structure can be used.

[ solution 11]

In the formula, R¹¹Is C1-10 alkylene, R¹²Is hydrogen or methyl.

Specific examples of isocyanate compounds having a polymerizable unsaturated bond that can be preferably used are: 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 1-bis (acryloyloxymethyl) ethyl isocyanate, 4- (2-isocyanatoisopropyl) styrene, preferably 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 1-bis (acryloyloxymethyl) ethyl isocyanate.

When an isocyanate compound having a polymerizable unsaturated bond is reacted with a group having an active hydrogen, a urethanization catalyst is used for the purpose of promoting the reaction.

The urethane-forming catalyst includes an organometallic urethane-forming catalyst and a tertiary amine urethane-forming catalyst.

Examples of the organometallic urethane catalyst include organometallic urethane catalysts such as tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octylate, lead naphthenate, nickel naphthenate, and cobalt naphthenate.

Examples of the tertiary amine-based urethanization catalyst include: triethylenediamine, N, N, N ', N ', N ' -pentamethyldipropylenetriamine, N, N, N ', N ', N ' -pentamethyldiethylenetriamine, N, N, N ', N ' -tetramethylhexamethylenediamine, bis (dimethylaminoethyl) ether, 2- (N, N-dimethylamino) -ethyl-3- (N, N-dimethylamino) propyl ether, N, N ' -dimethylcyclohexylamine, N, N-dicyclohexylmethylamine, methylenebis (dimethylcyclohexyl) amine, triethylamine, N, N-dimethylacetylamine, N, N-dimethyldodecylamine, N, N-dimethylhexadecylamine, N, N, N ', N ' -tetramethyl-1, 3-butanediamine, N, N-dimethylbenzylamine, Morpholine, N-methylmorpholine, N-ethylmorpholine, N- (2-dimethylaminoethyl) morpholine, 4' -oxydiethylenedimorpholine, N, N ' -dimethylpiperidine, N, N ' -diethylpiperidine, N, -methyl-N ' -dimethylaminoethylpiperidine, 2,4, 6-tris (dimethylaminomethyl) phenol, tetramethylguanidine, 3-dimethylamino-N, N-dimethylpropionamide, N, N, N ', N ' -tetrakis (3-dimethylaminopropyl) methanediamine, N, N-dimethylaminoethanol, N, N, N ', N ' -tetramethyl-1, 3-diamino-2-propanol, N, N, N ' -trimethylaminoethylethanolamine, ethanolamine, N- (2-dimethylaminoethyl) morpholine, N-dimethylaminoethylethanolamine, N-dimethylolpiperidine, N-dimethylolpiperidine, N, N-, 1, 4-bis (2-hydroxypropyl) -2-methylpiperidine, 1- (2-hydroxypropyl) imidazole, 3-diamino-N-methylpropylamine, 1, 8-diazabicyclo [5.4.0] -undecene-7, N-methyl-N-hydroxyethylpiperidine and the like.

These may be used alone or in combination of two or more. The amount of the catalyst used may be any amount relative to the isocyanate group, and is preferably 0.0001 to 1 mol%, more preferably 0.001 to 1 mol%, based on the isocyanate group.

In order to obtain the fluorine-containing polymer (a) using the isocyanate compound having a polymerizable unsaturated bond, a solvent may be used as needed. The solvent used may be any solvent which is inert to the group having an active hydrogen and the isocyanate group, and examples thereof include: aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone and cyclohexanone; glycol ether ester solvents such as ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, and ethyl-3-ethoxypropionate; ether solvents such as tetrahydrofuran and dioxane; and polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and furfural, and these may be used alone or in combination of two or more. The amount of the solvent used may be such that the concentration of the polymer containing a group having an active hydrogen becomes about 10 to 80% by weight.

The reaction temperature is usually from 0 ℃ to 120 ℃ and preferably from 20 ℃ to 100 ℃. If the temperature is less than 0 ℃, the reaction is very slow, and if the temperature exceeds 120 ℃, polymerization may occur.

The molar ratio in the reaction is isocyanate group: group with active hydrogen ═ 100: 1-0.01: 1, preferably 20: 1-0.1: 1.

in addition, a polymerization inhibitor may be present for the purpose of inhibiting polymerization when an isocyanate group reacts with a group having an active hydrogen. As the polymerization inhibitor, there may be mentioned: p-benzoquinone, naphthoquinone, phenanthrenequinone, p-quinonediquinone (p-xyloquinone), p-toluquinone (p-tolaquinone), 2,6-dichloroquinone (2,6-dichloroquinone), 2, 5-diphenyl-p-benzoquinone, 2, 5-diacetoxy-p-benzoquinone, 2, 5-dihexanyloxy-p-benzoquinone, 2, 5-diacetoxy-p-benzoquinone, hydroquinone, p-tert-butylcatechol, 2, 5-tert-butylhydroquinone, mono-tert-butylhydroquinone, or 2, 5-di-tert-amylhydroquinone, and the like are used in an amount of 10ppm to 10,000ppm, preferably 50ppm to 1,000ppm, based on the total amount of the precursor of the fluorine-based polymer (a) and the isocyanate compound having a polymerizable unsaturated bond.

On the other hand, examples of the acid halide having a polymerizable unsaturated bond include: chloride compounds such as acryloyl chloride, methacryloyl chloride, styrene carbonyl chloride, styrene sulfonyl chloride, 2-methacryloyloxyethylsuccinyl chloride, and 2-methacryloyloxyethylhexahydrophthaloyl chloride; bromide compounds such as acryloyl bromide, methacryloyl bromide, styrene carbonyl bromide, styrene sulfonyl bromide, 2-methacryloyloxyethyl succinyl bromide, and 2-methacryloyloxyethyl hexahydrophthaloyl bromide, and halides of acrylic acid and methacrylic acid are preferred from the viewpoint of ultraviolet curability.

When the fluorine-containing polymer (a) having a polymerizable unsaturated bond in a side chain is obtained using an acid halide having a polymerizable unsaturated bond, a known esterification reaction can be used. Here, the esterification reaction is a dehydrohalogenation reaction of an acid halide with a group having an active hydrogen (preferably a hydroxyl group).

Hydrogen halide is by-produced in the reaction. In general, it is preferable that a base is coexistent as a hydrogen halide scavenger in the reaction system in order to remove the hydrogen halide from the reaction system. The base as the hydrogen halide scavenger is not particularly limited, and a known one can be used. As the base which can be preferably used in general, there can be mentioned: trialkylamines such as trimethylamine, triethylamine and tripropylamine, pyridine, tetramethylurea, sodium hydroxide and sodium carbonate. The amount of the base is preferably 1 mole or more based on 1 mole of formyl chloride (carboxylic acid chloride).

When the reaction is carried out, it is generally preferred to use an organic solvent. Examples of the solvent which can be preferably used include: aliphatic or aromatic hydrocarbons or halogenated hydrocarbons such as benzene, toluene, xylene, hexane, heptane, petroleum ether, chloroform, dichloromethane, dichloroethane; ethers such as diethyl ether, dioxane, and tetrahydrofuran; n, N-dialkylcarboxamides such as N, N-dimethylformamide and N, N-diethylformamide; dimethyl sulfoxide, and the like.

The temperature in the reaction can be selected from a wide range, and can be selected from a range of usually-20 ℃ to 100 ℃, preferably 0 ℃ to 50 ℃. The reaction time varies depending on the kind of the raw material, and may be selected from the range of usually 5 minutes to 24 hours, preferably 1 hour to 4 hours. In addition, stirring is preferably performed during the reaction.

The reaction product may be usually separated by removing the solvent by distillation after washing with water and drying after the reaction, but the reaction product may be directly subjected to the second stage esterification reaction without performing a separation operation after the reaction is completed.

Examples of the carboxylic acid compound having a polymerizable unsaturated bond include: acrylic acid, methacrylic acid, vinyl benzoic acid, and the like.

When the fluorine-based polymer (a) having a polymerizable unsaturated bond in a side chain is obtained using a carboxylic acid compound having a polymerizable unsaturated bond, a known esterification reaction can be used. Here, the esterification reaction is a dehydration condensation reaction of a carboxylic acid compound and a group having an active hydrogen (preferably a hydroxyl group).

Examples of the carboxylate compound having a polymerizable unsaturated bond include: methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, 1-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.

When the fluorine-based polymer (a) having a polymerizable unsaturated bond in a side chain is obtained using a carboxylate compound having a polymerizable unsaturated bond, a known esterification reaction can be used. Here, the esterification reaction is a transesterification reaction of a carboxylate compound with a group having an active hydrogen (preferably a hydroxyl group).

Examples of the epoxy compound having a polymerizable unsaturated bond include: glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, and the like.

When the fluorine-containing polymer (a) having a polymerizable unsaturated bond in a side chain is obtained using a compound having a polymerizable unsaturated bond, a known epoxy ring-opening reaction of a cyclic ether and a hydroxyl group can be utilized.

Further, the fluorine-based polymer (a) having a polymerizable unsaturated bond in a side chain can be obtained by urethanizing a part of the isocyanate groups of a compound having a plurality of isocyanate groups such as isophorone diisocyanate and a hydroxyl group-containing addition polymerizable monomer such as 2-hydroxyethyl acrylate to form an isocyanate compound having a polymerizable unsaturated bond, and further performing a urethanization reaction of the isocyanate compound and a group having an active hydrogen (preferably a hydroxyl group).

From the viewpoint of the abrasion resistance of the cured film obtained, the fluorine-containing polymer (a) is contained in the resin composition in an amount of preferably 0.01 to 3% by weight, more preferably 0.5 to 2% by weight, based on 100% by weight of the total solid content (in the present invention, the remaining component after the solvent is removed from the photocurable composition is referred to as "solid content").

< urethane (meth) acrylate (B) >

The photocurable resin composition according to one embodiment of the present invention contains a 6-functional urethane (meth) acrylate (B). The fluorine-based polymer can be used as a surface modifier alone in patent document 2, and can be used as a surface modifier (so-called coating agent) by being combined with another resin (hereinafter referred to as a binder resin) or a resin monomer (hereinafter referred to as a binder resin monomer) as needed, and dissolved or dispersed in various solvents as needed, and specifically, characteristics of repelling contamination by a universal pen or the like and also of good wiping properties are described, and the present inventors have surprisingly found that a cured film having high transparency and excellent abrasion resistance can be obtained by combining a specific fluorine-based polymer (a) with a 6-functional urethane (meth) acrylate (B).

From the viewpoint of exhibiting the effects of the present invention, the urethane (meth) acrylate (B) is 6-functional, and the viscosity at 40 ℃ is preferably 20,000mPa · s or less, more preferably 10,000mPa · s or less, and still more preferably 8,000mPa · s or less. Further, the viscosity at 40 ℃ is preferably 2,000 mPas or more. The viscosity is measured by an E-type viscometer at 40 ℃.

The urethane (meth) acrylate (B) may be synthesized and used, or may be purchased as a commercial product.

Examples of commercially available products include Elisate (EXCELATE) RUA-076MG, Elisate (EXCELATE) RUA-071 (manufactured by Asian industries, Ltd.), EBECRYL (EBECRYL)1290, KRM 8200 (manufactured by Daicel-Allnex (Ltd.), Zhan Ji), and Violet UV-7605B (manufactured by Nippon Synthesis chemical industries, Ltd.).

In addition, from the viewpoint of the abrasion resistance of the cured film obtained, the urethane (meth) acrylate (B) is preferably contained in an amount of 50 to 98% by weight, more preferably 53 to 98% by weight, and even more preferably 55 to 97% by weight, based on 100% by weight of the total solid content (the remaining components after the solvent is removed from the photocurable composition).

< photopolymerization initiator (C) >

In the present invention, the fluorine-based polymer (a) and the urethane (meth) acrylate (B) are mixed, and the photopolymerization initiator (C) is used for the purpose of accelerating the curing of these. As such a photopolymerization initiator, a photopolymerization initiator that generates radicals by ultraviolet rays or visible rays is preferable.

As the photopolymerization initiator, the active energy ray polymerization initiator described in the section < fluorine-based polymer (A) > can be used.

< other ingredients >

The photocurable composition containing a fluoropolymer according to an embodiment of the present invention may further contain other components than (a) to (C) from the viewpoint of adjusting the physical properties of the composition and from the viewpoint of curing at the time of forming a subsequent coating. Examples of such other components include solvents, resins other than the fluorine-based resin (a), and inorganic fine particles. The photocurable composition containing a fluorine-based resin may further contain any component such as an active energy ray sensitizer, a polymerization inhibitor, a polymerization initiation aid, a leveling agent, a wettability improver, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, an inorganic filler typified by silica or alumina, or an organic filler, within a range that does not adversely affect the antifouling property and abrasion resistance of the composition.

Inorganic microparticle (D)

In the composition of the present invention, from the viewpoint of improving the wear resistance, inorganic fine particles (D) (hereinafter also referred to as component (D)) are preferably contained. Examples of the inorganic fine particles (D) include silicon oxide and aluminum oxide.

The average particle diameter of the inorganic fine particles (D) is not particularly limited as long as it is on the order of nanometers, but is preferably 1nm to 100nm, more preferably 1nm to 40nm, and even more preferably 1nm to 20nm from the viewpoint of transparency. In addition, the particle size distribution is preferably narrow.

The shape of the inorganic fine particles (D) is not particularly limited, and may be any of spherical, irregular, scaly, and the like. From the viewpoint of improving adhesiveness and transparency, a spherical shape is preferable. When the shape of the inorganic fine particles (D) is other than spherical, the average particle diameter of the inorganic fine particles (D) means the average maximum diameter of the inorganic fine particles (D).

The inorganic fine particles (D) may be surface-treated with a silane coupling agent or the like, and are preferably surface-modified colloidal silica.

In the composition of the present invention, the content of the inorganic fine particles (D) as the component (D) is preferably 5 to 50% by weight, more preferably 10 to 45% by weight, in terms of% by weight relative to the total solid content of the composition.

In the present embodiment, the inorganic fine particles (D) may be added to the resin composition and used, or a commercially available product in which the inorganic fine particles (D) are dispersed in a resin may be used.

Examples of such commercially available products include: a nano-silica-dispersed epoxy resin manufactured by the winning industry (EVONIK INDUSTRIES) having 40 mass% of nano-silica dispersed in an epoxy resin [ nano-pos (registered trademark) series (C620, F400, E500, E600, E430) ]; and nanograin (Nanocryl) (registered trademark) series (C130, C140, C145, C146, C150, C153, C155, C165, and C350) in which 50 mass% of nano silica is dispersed in an acrylate resin.

In order to form a coating on the surface of a base material such as plastic, glass, metal, or the like and to exhibit abrasion resistance, 1) the composition may be used as a composition containing only the components (a) to (C), and 2) the composition may be further used in combination with a binder resin and a binder resin monomer. In order to develop these functions on the surface of the substrate, it is important to adhere to the substrate, and in order to further fix the polymer and the substrate, it is preferable to use the polymer and the substrate in combination with a binder resin, and 3) by selecting a binder resin having a functional group reactive with the polymer (hereinafter referred to as a reactive binder resin) and a component that is crosslinked by a reaction with the polymer and the reactive binder resin, the polymer and the substrate can be further firmly fixed via the binder resin. In the case of applications requiring properties such as heat resistance, light resistance, and scratch resistance, the surface can be modified without impairing the original properties of the resin by selecting a binder resin having these properties.

As described above, the composition of the present invention may be used as a coating agent (protective coating agent or the like) in the form of a composition containing only the components (a) to (C) as described in the above 1), may be used as a coating agent by being mixed with another binder resin as described in the above 2), or may be used as a coating agent by being mixed with a binder resin monomer (hereinafter also referred to as a reactive binder resin monomer) capable of reacting with the fluorine-based polymer (a) as described in the above 3).

The binder resin may be any one of a thermoplastic resin, a thermosetting resin, and an active energy ray-curable resin, or may be a plurality of resins.

Examples of the binder resin include: polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, poly (meth) acrylate resin, ultra-high molecular weight polyethylene, poly-4-methylpentene, syndiotactic polystyrene (syndiotic polystyrene), polyamide (nylon 6: trade name of DuPont, nylon 6, 10: trade name of DuPont, nylon 6, T: trade name of DuPont, Nylon MXD 6: trade name of DuPont), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene 2, 6-naphthalenedicarboxylate, etc.), polyacetal, polycarbonate, polyphenylene ether, fluororesin (polytetrafluoroethylene, polyvinylidene fluoride, etc.), polyphenylene sulfide, polysulfone, polyethersulfone, polyphenylene ether, fluororesin (polytetrafluoroethylene, polyvinylidene fluoride, etc.), polyphenylene sulfide, polyethylene terephthalate, etc, Polyether ether ketone, polyarylate (trade name of U polymer: Unitika (stock), vickers (Vectra): trade name of plastic for jewelry (polyplasics) (stock), etc.), polyimide (trade name of Kapton (Kapton): dongli (stock), trade name of ohmar (Aurum): trade name of mitsui chemical (stock), etc.), polyetherimide, polyamideimide, phenol resin, alkanol resin, melamine resin, epoxy resin, urea resin, bismaleimide resin, polyester urethane resin, polyether urethane resin, silicone resin, etc.

These resins may be used alone, or a plurality of resins may be used in combination.

Alternatively, a reactive binder resin monomer may be mixed and used as described in 3). In particular, a resin obtained by curing a fluorine-based polymer having a polymerizable unsaturated bond in a side chain and a reactive binder resin monomer is crosslinked and bonded to the fluorine-based polymer, and as a result, a composite resin having excellent mechanical properties, surface and interface characteristics, and compatibility can be obtained.

Specifically, a solution containing a fluorine-based polymer (a) having a polymerizable unsaturated bond in a side chain, a urethane (meth) acrylate (B), a reactive binder resin monomer, and a photopolymerization initiator (C) is applied to a substrate, and a coating film is dried and cured, whereby a coating film (composite film) containing a composite resin with a binder resin can be formed on the substrate.

The formed composite film has high antifouling property and wear resistance.

Preferred examples of the reactive binder resin monomer include monomers forming Ultraviolet (UV) curable resins that can be cured by irradiation with ultraviolet light.

< monomer for forming UV curable resin >

Examples of the resin that can be cured by radical irradiation with ultraviolet rays include: a resin having an unsaturated bond capable of radical polymerization, such as a (meth) acrylate monomer, an unsaturated polyester resin, a polyester (meth) acrylate resin, an epoxy (meth) acrylate resin, and a urethane (meth) acrylate resin other than the component (B).

Examples of the (meth) acrylate monomer include compounds obtained by reacting a polyol with an α, β -unsaturated carboxylic acid. Examples thereof include: polyalkylene glycol di (meth) acrylate, ethylene glycol (meth) acrylate, propylene glycol (meth) acrylate, polyethylene polytrimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropane tetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol penta (meth) acrylate, polyethylene glycol ditrimethylolpropane di (meth) acrylate, polyethylene glycol ditrimethylolpropane tri (meth) acrylate, trimethylolpropane tri, Dipentaerythritol hexa (meth) acrylate, and the like. Further, compounds having a silsesquioxane skeleton and a (meth) acrylate group as a functional group are also exemplified.

Examples of the unsaturated polyester resin include those obtained by dissolving a condensation product (unsaturated polyester) of an esterification reaction between a polyhydric alcohol and an unsaturated polybasic acid (and optionally a saturated polybasic acid) in a polymerizable monomer.

The unsaturated polyester can be produced by polycondensing an unsaturated acid such as maleic anhydride with a glycol such as ethylene glycol. Specific examples thereof include: reacting a polybasic acid having a polymerizable unsaturated bond such as fumaric acid, maleic acid or itaconic acid or an acid anhydride thereof as an acid component with a polyhydric alcohol such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2-methyl-1, 3-propanediol, 2-dimethyl-1, 3-propanediol, cyclohexane-1, 4-dimethanol, an ethylene oxide adduct of bisphenol A, or a propylene oxide adduct of bisphenol A as an alcohol component, and optionally further adding a polybasic acid having no polymerizable unsaturated bond such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid, or an anhydride thereof as an acid component.

As the polyester (meth) acrylate resin, there may be mentioned: (1) a (meth) acrylate obtained by reacting a polyester having a terminal carboxyl group obtained from a saturated polybasic acid and/or an unsaturated polybasic acid and a polyhydric alcohol with an epoxy compound containing an α, β -unsaturated carboxylic acid ester group, (2) a (meth) acrylate obtained by reacting a polyester having a terminal carboxyl group obtained from a saturated polybasic acid and/or an unsaturated polybasic acid and a polyhydric alcohol with an acrylate having a hydroxyl group, and (3) a (meth) acrylate obtained by reacting a polyester having a terminal hydroxyl group obtained from a saturated polybasic acid and/or an unsaturated polybasic acid and a polyhydric alcohol with a (meth) acrylic acid.

Examples of the saturated polybasic acid used as a raw material of the polyester (meth) acrylate include: polybasic acids having no polymerizable unsaturated bond such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid, or anhydrides thereof, and polymerizable unsaturated polybasic acids such as fumaric acid, maleic acid, and itaconic acid, or anhydrides thereof. Further, the polyol component is the same as the unsaturated polyester.

Examples of the epoxy (meth) acrylate resin that can be used in the present invention include: a compound (vinyl ester) having a polymerizable unsaturated bond, which is generated by a ring-opening reaction of a compound having a glycidyl group (epoxy group) with a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid, is dissolved in a polymerizable monomer.

The vinyl ester is produced by a known method, and an epoxy (meth) acrylate obtained by reacting an epoxy resin with an unsaturated monobasic acid such as acrylic acid or methacrylic acid is exemplified.

In addition, various epoxy resins may be reacted with bisphenol (e.g., type A) or dibasic acids such as adipic acid, sebacic acid, and dimer acid (Harley dimer (HARIDIMER) 270S: Harima (Harima) converted (stranded)), to impart flexibility.

Examples of the epoxy resin used as a raw material include bisphenol a diglycidyl ether and its high molecular weight homologues, novolak-type glycidyl ethers, and the like.

Examples of the urethane (meth) acrylate resin include oligomers containing a radical polymerizable unsaturated group, which can be obtained by: after the polyisocyanate is reacted with the polyol or the polyol, it is further reacted with a hydroxyl group-containing (meth) acrylic compound and, if necessary, a hydroxyl group-containing allyl ether compound.

Specific examples of the polyisocyanate include: 2, 4-tolylene diisocyanate and isomers thereof, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, carnock (Burnock) D-750, CRISVON NK (trade name; di ex DIC) (stock), Desmodur (Desmodur) L (trade name; manufactured by vestigial kosa carbamate (stock)), cronerite (cornate) L (trade name; manufactured by tokoa (stock)), tokenate (Takenate) D102 (trade name; manufactured by mitsui Chemical (stock)), isolotite (Isonate)143L (trade name; manufactured by Dow Chemical (stock)).

The polyol includes polyester polyol, polyether polyol and the like, and specifically includes: glycerin-ethylene oxide adduct, glycerin-propylene oxide adduct, glycerin-tetrahydrofuran adduct, glycerin-ethylene oxide-propylene oxide adduct, trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct, trimethylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol-propylene oxide adduct, dipentaerythritol-tetrahydrofuran adduct, dipentaerythritol-ethylene oxide-propylene oxide adduct, and the like.

Specific examples of the polyhydric alcohols include: ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1, 3-propanediol, 1, 3-butanediol, an adduct of bisphenol a with propylene oxide or ethylene oxide, 1,2,3, 4-tetrahydroxybutane, glycerol, trimethylolpropane, 1, 3-butanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, p-xylylene glycol, dicyclohexyl-4, 4-diol, 2, 6-decahydronaphthalene diol, 2, 7-decahydronaphthalene diol, and the like.

The hydroxyl group-containing (meth) acrylic compound is not particularly limited, and is preferably a hydroxyl group-containing (meth) acrylate, and specific examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris (hydroxyethyl) isocyanurate di (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like.

Examples of the acrylate monomer include the following fluorine-based silicon compounds: as disclosed in japanese patent No. 2655683, the silane coupling agent can be obtained by polymerizing silanol having a fluorine-containing hydrocarbon group with hexamethylcyclotrisiloxane and then reacting with chlorosilane having a polymerizable unsaturated group to stop the polymerization. In the fluorine-containing silicon compound, preferable examples thereof include the following formulas (I-1) and (I-2) (both n represents 0 to 500, R¹³Represents hydrogen or methyl).

[ solution 12]

[ solution 13]

The resin composition of the present invention may contain a solvent from the viewpoint of adjusting the concentration of the fluorine-containing polymer or the physical properties of the photocurable resin composition containing the fluorine-containing polymer, and from the viewpoint of curing the photocurable resin composition containing the fluorine-containing polymer at the time of the subsequent film formation.

In addition, the fluorine-based polymer and the binder resin monomer may be dissolved in a solvent and used. Examples of the solvent used include: hydrocarbon solvents (benzene, toluene, etc.), ether solvents (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbon solvents (dichloromethane, chloroform, chlorobenzene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, butanol, t-butanol, etc.), glycol ether solvents (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc.), nitrile solvents (acetonitrile, propionitrile, benzonitrile, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), ester solvents (ethylene carbonate, propylene carbonate, etc.), amide solvents (N, N-dimethylformamide, N-dimethylacetamide), hydrochlorofluorocarbon solvents (HCFC-141b, N-dimethylacetamide, etc.), hydrochlorofluorocarbon solvents (HCFC-141b, N-dimethylformamide, N-dimethylacetamide, etc.), and the like, HCFC-225), Hydrofluorocarbon (HFCs) solvents (HFCs with 2-4, 5 and 6 or more carbon atoms), perfluorocarbon solvents (perfluoropentane, perfluorohexane), alicyclic hydrofluorocarbon solvents (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorine solvents (fluoroether, fluoropolyether, fluoroketone, fluoroalcohol), aromatic fluorosolvents (α, α, α -trifluorotoluene, hexafluorobenzene), and water. These may be used alone or in combination of two or more.

The amount of the solvent used may be about 1 to 50 wt% based on the total amount of the fluorine-based polymer and the binder resin monomer.

Examples of the curing assistant which can be contained in the composition of the present invention and improves the curability and the adhesiveness to a substrate of the photocurable composition containing a fluororesin include compounds having two or more mercapto groups (thiols) in one molecule. More specifically, there may be mentioned: hexanedithiol, decanedithiol, 1, 4-dimethylmercaptobenzene, butanediol diacetate, ethylene glycol dimercaptoacetate, trimethylolpropane trimercaptoacetate, butanediol dimercaptopropionate, trimethylolpropane trimercaptopropionate, trimethylolpropane trimercaptoacetate, pentaerythritol tetramercaptopropionate, pentaerythritol tetramercaptoacetate, trihydroxyethyl trimercaptopropionate, 1, 4-bis (3-mercaptobutyryloxy) butane (trade name: Carrenz (Karenz) MT BD1, manufactured by Showa Denko K.K.), pentaerythritol tetrakis (3-mercaptobutyrate) (trade name: Carrenz (Karenz) MT PE1, manufactured by Showa Denko K.K.), 1,3, 5-tris (3-mercaptobutyloxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione (trade name: karenz (Karenz) MT NR1, Showa Denko K.K.), and the like.

< skin film and laminate >

The film and the laminate having the film of the present invention can be obtained from the composition of the present invention. More specifically, the coating film of the present invention can be obtained by a step of forming a film of the composition of the present invention and a step of hardening the film. The film can be formed by coating, for example, and the film can be cured by one or more of drying, heating, and irradiation with active energy rays.

The method for applying the composition of the present invention to a substrate is not particularly limited, and there are spin coating, roll coating, slit coating, dipping, spray coating, gravure coating, reverse coating, bar coating, die coating, kiss coating, reverse kiss coating, air knife coating, curtain coating and the like.

Examples of substrates to be coated include: transparent glass substrates such as white plate glass, green plate glass, and silica-coated green plate glass; sheets and films made of synthetic resins such as polycarbonate, polyester, acrylic resin, vinyl chloride resin, polyamide resin, polyamideimide, polyimide, triacetate, and diacetate; transparent resin substrates for optical applications such as cycloolefin resins (trade names: Reno (ZEONOR), Rewinkle-resistant (ZEONEX), and Nippon Raynaud (Zeon) (stock.); trade names: Arton (Arton), and JSR (stock)), styrene methacrylate, polysulfone, alicyclic acrylic resins, and polyarylate, which include norbornene resins; metal substrates such as aluminum plates, copper plates, nickel plates, and stainless steel plates; other ceramic plate, semiconductor substrate with photoelectric conversion element; urethane rubber, styrene rubber, and the like.

These substrates may be pretreated, examples of which include: chemical treatment with a silane coupling agent or the like, sandblast treatment, corona discharge treatment, ultraviolet treatment, plasma treatment, ion plating, sputtering, vapor phase reaction method, vacuum evaporation, and the like.

Drying of the coated solution may be carried out at ambient temperatures to about 200 ℃.

In the present invention, a photopolymerization initiator is used, and therefore, after coating and drying, an optically active energy ray is irradiated by an active energy ray source to be cured.

The active energy ray source is not particularly limited, and examples thereof include a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, a gas laser, a solid laser, an electron beam irradiation device, and a Light Emitting Diode (LED) lamp, depending on the nature of the active energy ray polymerization initiator used.

In one embodiment of the present invention, a cured film is preferably obtained by curing a substrate and a photocurable composition comprising a fluorine-containing polymer (a), a 6-functional urethane (meth) acrylate (B) having a viscosity of 20,000mPa · s or less at 40 ℃, a photopolymerization initiator (C), and inorganic fine particles (D), wherein the photocurable composition has a Δ haze of 3 or less in evaluation method 1. The Δ haze is more preferably 2.5% or less.

[ evaluation method 1]

A cured film having a thickness of 5 μm comprising the photocurable composition was formed on a polyethylene terephthalate (PET) film substrate having a thickness of 100 μm.

The cured film-attached PET was measured for haze (haze) according to ASTM D1044, subjected to taber abrasion test under a load of 1kg (9.8N) and then measured for haze (%) according to ASTM D1044, and the difference Δ haze was determined.

Delta haze (%) (haze (%) after taber abrasion test under a load of 1kg (9.8N) applied thereto) (haze (%) before taber abrasion test)

In one embodiment of the present invention, a laminate including a cured film obtained by curing the composition of the present invention is also preferable. Further, an optical member including the laminate is also preferable.

That is, the use of the coating film (cured film) obtained from the composition of the present invention includes: automotive topcoats, hardcoats for antifouling purposes; a coating layer of a resin for optical use of lenses and the like; protective films for displays, coatings for protective films; coatings to prevent damage to the touch screen, and the like.

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Photocurable composition containing fluorine-based polymer

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