TW201710311A - Fluorine-containing compound, photocurable composition, coating liquid, composition for forming hard coat layer, and article - Google Patents

Abstract

Provided is a fluorine-containing compound that provides excellent anti-contamination properties (oil-based ink repellency and fingerprint removal properties) to an object (e.g., a barcode layer), and is highly compatible with non-fluorine-based photopolymerizable compounds. The fluorine-containing compound is represented by [D-O-{(CmF2mO)a(CnF2n-iHiO)b}-]dA. D is a C1-6 perfluoroalkyl group or the like; m is an integer from 1 to 6; a is an integer from 0 to 200; n is an integer from 1 to 6; i is an integer from 1 to 2n-1; b is an integer from 6 to 200; d is an integer of at least 1; and A is a d valent organic group having at least one polymerizable carbon-carbon double bond.

Description

Fluorine-containing compound, photocurable composition, coating liquid, composition for forming a hard coat layer, and article

The present invention relates to a fluorine-containing compound, a photocurable composition containing the fluorine-containing compound, a coating liquid, and a composition for forming a hard coat layer comprising the photocurable composition or the coating liquid, and An article of hard coating formed by the composition.

An optical article, a display, an optical recording medium, or the like usually has a hard coat layer on the surface to prevent scratching or the like. Further, the article preferably has antifouling property, that is, a property in which dirt (fingerprint, sebum, sweat, cosmetics, food, oily ink, etc.) is hard to adhere to the surface and can be easily removed even if the dirt adheres to the surface. For example, once the surface of the spectacle lens is attached with dirt, it will impede a good view and demonize the appearance. Once the surface of the optical recording medium is attached with dirt, the recording and reproduction of the signal may malfunction. Once the surface of the display is attached with dirt, the visibility is lowered, which adversely affects the operability of the display with the touch panel.

The following proposals have been made for a fluorine-containing compound which imparts antifouling properties to a hard coat layer. (1) A fluorine-containing compound obtained by reacting a triisocyanate, a perfluoropolyether having an active hydrogen and a poly(oxyperfluoroalkylene) chain, and a monomer having an active hydrogen and a polymerizable carbon-carbon double bond (Patent Document 1). (2) A fluorine-containing compound having a terminal CF ₃ -, an oxyfluoroalkyl group having one or more hydrogen atoms, a poly(oxyperfluoroalkylene) chain, and a (meth)acryl fluorenyl group (Patent Document 2). (3) A fluorine-containing compound having a poly(CH ₂ CF ₂ CF ₂ O) chain and a polymerizable carbon-carbon double bond (Patent Document 3). Prior art document patent document

Patent Document 1: Japanese Patent No. 3963169 Patent Document 2: International Publication No. 2015/056731 Patent Document 3: US Patent Application Publication No. 2014/0123876

Disclosure of the Invention Problems to be Solved by the Invention When a hard coat layer is formed using the fluorine-containing compound of (1) to (3), a non-fluorine-based photopolymerizable compound is usually used in combination. However, according to the study by the inventors of the present invention, the compatibility between the fluorine-containing compound of (1) and the non-fluorine-based photopolymerizable compound is insufficient. Therefore, when the composition for forming a hard coat layer containing the fluorine-containing compound (1) and the non-fluorine-based photopolymerizable compound is applied to the surface of the substrate, defects in the coating film are likely to occur, and the appearance of the hard coat layer is easily changed. difference. Further, precipitation is caused when the composition is stored at a low temperature in order to suppress the polymerization reaction. Hereinafter, the property in which the coating film is less likely to cause defects is referred to as "film forming property", and the property in which precipitation is less likely to occur during low-temperature storage is referred to as "low-temperature storage stability".

Since the fluorine-containing compound (2) has an oxyfluoroalkyl group having one or more hydrogen atoms, it is more compatible with the non-fluorine-based photopolymerizable compound than the fluorine-containing compound of (1). Therefore, the composition for forming a hard coat layer containing the fluorine-containing compound (2) and the non-fluorine-based photopolymerizable compound is excellent in film formability. However, the low temperature storage stability of the composition is still insufficient.

Since the fluorine-containing compound (3) has a poly(CH ₂ CF ₂ CF ₂ O) chain, it is more compatible with the non-fluorine-based photopolymerizable compound than the fluorine-containing compound of (2). Therefore, the composition for forming a hard coat layer containing the fluorine-containing compound (3) and the non-fluorine-based photopolymerizable compound is excellent in film formability and low-temperature storage stability. However, since the end of the fluorine-containing compound of (3) is FCH ₂ -, the antifouling property of the hard coat layer is insufficient.

An object of the present invention is to provide a fluorine-containing compound which is excellent in antifouling property (oily ink repellency and fingerprint soil removal property) and which has high compatibility with a non-fluorine-based photopolymerizable compound. A photocurable composition and a coating liquid which are excellent in antifouling properties and excellent in film formability and low-temperature storage stability, and can form a hard coat layer excellent in antifouling properties and have good film formability and low-temperature storage stability. A good composition for forming a hard coat layer; and an article having a hard coat layer excellent in antifouling property and appearance. Means to solve the problem

The present invention provides a fluorine-containing compound, a photocurable composition, a coating liquid, a composition for forming a hard coat layer, and a fluorine-containing compound of the article [1] having the following structures [1] to [13], which are as follows. (1) Compound shown: [DO-{(C _m F _2m O) _a (C _n F _2n-i H _i O) _b }-] _d A・・・(1) However, D is (R ^f1 ) _e -R ¹ - or R ^f2 -; R ^f1 is a perfluoroalkyl group having 1 to 6 carbon atoms; e is an integer of 1 to 3; and R ¹ is an (e+1)-valent hydrocarbon group having 1 to 6 carbon atoms; ^F2 is a perfluoroalkyl group having a carbon number of 1 to 6; m is an integer of 1 to 6; a is an integer of 0 to 200, and when a is 2 or more, (C _m F _2m O) _a may be different from each other by m More than C _m F _2m O; n is an integer from 1 to 6; i is an integer from 1 to 2n-1; b is an integer from 6 to 200, and (C _n F _2n-i H _i O) _b can be n And one or more of i or two different from each other: C _n F _2n-i H _i O; d is an integer of 1 or more; A is a d-valent organic having one or more polymerizable carbon-carbon double bonds The bonding order of a C _m F _2m O and b C _n F _2n-i H _i O is not limited.

[2] The fluorine-containing compound according to [1], wherein the compound represented by the above formula (1) is a compound represented by the following formula (11); [DO-{(C _m F _2m O) _a }-{(C _n F _2n-i H _i O) _b }-] _d A・・・(11) However, D, m, n, i, b, d, and A are D, m, n, i, b of the above formula (1) , d and A are the same; a is an integer from 1 to 200, and when a is 2 or more, (C _m F _2m O) _a may be composed of two or more kinds of C _m F _2m O different from each other; when a is 2 or more, {(C _m F _2m O) _a } is a block composed of a C _m F _2m O; {(C _n F _2n-i H _i O) _b } is b C _n F _2n-i H _i O The block formed. [3] The fluorine-containing compound according to [2], wherein the compound represented by the above formula (1) is a compound represented by the following formula (111); [DO-{(CF ₂ CF ₂ O) _a }-{CF ₂ CH ₂ O-(CF ₂ CFHO-CF ₂ CF ₂ CF ₂ CH ₂ O) _b/2-1 }-] _d A・・・(111) However, D, d and A and D, d of the above formula (1) Same as A, and b is an even number in b of the above formula (1).

[4] The fluorine-containing compound according to [1], wherein the compound represented by the above formula (1) is a compound represented by the following formula (12); [DO-{(C _n F _2n-i H _i O) _c }-{ (C _m F _2m O) _a }-{(C _n F _2n-i H _i O) _bc }-] _d A・・・(12) However, D, m, n, i, b, d, and A are D, m, n, i, b, d and A of the above formula (1) are the same; a is an integer from 1 to 200, and when a is 2 or more, (C _m F _2m O) _a can be different from m More than C _m F _2m O; c is 2 or 3, (C _n F _2n-i H _i O) _c may be one or more of n and i different from each other 2 or more C _n F _2n-i H _i O is composed; {(C _n F _2n-i H _i O) _c } is a block composed of c C _n F _2n-i H _i O; when a is 2 or more, {(C _m F _2m O _a } is a block composed of a C _m F _2m O; {(C _n F _2n-i H _i O) _bc } is a block composed of bc C _n F _2n-i H _i O .

[5] The fluorine-containing compound according to [1], wherein the compound represented by the above formula (1) is a compound represented by the following formula (112); [DO-(CH ₂ CF ₂ CF ₂ O) _b-1 -CH ₂ CF ₂ CH ₂ O-] _d A (112) However, b, d, and A are the same as b, d, and A of the above formula (1), and D is (R ^f1 ) _{e -} R ¹ -. [6] The fluorine-containing compound according to any one of [1] to [4] wherein the ratio of the a to the above b, represented by a/b, is from 20/1 to 1/20. [A] The fluorine-containing compound according to any one of [1] to [6] wherein the A is a d-valent organic group having one or more (meth) propylene fluorenyloxy groups. [8] The fluorine-containing compound according to any one of [1] to [7] wherein the fluorine-containing compound is a reaction product of the following three and has no unreacted isocyanate group: DO-{(C _m F _2m O _a (C _n F _2n-i H _i O) _b }-H represents a hydroxy compound, a hydroxy compound having one or more (meth) acryloxy groups, and a polyisocyanate having two or more isocyanate groups. [9] The fluorine-containing compound according to any one of [1] to [8], which has a number average molecular weight of 1,200 to 8,000.

[10] A photocurable composition comprising the fluorine-containing compound according to any one of [1] to [9], a photopolymerizable compound (except for the fluorine-containing compound), and a photopolymerization initiator ( However, it does not contain liquid media). [11] A coating liquid comprising the photocurable composition of [10] and a liquid medium. [12] A composition for forming a hard coat layer comprising the photocurable composition of [10] or the coating liquid of [11]. [13] An article characterized by having a substrate and a hard coat layer formed of a photocurable composition such as [10] or a coating liquid such as [11]. Effect of the invention

The fluorine-containing compound of the present invention can impart excellent antifouling properties to a target material and has high compatibility with a non-fluorine-based photopolymerizable compound. The photocurable composition and the coating liquid of the present invention can form an object excellent in antifouling property and have good film formability and low-temperature storage stability. The hard-coat layer forming composition of the present invention can form a hard coat layer excellent in antifouling properties and has good film formability and low-temperature storage stability. The article of the present invention has a hard coat layer excellent in antifouling properties and appearance.

In the present specification, the compound represented by the formula (1) is represented by the compound (1). Compounds represented by other formulas are also expressed in the same manner. In the present specification, the photocurable composition, the coating liquid, and the composition for forming a hard coat layer are collectively referred to as "composition". In the present specification, the "polymerizable carbon-carbon double bond" is also referred to as "polymerizable double bond" unless otherwise stated. The meanings of the following terms in this manual are as follows. "Fluoroalkylene" means a group in which a part or all of a hydrogen atom of an alkyl group is substituted by a fluorine atom, and "perfluoroalkylene group" means a group in which all hydrogen atoms of an alkyl group are substituted by a fluorine atom. "Perfluoroalkyl" means a group in which all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms. "(Meth)acrylonitrile" is a generic term for propylene fluorenyl and methacryl fluorenyl. "Object" means an object to which antifouling property is imparted. Examples of the object include a hard coat layer, a liquid-repellent layer, a release layer, and a molded article.

[Fluorine-Containing Compound] The fluorine-containing compound of the present invention is the compound (1). [DO-{(C _m F _2m O) _a (C _n F _2n-i H _i O) _b }-] _d A・・・(1)

(About D) D is (R ^f1 ) _e -R ¹ - or R ^f2 -. By the compound (1) having D, one of the ends of the compound (1) can be made into CF ₃ -. Therefore, the compound (1) can sufficiently impart antifouling properties to an object (hard coat layer or the like).

R ^f1 is a perfluoroalkyl group having 1 to 6 carbon atoms. The perfluoroalkyl group may be linear or branched. From the viewpoint of sufficiently imparting antifouling properties to the object, R ^f1 is preferably a perfluoroalkyl group having 1 to 3 carbon atoms, CF ₃ - or CF ₃ CF ₂ - is preferable, and CF ₃ - is particularly preferable. e is an integer from 1 to 3. From the viewpoint of the controllability of the compound (1), e is preferably 1 or 2, and particularly preferably 1. R ¹ is an (e+1)-valent hydrocarbon group having 1 to 6 carbon atoms. From the viewpoint of the controllability of the compound (1), R ^{1 is} preferably -CH ₂ -, >CH- or -CH ₂ CH ₂ -, and -CH ₂ - or -CH ₂ CH ₂ - is particularly preferred.

(R ^f1 ) _{e -} R ¹ - may, for example, be the following groups (g1) to (g3). R ^f1 (CH ₂ ) _h1 -・・・(g1), (R ^f1 ) ₂ CH(CH ₂ ) _h2 -・・・(g2), (R ^f1 ) ₃ C(CH ₂ ) _h3 -・・・( G3). However, h1 is an integer from 1 to 3, h2 is an integer from 0 to 2, and h3 is an integer from 1 to 3. From the viewpoint of the controllability of the compound (1), (R ^f1 ) _e -R ¹ - is preferably CF ₃ CH ₂ -, (CF ₃ ) ₂ CH-, CF ₃ CF ₂ CH ₂ -, CF ₃ CF ₂ CF ₂ CH ₂ CH ₂ -, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ -.

R ^f2 is a perfluoroalkyl group having 1 to 6 carbon atoms. The perfluoroalkyl group may be linear or branched. From the viewpoint of sufficiently imparting antifouling properties to the object, the carbon number of R ^f2 is preferably from 1 to 3, preferably 1 or 2, more preferably 1 or more. From the viewpoint of the ease of production of the compound (1), R ^{f2 is} preferably CF ₃ -, CF ₃ CF ₂ -, CF ₃ CF ₂ CF ₂ -.

(About (C _m F _2m O) _a ) (C _m F _2m O) _a can further impart antifouling properties to an object. m is an integer from 1 to 6. From the viewpoint of sufficiently imparting antifouling properties to the object, m is preferably 1 to 3, and 1 or 2 is particularly preferred. When m is 2 or more, C _m F _2m may be linear or branched. From the viewpoint of sufficiently imparting antifouling properties to the object, it is preferably a linear shape. Specific examples of C _m F _2m O include CF ₂ O, CF ₂ CF ₂ O, CF ₂ CF ₂ CF ₂ O, CF(CF ₃ )CF ₂ O, CF ₂ CF ₂ CF ₂ CF ₂ O, and the like.

a is an integer from 0 to 200. When a is 2 or more, (C _m F _2m O) _a may be composed of two or more kinds of C _m F _2m O in which m is different from each other. From the viewpoint of sufficiently imparting antifouling properties to the object, a is preferably an integer of 3 or more, and an integer of 4 or more is preferable, and an integer of 5 or more is particularly preferable. When the number average molecular weight of the compound (1) is too large, the number of polymerizable double bonds per unit molecular weight of the compound (1) is decreased and the abrasion resistance of the object is lowered, and further, the compound (1) and other components are The compatibility is good. From the above viewpoint, a is preferably an integer of 100 or less, and an integer of 80 or less is preferable, and an integer of 60 or less is particularly preferable.

M the presence of two or more mutually different _{C m F 2m O (C m} F 2m O) a , the bond order of the C _m F _2m O is not limited, may be bonded may also be a random interlaced bond , or can be bonded into a block shape. For example, when CF ₂ O and CF ₂ CF ₂ O are present, CF ₂ O and CF ₂ CF ₂ O may be randomly or staggered, or may be a block composed of a plurality of CF ₂ O and a plurality of CF _{2 .} The block formed by CF ₂ O is bonded. Further, for example, when CF ₂ CF ₂ O and CF ₂ CF ₂ CF ₂ CF ₂ O are interlaced, (C _m F _2m O) _a can be expressed as (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _a/2 . At this time, it is indicated that a/2 (CF ₂ CF ₂ O) and a/2 (CF ₂ CF ₂ CF ₂ CF ₂ O) are arranged in a staggered manner. In addition, a in this case is an even number.

From the viewpoint of imparting sufficient antifouling property to the object, (C _m F _2m O) _{a is} preferably {(CF ₂ O) _a1 (CF ₂ CF ₂ O) _a2 } (however, a1 is an integer of 1 or more, a2 For an integer of 1 or more, a1+a2 is an integer of 2 to 200, and the bonding order of a1 CF ₂ O and a2 CF ₂ CF ₂ O is not limited). At this time, CF ₂ O and CF ₂ CF ₂ O are preferably randomly bonded. Since {(CF ₂ O) _a1 (CF ₂ CF ₂ O) _a2 } has good mobility, the object is excellent in lubricity. In particular, (CF ₂ O) _{a1 has} a carbon number of 1 and is a group having an oxygen atom, so that the mobility is preferred.

The compound (1) can be produced as a mixture of a plurality of compounds having a different amount of (C _m F _2m O) _a . At this time, the average value of a as the mixture is preferably 2 to 100, and particularly preferably 4 to 80.

(About (C _n F _2n-i H _i O) _b ) (C _n F _2n-i H _i O) _b Since one part of the fluorine atom can be substituted by a hydrogen atom, compared to (C _m F _2m O) _a , The polarization due to the hydrogen atom is large, and the compatibility of the compound (1) with the non-fluorine-based photopolymerizable compound is imparted. Further, since one of the fluorine atoms can be substituted by a hydrogen atom, the mobility of the molecule is higher than that of (C _m F _2m O) _a , and the object is lubricated.

n is an integer from 1 to 6. From the viewpoint of sufficiently imparting antifouling properties to the object, n is preferably 1 to 3, and 1 or 2 is particularly preferable. When n is 2 or more, C _n F _2n-i H _i O may be linear or branched. From the viewpoint of sufficiently imparting antifouling properties to the object, it is preferably a linear shape. i is an integer from 1 to 2n-1. From the viewpoint of sufficiently imparting compatibility between the compound (1) and the non-fluorine-based photopolymerizable compound, i is preferably an integer of 2 or more (except when n is 1). From the viewpoint of sufficiently imparting antifouling properties to the object, i is preferably an integer of n or less. Specific examples of C _n F _2n-i H _i O include CFHCF ₂ O, CH ₂ CF ₂ O, CF ₂ CH ₂ O, CH ₂ CF ₂ CF ₂ O, CH ₂ CF ₂ CH ₂ O, and CF ₂ CF _{2 .} CH ₂ O, CF(CF ₃ )CH ₂ O, CF ₂ CF ₂ CF ₂ CH ₂ O, CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ O, and the like.

b is an integer from 6 to 200. (C _n F _2n-i H _i O) _b may be composed of two or more C _n F _2n-i H _i O in which one or both of n and i are different from each other. From the viewpoint of sufficiently imparting compatibility between the compound (1) and the non-fluorine-based photopolymerizable compound, b is preferably an integer of 6 or more, and an integer of 10 or more is preferable, and an integer of 15 or more is particularly preferable. When the number average molecular weight of the compound (1) is too large, the compound (1) has a decrease in the number of polymerizable double bonds per unit molecular weight and the abrasion resistance of the object is lowered, and b is an integer of 100 or less. Preferably, an integer of 80 or less is preferred, and an integer of 60 or less is particularly preferred.

And i n the presence of one or both of the mutually different two or more kinds of _{C n F 2n-i H i} O b in the _{(C n F 2n-i H} i O), each of the C _n F _2n-i H _i The order of bonding of O is not limited. For example, when there are two kinds of C _n F _2n-i H _i O, the two C _n F _2n-i H _i O may be randomly configured or staggered, or may be one of a plurality of C _n F _2n-i H _i The block formed by O is a block of a plurality of other C _n F _2n-i H _i O. For example, when CF ₂ CFHO and CF ₂ CF ₂ CF ₂ CH ₂ O are interlaced, (C _n F _2n-i H _i O) _{b can} be (CF ₂ CFHO-CF ₂ CF ₂ CF ₂ CH ₂ O ) _b/2 indicates. At this time, it is shown that b/2 (CF ₂ CFHO) and b/2 (CF ₂ CF ₂ CF ₂ CH ₂ O) are arranged in a staggered manner. In addition, b in this case is an even number.

The compound (1) can be produced as a mixture of a plurality of compounds having different amounts of (C _n F _2n-i H _i O) _b . At this time, the average value of b as a mixture is preferably 6 to 100, and particularly preferably 10 to 80.

(About A) A is a d-valent organic group having one or more polymerizable double bonds. d is an integer of 1 or more, and preferably 1 to 4. From the viewpoint of the ease of the compound (1), it is preferably 1 or 2, and more preferably 2 from the viewpoint of sufficiently imparting antifouling properties to the object.

The polymerizable double bond can be reacted with the photopolymerizable compound described later in the composition by light irradiation to impart abrasion resistance to the object. Examples of the group having a polymerizable double bond include a (meth)acryl fluorenyl group, a vinyl group, an allyl group, a styryl group, and a maleinium group. From the viewpoint of sufficiently imparting abrasion resistance to the object, a (meth) acrylonitrile group is preferred, and an acryl oxime group is particularly preferred. The number of polymerizable double bonds is preferably from 1 to 8 per molecule of the compound (1), preferably from 1 to 4, and particularly preferably 1.

The compound (1) is preferably a reaction product of a compound (x) which is a monohydroxy compound described later and a compound having a functional group capable of reacting with a hydroxyl group and a polymerizable double bond (the compound (w) described later), or preferably the following three Reaction product: a compound (x) to be described later, a compound having an active hydrogen group and a polymerizable double bond (such as a compound (y) described later), and a compound having two or more functional groups capable of reacting with an active hydrogen group ( Polyisocyanate (z), etc.) will be described later. The compound having a functional group capable of reacting with the above hydroxyl group and a polymerizable double bond is preferably a compound having one functional group and one to three (meth)acryloxycarbonyl groups, and examples thereof include (meth)acrylofluorene chloride, Glycidyl methacrylate, isocyanate alkyl (meth) acrylate, and the like. The compound having the above active hydrogen group-containing and polymerizable double bond is preferably a compound having one hydroxyl group and one to three (meth)acryloxycarbonyl groups, and examples thereof include hydroxyalkyl (meth)acrylate and trishydroxyl. Propane di(meth)acrylate, neopentyl alcohol triacrylate, and the like. The compound having two or more functional groups reactive with the active hydrogen-containing group is preferably a polyisocyanate having 2 to 6 isocyanate groups, and preferably a polyisocyanate having 2 or 3 isocyanate groups, particularly preferably a triisocyanate. A is preferably a moiety other than the compound (x) moiety (the portion other than the hydrogen atom of the hydroxyl group) of the above reaction product.

Specific examples of A can be enumerated as follows. -C(=O)C(R)=CH ₂ , -CH ₂ CH(OH)CH ₂ OC(=O)C(R)=CH ₂ , -C(=O)NHCH ₂ CH ₂ OC(=O ) C(R) = CH ₂ . -C(=O)NH-Rz-(NHC(=O)O-Ry) ₂ (-C(=O)NH) ₂ -Rz-NHC(=O)O-Ry However, R is a hydrogen atom or a Ry is a residue in which a hydroxyl group is removed from a monohydroxy compound in a compound (y) having a polymerizable double bond and a hydroxyl group, and Rz is a residue in which three isocyanate groups are removed from a triisocyanate in a polyisocyanate (z) to be described later. .

(Arrangement of C _m F _2m O and C _n F _2n-i H _i O) In the compound (1), when a is an integer of 1 or more, a C _m F _2m O and b C _n F _2n-i The bonding order of H _i O is not limited. For example, C _m F _2m O and C _n F _2n-i H _i O may be randomly or staggered, or may be composed of one C _m F _2m O or a plurality of C _m F _2m O blocks and The blocks formed by C _n F _2n-i H _i O are linked.

The compound (1) having a block composed of a plurality of C _n F _2n-i H _i O and having a C _m F _2m O or a block composed of a plurality of C _m F _2m O as required may be enumerated as Compounds (11) to (14). [DO-{(C _m F _2m O) _a }-{(C _n F _2n-i H _i O) _b }-] _d A・・・(11) [DO-{(C _n F _2n-i H _i O) _c }-{(C _m F _2m O) _a }-{(C _n F _2n-i H _i O) _bc }-] _d A・・・(12) [DO-{(C _n F _{2n -i} H _i O) _b-1 }-{(C _m F _2m O) _a }-{C _m-1 F _2(m-1) CH ₂ O}-] _d A・・・(13) [DO -{(C _n F _2n-i H _i O) _b }-] _d A・・・(14) However, D, m, n, i, b, d, and A are D and m of the above formula (1) , n, i, b, d, and A are the same, a is an integer from 1 to 200, and when a is 2 or more, (C _m F _2m O) _a may be composed of two or more types of C _m F _2m O. c is 2 or 3, and (C _n F _2n-i H _i O) _c may be composed of two or more C _n F _2n-i H _i O in which one or both of n and i are different from each other. When a is 2 or more, {(C _m F _2m O) _a } is a block composed of a C _m F _2m O . {(C _n F _2n-i H _i O) _b } is a block composed of b C _n F _2n-i H _i O . {(C _n F _2n-i H _i O) _c } is a block composed of c C _n F _2n-i H _i O . {(C _n F _2n-i H _i O) _bc } is a block composed of bc C _n F _2n-i H _i O . {(C _n F _2n-i H _i O) _{b -1} } is a block composed of b-1 C _n F _2n-i H _i O .

From the viewpoint of sufficiently imparting antifouling properties to the object, the compound (11) is preferably used as the compound (1). From the viewpoint of the balance between the antifouling property of the object and the compatibility of the compound (1) with the non-fluorine photopolymerizable compound, the compound (12) is preferably used as the compound (1). The ratio of a to b expressed by a/b is preferably 20/1 to 1/20, and particularly preferably 10/1 to 1/10. When a/b is within the above range, the balance between the antifouling property of the object and the compatibility of the compound (1) with the non-fluorine photopolymerizable compound is preferable.

(Quantitative average molecular weight of the compound (1)) The number average molecular weight of the compound (1) is preferably 1,200 to 8,000, more preferably 1,200 to 7,000, and particularly preferably 1,200 to 5,000. When the number average molecular weight is within this range, the antifouling property and the abrasion resistance of the object (such as a hard coat layer) can be sufficiently imparted, and the compatibility of the compound (1) with other components in the composition is excellent. The number average molecular weight of the compound (1) is a number average molecular weight in terms of polymethyl methacrylate determined by gel permeation chromatography (GPC).

(Manufacturing Method of Compound (1)) The compound (1) can be produced, for example, by reacting the compound (x) with the precursor of A. DO-{(C _m F _2m O) _a (C _n F _2n-i H _i O) _b }-H・・・(x) However, D, m, a, n, i, and b are the same as the above formula (1) ) D, m, a, n, i, and b are the same.

Since the compound (x) is a monohydroxy compound, when the precursor is a monofunctional compound before the reaction with the compound (x), the compound (1) wherein d is 1 can be produced. When the precursor before A is a polyfunctional compound, the compound (1) wherein d is 2 or more can be produced. Further, when the precursor of A is two or more kinds of compounds, the compound (1) wherein d is 1 or the compound (1) wherein d is 2 or more can be produced, and the compound (1) wherein d is 1 and the ratio of d to 2 or more can be produced. a mixture of compounds (1).

<Method for Producing Compound (1) (Part 1)> The compound (1) can be produced, for example, by reacting a compound (x) with a compound (w) having a group capable of reacting with a hydroxyl group and polymerizing Sexual double bonds. The compound (w) is a compound having one or more reactive groups capable of reacting with a hydroxyl group and having one or more polymerizable double bonds. When the number of groups capable of reacting with a hydroxyl group is one, a compound (1) wherein d is 1 can be produced, and when two or more groups capable of reacting with a hydroxyl group are used, a compound (1) wherein d is 2 or more can be produced. The number of the compounds (w) capable of reacting with the hydroxyl group is preferably one or two, and particularly preferably one. The number of polymerizable double bonds is preferably from 1 to 3, and more preferably one. The compound (w) is preferably a compound having a (meth) propylene fluorenyloxy group, and particularly preferably a compound having an acryloxy group. Examples of the functional group reactive with a hydroxyl group include a carboxyl group and a reactive derivative group (such as a halogenated group), an epoxy group, and an isocyanate group. The compound (w) may, for example, be (meth)acrylofluorene chloride, alkylene oxide (meth)acrylate or isocyanate alkyl (meth)acrylate. Specific examples of the compound (w) include the following compounds. Cl-C(=O)C(R)=CH ₂ , Ep-CH ₂ OC(=O)C(R)=CH ₂ , OCN-CH ₂ CH ₂ OC(=O)C(R)=CH ₂ . However, R is a hydrogen atom or a methyl group, and Ep is an epoxy group.

A basic compound is used when reacting a hydroxyl group with ruthenium chloride. When the hydroxyl group is reacted with an isocyanate group, an urethane ethyl carboxylate catalyst is used. When the compound (1) is produced, an additive required for production (hereinafter also referred to as "additive for manufacturing") can also be used. The additive for production may, for example, be a polymerization inhibitor or the like. Further, when the unreacted compound (x) remains in the reaction product, the compound (x) remains in the finally obtained compound (1). Since the compound (x) has low compatibility with other components, the composition may be cloudy when the compound (x) remains in the resulting compound (1). Therefore, it is preferred to react the compound (x) with the excess equivalent compound (w) such that substantially all of the compound (x) is reacted with the compound (w), and the unreacted compound is removed from the reaction product as required (w) ).

<Method for Producing Compound (1) (Part 2)> The compound (1) can also be produced by combining a compound (x) with a compound having a polymerizable double bond and a reactive group through a polyfunctional compound capable of linking two compounds. . The polyfunctional compound is preferably a compound having two or more isocyanate groups (hereinafter referred to as polyisocyanate (z)), and a compound having a polymerizable double bond and a reactive group is a compound having a polymerizable double bond and an active hydrogen group. (The following table is a compound (y)).

The compound (y) is a compound having one or more active hydrogen groups and one or more polymerizable double bonds, and examples of the active hydrogen group include a hydroxyl group, a primary amine group, a secondary amine group, and a carboxyl group. The active hydrogen group is preferably a hydroxyl group. The number of active hydrogen-containing groups in one molecule is preferably 1 or 2, and 1 is particularly preferable. The number of polymerizable double bonds in one molecule is preferably from 1 to 3, and one is particularly preferred. The compound (y) is preferably a compound having one hydroxyl group and one to three (meth)acryloxycarbonyl groups, and examples thereof include hydroxyalkyl (meth)acrylate and trimethylolpropane di(meth)acrylate. Neopentyl triol (meth) acrylate, and the like. Examples of the compound having an active hydrogen group other than a hydroxyl group include an amine alkyl (meth)acrylate such as 2-aminoethyl acrylate. The polyisocyanate (z) is a compound having two or more isocyanate groups, preferably a compound having 2 to 4 isocyanate groups, and particularly preferably a triisocyanate.

Since the polyisocyanate (z) is polyfunctional, even if the compound (y) is monofunctional, the reaction product of the compound (x), the compound (y) and the polyisocyanate (z) can easily be a mixture of a plurality of compounds. In the reaction product, the reaction product having the residue of the compound (x) and the residue of the compound (y) is the compound (1), and the compound having only one of the residues is the reaction of the non-compound (1). Product. The reaction product composed of the residue of the compound (x) and the residue of the compound (y) and the residue of the polyisocyanate (z) is hereinafter referred to as a by-product (v). The compound having a residue of the compound (y) in the by-product (v) is a compound having a polymerizable double bond, and is a photopolymerizable compound, even if it is contained in the compound (1), the physical properties of the photocurable composition. The impact is still less. On the other hand, since the compound having the residue of the compound (x) in the by-product (v) is a compound having no polymerizable double bond, the photocurable composition is the same as the compound (1) containing the unreacted compound (x). The influence of physical properties is greater. Therefore, in this production method, it is preferred to use a method of generating by-product (v) less, and it is particularly preferable to use a compound having a residue of the compound (x) in the by-product (v) to produce a lesser method. Specifically, compared with the method of mixing the compound (x), the compound (y) and the polyisocyanate (z) 3, the following method is preferred: one of the compound (x) or the compound (y) is excessive The equivalent polyisocyanate (z) is reacted to produce an intermediate reaction product having an isocyanate group, and then the other of the compound (x) or the compound (y) is reacted to form a reaction product having no isocyanate group. In particular, it is preferred to react the compound (x) with an excess equivalent of the polyisocyanate (z) to produce an intermediate reaction product having an isocyanate group, and then to use an equivalent equivalent or more of the compound (y) for the intermediate reaction product. The reaction is carried out to produce a reaction product which does not have an isocyanate group. Further, in order to suppress the formation of by-product (v), it is preferred to use a polyisocyanate (z) having an isocyanate group number of 3 or more.

When the compound (y) is a monohydroxy compound and the polyisocyanate (z) is a triisocyanate, the following compounds may be formed in the case of the reaction product. Among these, the compound represented by the formula (1-1) and the formula (1-2) is the compound (1), and the compound represented by the formula (2) and the formula (3) is a by-product (v). Rx-C(=O)NH-Rz-(NHC(=O)O-Ry) ₂・・・(1-1) (Rx-C(=O)NH) ₂ -Rz-NHC(=O)O -Ry・・・(1-2) (Rx-C(=O)NH) ₃ -Rz・・・(2) Rz-(NHC(=O)O-Ry) ₃・・・(3) Rx has removed the residue of the hydroxyl group from the compound (x), the Ry has removed the residue of the hydroxyl group from the compound (y) of the monohydroxy compound, and the Rz has removed the residue of the isocyanate group from the polyisocyanate (z) of the triisocyanate. .

The reaction product obtained by the above production method usually contains a mixture of the compound (1-1) and the compound (1-2), and may optionally contain the compound (2) or the compound (3). As described above, the content of the compound (2) is not particularly high, and the content of the compound (3) does not have much problem to a certain extent. The fluorine-containing compound contained in the photocurable composition of the present invention may be a fluorine-containing compound of the above mixture. Hereinafter, the photocurable composition containing the fluorine-containing compound of the present invention also represents a photocurable composition containing the above reaction product.

In the above production method, when the compound (x) or the compound (y) is reacted with the polyisocyanate (z) or an intermediate reaction product having the above-mentioned isocyanate group, it can be carried out in the presence of a reaction catalyst such as a urethane conversion catalyst. reaction. Further, the reaction may be carried out in the presence of an additive for production such as a polymerization inhibitor. Further, when the unreacted compound (x) remains in the compound (1), the compound (x) remains in the finally obtained composition. Since the compound (x) has low compatibility with other components, when the compound (x) remains in the composition, the composition may become cloudy. Therefore, in order to prevent the unreacted compound (x) from remaining, it is preferred to first react the compound (x) with the excess polyisocyanate (z), and after completely consuming the compound (x), it is equivalent to the equivalent of the remaining isocyanate group. The compound (y) is reacted.

The mass ratio of the compound (x) to the compound (y) may be appropriately set in accordance with the desired properties (antifouling property, abrasion resistance, etc.) of the object. From the viewpoint of balance between the antifouling property and the abrasion resistance of the object to be applied, the mass ratio of the compound (x) to the compound (y) is preferably 9:1 to 5:5, and 8:2 to 6:4 is particularly preferable. .

<Compound (x)> The compound (x) may, for example, be a compound (x1) to (x4). DO-{(C _m F _2m O) _a }-{(C _n F _2n-i H _i O) _b }-H・・・(x1) DO-{(C _n F _2n-i H _i O) _c }-{(C _m F _2m O) _a }-{(C _n F _2n-i H _i O) _bc }-H・・・(x2) DO-{(C _n F _2n-i H _i O) _{b -1} }-{(C _m F _2m O) _a }-{C _m-1 F _2(m-1) CH ₂ O}-H・・・(x3) DO-{(C _n F _2n-i H _i O) _b }-H・(x4) However, D, m, a, n, i, and b are the same as D, m, a, n, i, and b of the above formulas (11) to (14).

<Method for Producing Compound (x1) (Part 1)> The compound (x1) can be obtained, for example, by subjecting the compound (21) to the compound (20) in the presence of a basic compound to obtain the compound (x11). DO-{(C _m F _2m O) _a }-C _m-1 F _2(m-1) CH ₂ -OH・(20) CF ₂ =CF-O-CF ₂ CF ₂ CF ₂ CH ₂ - OH・・・(21) DO-{(C _m F _2m O) _a }-{C _m-1 F _2(m-1) CH ₂ O-(CF ₂ CFHO-CF ₂ CF ₂ CF ₂ CH ₂ O ) _(b-1)/2 }-H・・・(x11) However, b is an odd number of 7 or more.

Specific examples of the compound (20) are as follows. CF ₃ -O-{(CF ₂ CF ₂ O) _a }-CF ₂ CH ₂ -OH, CF ₃ -O-{(CF ₂ O) _a1 (CF ₂ CF ₂ O) _a2 }-CF ₂ CH ₂ - OH, CF ₃ CF ₂ CF ₂ -O-{(CF ₂ CF ₂ CF ₂ O) _a }-CF ₂ CF ₂ CH ₂ -OH, CF ₃ CF ₂ CF ₂ -O-{(CF(CF ₃ )CF ₂ O) _a }-CF(CF ₃ )CH ₂ -OH, CF ₃ -O-{(CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _(a-1)/2 -CF ₂ CF ₂ O}-CF ₂ CF ₂ CF ₂ CH ₂ -OH (except that a is an odd number of 3 or more).

The compound (20) can be produced by the method described in, for example, Japanese Laid-Open Patent Publication No. 2009-116947, and the like. The compound (21) can be produced, for example, by reducing a compound (22) with a reducing agent (sodium borohydride or the like). CF ₂ =CF-O-CF ₂ CF ₂ CF ₂ C(=O)OCH ₃・・・(22)

<Method for Producing Compound (x1) (Part 2)> The compound (x1) can be obtained, for example, in the form of the compound (x12) by the following method. The compound (24) can be obtained by subjecting the compound (23) (2,2,3,3-tetrafluorooxetane) to the above compound (20) in the presence of a basic compound.

[Chemical 1]

DO-{(C _m F _2m O) _a }-{C _m-1 F _2(m-1) CH ₂ O-(CH ₂ CF ₂ CF ₂ O) _b-2 }-CH ₂ CF ₂ C(= O) F (24) The compound (23) can be produced by the method described in International Publication No. 2005/080365.

Compound (26) can be obtained by reacting compound (25) with the aforementioned compound (24). HOR ²・・・(25) DO-{(C _m F _2m O) _a }-{C _m-1 F _2(m-1) CH ₂ O-(CH2CF ₂ CF ₂ O) _b-2 }-CH ₂ CF ₂ C(=O)OR ² (26) However, R ² is an alkyl group.

The compound (x12) can be obtained by reducing the aforementioned compound (26) with a reducing agent (sodium borohydride or the like). DO-{(C _m F _2m O) _a }-{C _m-1 F _2(m-1) CH ₂ O-(CH ₂ CF ₂ CF ₂ O) _b-2 -CH ₂ CF ₂ CH ₂ O} -H・・・(x12)

<Method for Producing Compound (x2) (Part 1)> The compound (x2) can be used in the same manner as the method for producing the compound (x1), for example, in addition to the compound (27). The manner is obtained in the form of the compound (x21). DO-{(C _n F _2n-i H _i O) _c }-{(C _m F _2m O) _a }-C _m-1 F _2(m-1) CH ₂ -OH・・・(27) DO -{(C _n F _2n-i H _i O) _c }-{(C _m F _2m O) _a }-{C _m-1 F _2(m-1) CH ₂ O-(CF ₂ CFHO-CF ₂ CF ₂ CF ₂ CH ₂ O) _(bc-1)/2 }-H・(x21) However, bc-1 is an even number of 2 or more.

Specific examples of the compound (27) are as follows. CF ₃ CF ₂ CF ₂ -O-{CFHCF ₂ O-CH ₂ CF ₂ O}-{(CF ₂ O) _a1 (CF ₂ CF ₂ O) _a2 }-CF ₂ CH ₂ -OH. The compound (27) can be produced by the method described in Patent Document 2 or the like.

(Manufacturing Method of Compound (x2) (Part 2)> The compound (x2) can be used, for example, in place of the above-mentioned compound (20), and can be used in the same manner as in the production method (2) of the compound (x1). The manner is obtained in the form of the compound (x22). DO-{(C _n F _2n-i H _i O) _c }-{(C _m F _2m O) _a }-{C _m-1 F _2(m-1) CH ₂ O-(CH ₂ CF ₂ CF ₂ O) _bc-2 -CH ₂ CF ₂ CH ₂ O}-H・・・(x22)

<Method for Producing Compound (x3) (Part 1)> The compound (x3) can be obtained, for example, in the form of the compound (x31) by the following method. Compound (29) can be obtained by subjecting compound (21) to addition reaction of compound (28) in the presence of a basic compound. D-OH · · · (28 ) DO - {(CF 2 CFHO-CF 2 CF 2 CF 2 CH 2 O) (b-2) / 2} -H · · · (29) However, D is (R ^f1 ) _e -R ¹ -, b is an even number of 6 or more.

Specific examples of the compound (28) are as follows. CF ₃ CH ₂ -OH, (CF ₃ ) ₂ CH-OH, CF ₃ CF ₂ CH ₂ -OH, CF ₃ CF ₂ CF ₂ CH ₂ CH ₂ -OH, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ -OH.

The compound (29) is reacted with the compound (30) to obtain a compound (x31). L-CH ₂ C _m-1 F _2(m-1) O-{(C _m F _2m O) _a }-C _m-1 F _2(m-1) CH ₂ -OH・(・)(30) DO -{(CF ₂ CFHO-CF ₂ CF ₂ CF ₂ CH ₂ O) _(b-2)/2 -CH ₂ C _m-1 F _2(m-1) O}-{(C _m F _2m O) _a }-{C _m-1 F _2(m-1) CH ₂ O}-H・・・(x31) However, L is a leaving group. L may, for example, be a toluenesulfonyl group, a trifluoromethanesulfonyl group or a nonafluorobutylsulfonyl group.

The compound (30) can be produced by the method described in JP-A-2011-116947 or the like, and the monohydroxy group is substituted with the cleavable group L. HO-CH ₂ C _m-1 F _2(m-1) O-{(C _m F _2m O) _a }-C _m-1 F _2(m-1) CH ₂ -OH・・・(31)

<Method for Producing Compound (x3) (Part 2)> The compound (x3) can be obtained, for example, in the form of the compound (x32) by the following method. The compound (32) can be obtained by subjecting the above compound (23) to the above compound (28) in the presence of a basic compound. DO-{(CH ₂ CF ₂ CF ₂ O) _b-3 }-CH ₂ CF ₂ C(=O)F・・・(32)

The compound (33) can be obtained by reacting the aforementioned compound (25) with the aforementioned compound (32). DO-{(CH ₂ CF ₂ CF ₂ O) _b-3 }-CH ₂ CF ₂ C(=O)OR ²・・・(33)

The compound (34) can be obtained by reducing the aforementioned compound (33) with a reducing agent (sodium borohydride or the like). DO-{(CH ₂ CF ₂ CF ₂ O) _b-3 -CH ₂ CF ₂ CH ₂ O}-H・・・(34)

The compound (34) is reacted with the aforementioned compound (30) to obtain a compound (x32). DO-{(CH ₂ CF ₂ CF ₂ O) _b-3 -CH ₂ CF ₂ CH ₂ O-CH ₂ C _m-1 F _2(m-1) O}-{(C _m F _2m O) _a } -{C _m-1 F _2(m-1) CH ₂ O}-H・・・(x32) However, L is a leaving group.

(Manufacturing Method of Compound (x4)) The compound (x4) can be produced, for example, by the method for producing the compound (29) of the compound (x3) or the method for producing the compound (x3) (these 2) The compound (34) is produced in the same manner as the compound (x41) or the compound (x42). DO-{(CF ₂ CFHO-CF ₂ CF ₂ CF ₂ CH ₂ O) _b/2 }-H・(x41) DO-{(CH ₂ CF ₂ CF ₂ O) _b-1 -CH ₂ CF ₂ CH ₂ O}-H・・・(x42)

(Quantitative average molecular weight of the compound (x)) The number average molecular weight of the compound (x) is preferably 1,000 to 6,000, preferably 1,000 to 5,000, more preferably 1,200 to 4,000. When the number average molecular weight of the compound (x) is within this range, the antifouling property of the object can be sufficiently imparted, and the compound (x) is excellent in compatibility with other components in the composition. The number average molecular weight of the compound (x) can be determined by comparing the elution time of GPC with polymethyl methacrylate or comparing the internal standard substance with the compound (x) by a nuclear magnetic resonance apparatus (NMR). The integral ratio of the terminal functional groups.

<Compound (y)> The compound (y) is a compound having a polymerizable double bond and an active hydrogen group as described above. The compound (y) is particularly preferably a compound having one hydroxyl group and one (meth) acryloxy group. Specific examples thereof include hydroxyalkyl (meth)acrylate, polyoxyalkylene glycol mono(meth)acrylate, and the like. The compound (y) is preferably a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 2 to 10 carbon atoms, particularly preferably a hydroxyalkyl acrylate having a linear hydroxyalkyl group having a hydroxyl group at the terminal.

Specific examples of the compound (y) are as follows. _{HOCH 2 CH 2 OC (= O} ) C (R) = CH 2, HO (CH 2 CH 2 O) j -C (= O) C (R) C = CH 2, CH 3 CH (OH) CH 2 OC (=O)C(R)C=CH ₂ , HOCH ₂ CH=CH ₂ , HO(CH ₂ ) _k CH=CH ₂ . However, R is a hydrogen atom or a methyl group, j is an integer of 2 to 10, and k is an integer of 2 to 20.

<Polyisocyanate (z)> The polyisocyanate (z) is a compound having two or more isocyanate groups. The isocyanate group is used to react with the hydroxyl group of the compound (x) or the active hydrogen group of the compound (y) to incorporate the structure of the polyisocyanate (z) into a part of the structure of the compound (1). The number of isocyanate groups is preferably 2 to 4, and 3 is particularly preferred.

The polyisocyanate (z) is preferably an aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate in which an isocyanate group is not directly bonded to an aromatic ring, and a modified triisocyanate or tetraisocyanate. Examples of the modified body include a trimerized isocyanate modified product, a biuret modified body, a triol modified form, and a tetraol modified form. Examples of the diisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and thiol group. Diisocyanate such as diisocyanate.

Specific examples of the triisocyanate include the followings. The trimerized isocyanate modified alkyl diisocyanate (cyclic dimer of alkyl diisocyanate) represented by the following formula (4-1), and the trimer isocyanate modified diisocyanate represented by the following formula (4-2) Acid toluene ester (cyclic 3 polymer of toluene diisocyanate), trimer isocyanate modified isophorone diisocyanate represented by the following formula (4-3) (cyclic 3 polymer of isophorone diisocyanate) The biuret modified alkyl diisocyanate represented by the following formula (4-4), and the glycerol modified alkyl diisocyanate represented by the following formula (4-5). However, s, t, and u are each independently an integer from 2 to 10.

[Chemical 2]

(Action mechanism) Since the fluorine-containing compound of the present invention described above has (C _n F _2n-i H _i O) _b , the polarization due to the hydrogen atom is larger than (C _m F _2m O) _a . Therefore, compatibility with a non-fluorine-type photopolymerizable compound is favorable. Other than _{(C m F 2m O) a} , (C n F 2n-i H i O) b would be more reduced antifouling properties of the object. However, since the fluorine-containing compound of the present invention has CF ₃ - at the terminal, the surface energy of the surface of the object (hard coat layer or the like) is lowered, and as a result, excellent antifouling properties can be imparted to the object. Moreover, when the fluorine-containing compound of the present invention further has (C _m F _2m O) _a , the object can be further provided with excellent antifouling properties.

[Photocurable composition] The photocurable composition of the present invention contains the fluorine-containing compound (compound (1)) of the present invention, a photopolymerizable compound (except for the fluorine-containing compound of the present invention), and a photopolymerization initiator ( However, it does not contain liquid media). The photocurable composition of the present invention may further contain an additive for a photocurable composition according to the demand.

(Photopolymerizable Compound) The photopolymerizable compound is a compound having one or more polymerizable double bonds by initiating a polymerization reaction by irradiation with light in the presence of a photopolymerization initiator to be described later. The photopolymerizable compound may be a non-fluorine-based photopolymerizable compound or a fluorine-containing photopolymerizable compound (except for the fluorine-containing compound of the present invention). From the viewpoint of excellent raw material properties and economical efficiency, a non-fluorine-based photopolymerizable compound is preferred.

The photopolymerizable compound may, for example, be a polyfunctional compound (a compound having two or more polymerizable double bonds) or a monofunctional compound (a compound having one polymerizable double bond). Examples of the photopolymerizable compound include a monoester or a polyester of (meth)acrylic acid, a reaction product of a hydroxyl group-containing (meth)acrylate and a polyisocyanate, a hydroxyl compound having no polymerizable double bond, and a hydroxyl group (methyl group). a reaction product of an acrylate and a polyisocyanate. Specifically, a polyester of a polyhydric alcohol and a (meth)acrylic acid; a reaction product of a polyhydric alcohol, a polyisocyanate and a hydroxyalkyl (meth)acrylate; and a hydroxyalkyl (meth)acrylate and a polyisocyanate are mentioned. A polyfunctional compound such as a reaction product. The polyhydric alcohol may, for example, be a polyhydric alcohol having a hetero ring such as an aliphatic polyhydric alcohol, an alicyclic polyhydric alcohol or a quinone (2-hydroxyethyl) trimeric isocyanate. The above polyisocyanate may, for example, be the above polyisocyanate (z). Further, the photopolymerizable compound may have a functional group which is inert to photopolymerization such as a hydroxyl group. From the viewpoint of the abrasion resistance of the object to be applied (such as a hard coat layer), it is preferred that at least a part of the photopolymerizable compound contained in the photocurable composition is a polyfunctional compound. The number of polymerizable double bonds in the molecule of the polyfunctional compound 1 is preferably from 3 to 6. One type of the photopolymerizable compound may be used alone or two or more types may be used in combination.

(Photopolymerization Initiator) The photopolymerization initiator may, for example, be a known photopolymerization initiator such as an arylketone photopolymerization initiator (acetophenone, diphenylketone, alkylamine diphenylketone, or benzophenone). Base, benzoin, benzoin ether, benzyl dimethyl ketal, benzamidine benzoate, α-mercapto oxime ester, etc.), sulfur-containing photopolymerization initiator ( Sulfide, 9-oxosulfur , etc.), mercaptophosphine oxides (fluorenyl diarylphosphine oxides, etc.) and other photopolymerization initiators. One type of the photopolymerization initiator may be used alone or two or more types may be used in combination. The photopolymerization initiator can also be used in combination with a photosensitizer such as an amine.

(Additive for photocurable composition) Examples of the additive for the photocurable composition include colloidal cerium oxide, a photosensitizer, an ultraviolet absorber, a light stabilizer, a thermosetting stabilizer, an antioxidant, a leveling agent, an antifoaming agent, and an increase. Thickener, anti-settling agent, pigment, dye, dispersant, antistatic agent, surfactant (anti-fogging agent, leveling agent, etc.), metal oxide particles, various resins (epoxy resin, unsaturated polyester resin, Polyurethane resin, etc.).

(Composition of Photocurable Composition) The content of the fluorine-containing compound of the present invention in the photocurable composition is preferably from 0.01 to 5% by mass, more preferably from 0.02 to 4% by mass, in the photocurable composition. ~3 mass% is especially good. The content of the fluorine-containing compound of the present invention is preferably within the above range, and the low-temperature storage stability of the photocurable composition, the appearance of the object (hard coat layer, etc.), abrasion resistance, and antifouling property are preferable.

The content of the photopolymerizable compound in the photocurable composition is preferably from 20 to 98.99% by mass, more preferably from 50 to 98.99% by mass, more preferably from 60 to 98.99% by mass, and more preferably from 80 to 98.9% by mass. 98.99% by mass is especially preferred. When the content of the photopolymerizable compound is within the above range, the low-temperature storage stability of the photocurable composition, the appearance of the object, the abrasion resistance, and the antifouling property are excellent.

The content of the photopolymerization initiator in the photocurable composition is preferably from 1 to 15% by mass, more preferably from 3 to 15% by mass, particularly preferably from 3 to 10% by mass, based on the photocurable composition. When the content of the photopolymerization initiator is within the above range, compatibility with the photopolymerizable compound is preferable. Further, the photocurable composition has good hardenability, and the cured film formed has good hardness.

When the additive for the photocurable composition is contained, the photocurable composition is preferably used in an amount of 0.5 to 20% by mass, more preferably 1 to 15% by mass, based on the photocurable composition. It is especially good at 1 to 10% by mass.

The photocurable composition of the present invention may contain by-products, unreacted raw materials (compound (x), compound (y), polyisocyanate (z), etc.) which are produced when the fluorine-containing compound of the present invention is produced, and the production of the present invention. An impurity such as a production additive (polymerization inhibitor or the like) used in the case of a fluorine-containing compound. In the impurities, the compatibility of the compound (x) with other components is insufficient, and therefore, when the compound (x) remains in the composition, the composition may be cloudy. Therefore, the content of the compound (x) is preferably 10% by mass or less, and particularly preferably 5% by mass or less based on the fluorine-containing compound of the present invention. In the impurities, the polyisocyanate (z) has high reactivity with other components, and therefore, when the polyisocyanate (z) remains in the composition, the storage stability of the composition may be lowered. Therefore, the content of the polyisocyanate (z) is preferably 4% by mass or less based on the fluorine-containing compound of the present invention, and particularly preferably 1% by mass or less. Identification and quantification of impurities can be carried out by using ¹ H-NMR and ¹⁹ F-NMR or gas chromatography.

[Coating Liquid] The coating liquid of the present invention contains the photocurable composition of the present invention and a liquid medium. The coating liquid of the present invention is prepared in order to allow the photocurable composition of the present invention to be easily applied onto a substrate.

(Liquid medium) The liquid medium is preferably an organic solvent. The organic solvent is preferably an organic solvent having a boiling point suitable for the coating method. The organic solvent may be a fluorine-based organic solvent or a non-fluorine-based organic solvent, or may be used in combination.

The liquid medium is preferably at least one organic solvent selected from the group consisting of fluorocarbons, fluorine aromatic compounds, fluoroalkyl ethers, fluoroalcohols, compounds consisting only of hydrogen atoms and carbon atoms, and only A compound composed of a hydrogen atom, a carbon atom and an oxygen atom; and a fluorine-based organic solvent selected from the group consisting of a fluorocarbon, a fluorine aromatic compound, a fluoroalkyl ether and a fluoroalcohol is particularly preferable. From the viewpoint of improving the solubility of the fluorine-containing compound, the liquid medium preferably contains at least one organic solvent selected from the group consisting of fluorocarbons and fluorine aromatics in total of 90% by mass or more of the entire liquid medium. A compound, a fluoroalkyl ether, a fluoroalcohol, and a compound consisting only of a hydrogen atom, a carbon atom, and an oxygen atom. The content of the liquid medium in the coating liquid is preferably from 5 to 80% by mass, more preferably from 10 to 70% by mass, particularly preferably from 20 to 60% by mass.

[Composition for forming a hard coat layer] The composition for forming a hard coat layer of the present invention is composed of the photocurable composition of the present invention or the coating liquid of the present invention. The coating film formed by the photocurable composition and the coating liquid of the present invention does not need to be heated during curing, and therefore is suitable for forming a hard coat layer on a substrate composed of a resin having lower heat resistance than glass or the like. The photocurable composition of the present invention and a coating liquid are used.

[Article] The article of the present invention has a substrate and a hard coat layer, and the hard coat layer is formed of the composition for forming a hard coat layer of the present invention.

(Hard Coat Layer) The hard coat layer may be formed directly on at least one surface of the substrate, or may be formed on at least one surface of the substrate via an undercoat layer described later. From the viewpoint of abrasion resistance and antifouling property, the thickness of the hard coat layer is preferably from 0.5 to 20 μm, and particularly preferably from 1 to 15 μm.

(Substrate) The substrate is a body portion of various articles (optical lenses, displays, optical recording media, etc.) that are resistant to abrasion and stain resistance, or members constituting the surface of the article. Examples of the material of the surface of the substrate include metal, resin, glass, ceramic, stone, and the like. The material of the surface of the substrate of the optical lens, the display, and the optical recording medium is preferably a glass or a transparent resin substrate.

(Undercoat layer) The article of the present invention may further have an undercoat layer between the substrate and the hard coat layer from the viewpoint of adhesion between the lifted substrate and the hard coat layer. The undercoat layer is exemplified by a known one. For example, an undercoat layer may be formed by applying a composition for forming an undercoat layer containing a liquid medium onto a surface of a substrate and then evaporating the liquid medium.

(Method for Producing Article) The article can be produced, for example, by the following steps (I) and (II). Step (I): a step of applying an undercoat layer-forming composition to a surface of a substrate to form an undercoat layer as required. Step (II): applying a composition for forming a hard coat layer on the surface of a substrate or a primer layer to obtain a coating film, and then removing the liquid medium when the composition for forming a hard coating layer contains a liquid medium, and then removing the light medium The step of hardening to form a hard coat layer. Example

Hereinafter, examples and comparative examples of the present invention will be described. However, the invention is not limited only to the embodiments. Examples 1 and 2 are examples, and examples 3 to 5 are comparative examples.

[Code] AK-225: Mixture of CF ₃ CF ₂ CHCl ₂ and CClF ₂ CF ₂ CHClF (ASHTIKLIN (registered trademark) AK-225, manufactured by Asahi Glass Co., Ltd., TMS: tetramethyl decane, L: liter, Mn: number average Molecular weight.

[Measurement/Evaluation] (Mn of Compound) The number average molecular weight of the compound was determined by comparing the integral ratio of the internal standard substance to the terminal functional group of the compound by a nuclear magnetic resonance apparatus (NMR).

(Compatibility) The appearance of the composition for forming a hard coat layer which was just prepared was visually evaluated in accordance with the following criteria. ○ (good): The solution was uniform and turbid. △ (acceptable): A slight turbidity can be observed. × (poor): turbidity can be clearly observed by the naked eye.

(Standard Storage Stability at Room Temperature) After the composition for forming a hard coat layer was allowed to stand at room temperature for 3 months, the appearance of the composition for forming a hard coat layer was visually evaluated. ○ (good): The solution was uniform and turbid. △ (acceptable): A slight turbidity can be observed. × (poor): turbidity can be clearly observed by the naked eye.

(Cryogenic Storage Stability) After the composition for forming a hard coat layer was allowed to stand in a freezer at -20 ° C for 3 months, the appearance of the composition for forming a hard coat layer was visually evaluated. ○ (good): The solution was uniform and turbid. △ (acceptable): A slight turbidity can be observed. × (poor): turbidity can be clearly observed by the naked eye.

(Appearance of hard coat layer) The appearance of the hard coat layer was visually evaluated according to the following criteria. ○ (good): no foreign matter was observed and the film thickness was uniform. △ (fair): Although no foreign matter was observed, the film thickness was not uniform. × (poor): Foreign matter was observed and the film thickness was uneven.

(fingerprint dirt removal property) The artificial fingerprint liquid (liquid of oleic acid and squalene) is attached to the flat surface of the rubber stopper, and the excess is wiped off by a non-woven fabric (made by Asahi Kasei Co., Ltd., BEMCOT (registered trademark) M-3). Oil to prepare the impression of the fingerprint. The fingerprint was placed on an article with a hard coat and pressed at a load of 9.8 N for 10 seconds. A reciprocating wire tester (manufactured by KNT Co., Ltd.) equipped with a wiper was attached to the place where the fingerprint was attached, and the wipe was performed at a load of 4.9 N. The haze was observed with the naked eye after each reciprocating wiping, and the evaluation was continued by visual observation until the haze after 10 reciprocations. The evaluation criteria are as follows. ○ (good): No haze was observed under the naked eye. △ (can still): Some haze can be found under the naked eye. × (poor): The haze can be clearly observed under the naked eye.

(Oil-based ink detachability) An oil-based pen (manufactured by Zebra, Mckee, extremely thick black) was drawn on the surface of the hard coat layer, and the adhesion state of the oil-based ink was visually observed. The evaluation criteria are as follows. ◎ (Excellent): The oily ink is plucked into a bead shape. ○ (good): The oily ink is not plucked into a bead shape but plucked into a line shape, and the line width is less than 50% of the width of the oil pen tip. △ (fair): The oily ink is not plucked into a bead shape but plucked into a line shape, and the line width is 50% or more and less than 100% of the width of the oil pen tip. × (bad): The oily ink cannot be plucked into a bead or a line, and the line can be clearly drawn on the surface.

(Abrasion resistance) A reciprocating wire tester (manufactured by KNT Co., Ltd.) was used for articles having a hard coat layer, and steel wool was produced under a load of 9.8 N (manufactured by NIHON STEEL WOOL Co., Ltd., Bonstar (registered trademark)# 0000) After 100 times of reciprocation, the water contact angle and the oleic acid contact angle were measured in accordance with JIS R3257:1999 "Test method for wettability of substrate glass surface" under the conditions of droplets: about 2 μL/drop and temperature: 20 °C. Each contact angle was measured at 3 places and the average of these was taken. The evaluation criteria are as follows. ○ (good): The difference between the water contact angle, the oleic acid contact angle and the initial contact angle obtained by the following formula is less than 10%. △ (acceptable): The difference between the water contact angle and the oleic acid contact angle and the initial contact angle obtained by the following formula is less than 10%. × (poor): The difference between the water contact angle, the oleic acid contact angle and the initial contact angle obtained by the following formula is 10% or more. Difference from initial contact angle (%) = (initial contact angle - contact angle after abrasion resistance test) / initial contact angle × 100

(Pencil Hardness) The pencil hardness of the surface of the hard coat layer was measured in accordance with JIS K5600-5-4:1999 (ISO 15184:1996) "Scoring Hardness (Pencil Method)".

[Example 1] (Example 1-1) 16.5 g of sodium borohydride and 200 g of AK-225 were placed in a 500-mL three-necked flask, and stirred in an ice bath. Further, a mixture of 200 g of the compound (22) and 27.2 g of methanol was slowly dropped thereinto at an internal temperature of not more than 15 °C. After all the dropwise additions, the mixture was stirred for 2 hours while being immersed in an ice bath. Further, 2N HCl 250 mL was added to complete the reaction. The reaction solution was washed three times with water and saturated brine. After drying over sodium sulfate, the solid was filtered off by filtration, and the solvent was evaporated under reduced pressure to give Compound (21) as a colorless transparent liquid. The product was analyzed by a gas chromatograph to obtain a compound (21) having a purity of 98.7%, and no unreacted compound (22) was detected. CF ₂ =CF-O-CF ₂ CF ₂ CF ₂ C(=O)OCH ₃・・・(22) CF ₂ =CF-O-CF ₂ CF ₂ CF ₂ CH ₂ -OH・・・(21)

(Example 1-2) The compound (20-1) was obtained by the method described in International Publication No. 2009/008380. CF ₃ -O-{(CF ₂ CF ₂ O) _a }-CF ₂ CH ₂ -OH (20-1) Average value of a: 6. Number average molecular weight: 730.

(Example 1-3) 22 g of the compound (21) obtained in Example 1-1 and 10 g of the compound (20-1) obtained in Example 1-2 were placed in a 100 mL eggplant-shaped flask to which a reflux condenser was attached, and potassium carbonate powder was added thereto. 1.47g. After stirring at 60 ° C for 8 hours under a nitrogen atmosphere, 1.74 g of potassium carbonate powder was further added, and the mixture was stirred at 80 ° C for 2 hours, and then at room temperature for 24 hours. After adding an aqueous solution of hydrochloric acid to remove excess potassium carbonate, water and AK-225 were added to carry out liquid separation treatment. After washing three times, the organic phase was recovered, and concentrated by an evaporator to obtain a high-viscosity product of 32.65 g. After further dilution with AK-225 30 g, it was developed by tapidine column chromatography (developing solvent: AK-225) for fractionation. The average value of b1 in the following formula (x11-1) was determined from the integral value of ¹⁹ F-NMR for each fraction. The compound (x11-1) 6.06 g obtained by combining the fractions having an average b1 of 7 to 15 was obtained. CF ₃ -O-{(CF ₂ CF ₂ O) _a }-{CF ₂ CH ₂ O-(CF ₂ CFHO-CF ₂ CF ₂ CF ₂ CH ₂ O) _b1 }-H・・・(x11-1)

NMR mass spectrum of the compound (x11-1); ¹ H-NMR (300.4 MHz, solvent: deuterated acetone, standard: TMS) δ (ppm): 4.1 (2H), 4.8 (22H), 6.7 to 6.9 (11H). ¹⁹ F-NMR (282.7 MHz, solvent: deuterated acetone, standard: CFCl ₃ ) δ (ppm): -55.3 (3F), -77.6 (2F), -83.7 to -85.1 (22F), -88.5 (24F) , -89.3~-90.4 (22F), -120.2 (20F), -122.0 (2F), -126.6 (22F), -145.1 (11F). Average of a: 6, average of b1: 11, number average molecular weight: 4,080.

(Example 1-4) 366 mg of polyisocyanate (z-1) (Sumika Bayer Urethane Co., Ltd., Sumidur N3300, manufactured by Sumika Bayer Urethane Co., Ltd., was placed in a 100 mL 2-necked flask equipped with a dropping funnel, a condenser, a thermometer, and a stirring device. The isocyanate group content: 21.8%, and the trimer isocyanate-modified hexamethylene diisocyanate represented by the formula (4-1) is dissolved in 5.9 g of a fluorine-based organic solvent (ZEORORA (registered trademark) H, manufactured by Japan ZEON Co., Ltd. 1.5 mg of dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 1,1,2,2,3,3,4-heptafluorocyclopentane, and the mixture was stirred at 40 ° C under a nitrogen atmosphere. At the same time, 911 mg of the compound (x11-1) was added dropwise over 1 hour, followed by stirring for 1 hour. 194 mg of the compound (y-1) (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER HOA, 2-hydroxyethyl acrylate) was added dropwise over a period of 30 minutes, followed by stirring for 4 hours. The absorption of the isocyanate group was completely disappeared by infrared absorption spectroscopy. 0.2 mg of dibutylhydroxytoluene was added to obtain a reaction product.

(Example 1-5) Into a 10 mL test tube, 50 mg of the reaction product, a photopolymerizable compound (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ACRYLATE PE-4A, pentaerythritol tetraacrylate), 200 mg, and a non-fluorine-based organic solvent were placed. (propylene glycol monomethyl ether) 200 mg, photopolymerization initiator (2-methyl-1-{4-(methylthio)phenyl}-2- After 0.1 mg of the morphyl propan-1-one), the mixture was stirred at room temperature for 1 hour while being light-shielded to obtain a composition for forming a hard coat layer.

(Example 1-6) A composition for forming a hard coat layer was applied onto a surface of a polyethylene terephthalate substrate by a bar coating method to form a coating film, which was then dried by a hot plate at 50 ° C for 1 minute. A dry film is formed on the surface of the substrate. A high-pressure mercury lamp was used to irradiate ultraviolet rays (light quantity: 300 mJ/cm ² , ultraviolet light accumulation energy of 365 nm) to form a hard coat layer having a thickness of 5 μm on the surface of the substrate. The evaluation results of the composition for forming a hard coat layer and the hard coat layer are shown in Table 2.

[Example 2] (Example 2-1) 0.36 g of a compound (28-1) was placed in a 100 mL eggplant-shaped flask to which a reflux condenser was connected (manufactured by Tokyo Chemical Industry Co., Ltd., 1H, 1H, 2H, 2H-perfluoro -1-octanol) and added 0.14 g of potassium carbonate powder. After stirring at room temperature for 30 minutes under a nitrogen atmosphere, the mixture was cooled to 0 ° C, and 1.3 g of a compound (23) (2,2,3,3-tetrafluorooxetane) was added. It was further stirred at 0 ° C for 24 hours. After confirming that the compound (23) was completely consumed by ¹⁹ F-NMR, 2 mL of methanol was added, and the mixture was stirred at room temperature for 1 hour. 20 mL of water was added to carry out liquid separation treatment to obtain 1.6 g of the compound (33-1). CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ -OH・(28-1). CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ -O-(CH ₂ CF ₂ CF ₂ O) _b3 -CH ₂ CF ₂ C(=O)OCH ₃・・・(33-1)

NMR mass spectrum of the compound (33-1); ¹ H-NMR (300.4 MHz, solvent: deuterated acetone, standard: TMS) δ (ppm): 1.7 (2H), 3.3 to 3.9 (23H), 4.1 (2H). ¹⁹ F-NMR (282.7 MHz, solvent: deuterated acetone, standard: CFCl ₃ ) δ (ppm): -80 (2F), -83 to -85 (18F), -86 (3F), -118 (2F) , -126~-132(26F). Average of b3: 9, number average molecular weight: 1,660.

(Example 2-2) 1.6 g of the compound (33-1) was placed in a 100 mL eggplant-shaped flask, and 80 mg of sodium borohydride was added thereto, followed by stirring at room temperature for 24 hours under a nitrogen atmosphere. 10% hydrochloric acid was added until the solution became acidic. After diluting with AK-225 100 mL, it was washed twice with 20 mL of water. The organic phase was recovered, concentrated with an evaporator, and dried in vacuo to give compound (x 42-1) 1.6 g. CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ -O-{(CH ₂ CF ₂ CF ₂ O) _b3 -CH ₂ CF ₂ CH ₂ O}-H・・・(x42-1)

NMR mass spectrum of the compound (x42-1); ¹ H-NMR (300.4 MHz, solvent: deuterated acetone, standard: TMS) δ (ppm): 1.7 (2H), 3.3 to 3.9 (24H). ¹⁹ F-NMR (282.7 MHz, solvent: deuterated acetone, standard: CFCl ₃ ) δ (ppm): -81 (2F), -83 to -85 (18F), -86 (3F), -118 (2F) , -126~-132(26F). Average of b3: 9, number average molecular weight: 1,660.

(Example 2-3) A composition containing a fluorine-containing compound was obtained in the same manner as in Example 1 except that the type and the amount of the raw material were changed as shown in Table 1, and a composition for forming a hard coat layer and a hard coat layer were obtained. . The evaluation results of the composition for forming a hard coat layer and the hard coat layer are shown in Table 2.

[Example 3] A reaction product was obtained in the same manner as in Example 1 except that the type and amount of the raw material were changed as shown in Table 1, and a composition for forming a hard coat layer and a hard coat layer were obtained. The evaluation results of the composition for forming a hard coat layer and the hard coat layer are shown in Table 2.

[Example 4] The compound (35) was obtained by the method described in Example 2 of Patent Document 3. F(CH ₂ CF ₂ CF ₂ O) _b2 CH ₂ CF ₂ CH ₂ OH (35) Average value of b2: 6. Number average molecular weight: 894.

The reaction product was obtained in the same manner as in Example 1 except that the type and amount of the raw material were changed as shown in Table 1, and then a composition for forming a hard coat layer and a hard coat layer were obtained. The evaluation results of the composition for forming a hard coat layer and the hard coat layer are shown in Table 2.

[Example 5] The compound (27-1) was obtained by the method described in Example 1-1 of Patent Document 2. CF ₃ CF ₂ CF ₂ -O-{CFHCF ₂ O-CH ₂ CF ₂ O}-{(CF ₂ O) _a1 (CF ₂ CF ₂ O) _a2 }-CF ₂ CH ₂ -OH・(・(27- 1). Average of a1: 8, average of a2: 10, number average molecular weight: 2,070.

The reaction product was obtained in the same manner as in Example 1 except that the type and amount of the raw material were changed as shown in Table 1, and then a composition for forming a hard coat layer and a hard coat layer were obtained. The evaluation results of the composition for forming a hard coat layer and the hard coat layer are shown in Table 2.

[Table 1]

[Table 2]

The fluorine-containing compound of Examples 1 and 2 has (C _n F _2n-i H _i O) _b and has CF ₃ - at the end, so that the composition for forming a hard coat layer has good low-temperature storage stability, and the anti-fouling of the hard coat layer Excellent in appearance and appearance. Further, since the fluorine-containing compound of Example 1 has (C _m F _2m O) _a , the antifouling property (oily ink detachability) of the hard coat layer is particularly excellent. Since the fluorine-containing compound of Example 3 does not have (C _n F _2n-i H _i O) _b , the compatibility with the non-fluorine-based photopolymerizable compound is insufficient, and the composition for forming a hard coat layer is stable at room temperature and low temperature. Insufficient sex, the appearance of the hard coat is not sufficient. The end of the fluorine-containing compound of the example (4) does not have CF ₃ -, so the antifouling property of the hard coat layer is insufficient. Although the fluorine-containing compound of Example 5 has (C _n F _2n-i H _i O) _b, the amount thereof is insufficient, so that the composition for forming a hard coat layer has insufficient low-temperature storage stability. Industrial availability

The fluorine-containing compound of the present invention is suitably used for imparting excellent antifouling properties to an object to be applied (such as a hard coat layer). The photocurable composition or coating liquid containing the fluorine-containing compound of the present invention can impart excellent antifouling properties to the input surface of the touch panel or the like. In addition, it is used for mixing with a resin material to impart antifouling properties to a molded article, a mold release agent such as a mold, a bearing or the like, oil leakage prevention, processing of electronic parts, etc., prevention of adhesion of a processing solution, moisture prevention of a processed product, and the like. Can also be used. The entire disclosure of Japanese Patent Application No. 2015-145875, the entire disclosure of which is incorporated herein in

(no)

Claims (13)

A fluorine-containing compound which is a compound represented by the following formula (1); [DO-{(C _m F _2m O) _a (C _n F _2n-i H _i O) _b }-] _d A・・・(1) However, D is (R ^f1 ) _e -R ¹ - or R ^f2 -; R ^f1 is a perfluoroalkyl group having 1 to 6 carbon atoms; e is an integer of 1 to 3; and R ¹ is a carbon number of 1 to 6 ( e+1) valence hydrocarbon group; R ^f2 is a perfluoroalkyl group having 1 to 6 carbon atoms; m is an integer of 1 to 6; a is an integer of 0 to 200, and when a is 2 or more, (C _m F _2m O _a can be composed of two or more different types of C _m F _2m O; n is an integer from 1 to 6; i is an integer from 1 to 2n-1; b is an integer from 6 to 200, and (C _n F _{2n- i} H _i O) _b may be composed of two or more C _n F _2n-i H _i O which are different from one or both of n and i; d is an integer of 1 or more; A is one or more polymerizable carbons - a d-valent organic group of a carbon double bond; the bonding order of a C _m F _2m O and b C _n F _2n-i H _i O is not limited. The fluorine-containing compound of claim 1, wherein the compound represented by the above formula (1) is a compound represented by the following formula (11); [DO-{(C _m F _2m O) _a }-{(C _n F _2n-i H _i O) _b }-] _d A・・・(11) However, D, m, n, i, b, d, and A are D, m, n, i, b, and d of the above formula (1). A is the same; a is an integer from 1 to 200, and when a is 2 or more, (C _m F _2m O) _a can be composed of two or more different kinds of C _m F _2m O; when a is 2 or more, {(C) _m F _2m O) _a } is a block composed of a C _m F _2m O; {(C _n F _2n-i H _i O) _b } is composed of b C _n F _2n-i H _i O Block. The fluorine-containing compound of claim 2, wherein the compound represented by the above formula (1) is a compound represented by the following formula (111); [DO-{(CF ₂ CF ₂ O) _a }-{CF ₂ CH ₂ O-( CF ₂ CFHO-CF ₂ CF ₂ CF ₂ CH ₂ O) _b/2-1 }-] _d A・・・(111) However, D, d and A are the same as D, d and A of the above formula (1) , b is an even number in b of the above formula (1). The fluorine-containing compound of claim 1, wherein the compound represented by the above formula (1) is a compound represented by the following formula (12); [DO-{( C _n F _2n-i H _i O) _c }-{(C _m F _2m O) _a }-{(C _n F _2n-i H _i O) _bc }-] _d A・・・(12) However, D, m, n, i, b, d, and A are as described above ( 1) D, m, n, i, b, d, and A are the same; a is an integer from 1 to 200, and when a is 2 or more, (C _m F _2m O) _a can be two or more different from each other. _m F _2m O; c is 2 or 3, (C _n F _2n-i H _i O) _c may be two or more of n and i different from each other, C _n F _2n-i H _i O Composition; {(C _n F _2n-i H _i O) _c } is a block composed of c C _n F _2n-i H _i O; when a is 2 or more, {(C _m F _2m O) _a } a block composed of a C _m F _2m O; {(C _n F _2n-i H _i O) _bc } is a block composed of bc C _n F _2n-i H _i O . The fluorine-containing compound of claim 1, wherein the compound represented by the above formula (1) is a compound represented by the following formula (112); [DO-(CH ₂ CF ₂ CF ₂ O) _b-1 -CH ₂ CF ₂ CH ₂ O-] _d A (112) However, b, d, and A are the same as b, d, and A of the above formula (1), and D is (R ^f1 ) _{e -} R ¹ -. The fluorine-containing compound according to any one of claims 1 to 4, wherein a ratio of the aforementioned a to the above b represented by a/b is from 20/1 to 1/20. The fluorine-containing compound according to any one of claims 1 to 6, wherein the A is a d-valent organic group having one or more (meth) propylene fluorenyloxy groups. The fluorine-containing compound according to any one of claims 1 to 7, which is a reaction product of the following three and has no unreacted isocyanate group: DO-{(C _m F _2m O) _a (C _n F _2n-i H _i O) hydroxy compound represented by _b }-H, a hydroxy compound having one or more (meth) acryloxy groups, and a polyisocyanate having two or more isocyanate groups. The fluorine-containing compound according to any one of claims 1 to 8, which has a number average molecular weight of 1,200 to 8,000. A photocurable composition comprising the fluorine-containing compound according to any one of claims 1 to 9, a photopolymerizable compound (except for the fluorine-containing compound), and a photopolymerization initiator (only, no liquid) medium). A coating liquid comprising the photocurable composition of claim 10 and a liquid medium. A composition for forming a hard coat layer, which is composed of the photocurable composition of claim 10 or the coating liquid of claim 11. An article characterized by having a substrate and a hard coat layer formed of the photocurable composition of claim 10 or the coating liquid of claim 11.