TWI558777B - A hard coat composition containing an antifouling property - Google Patents

Description

Hard coating composition imparting antifouling properties

The present invention relates to a hard coat material which imparts antifouling properties, and more specifically, to an antifouling imparting agent having a fluorine-containing organic group and a hydrocarbon group and a (meth)acrylic group in the same molecule, and in the same molecule A hard coat composition which imparts antifouling properties to an antifouling property imparting agent having a perfluoropolyether group and a (meth)acrylic group.

The resin material is widely used in various electronic products, electronic cases such as personal computers and mobile phones, and the like, because it has characteristics such as no rust and lightness compared with metal. In addition, compared with glass, it has characteristics such as being difficult to be broken, and a resin having high hardness and high transparency such as an acrylic resin or a polycarbonate resin is used as a monomer or a hard coat material for a liquid crystal display or A display body such as a touch panel.

In recent years, particularly in the casing of an electronic machine or the like, a high gloss surface is required from the viewpoint of design. In addition, in the case of a mobile phone or a display for a personal computer, there are also a number of specifications including a touch panel. On the outermost surface, a hard coat such as an acrylic resin or a polyoxymethylene resin is applied for the purpose of preventing scratches and the like. Layer material.

Since such contact with a human hand or the like frequently occurs, sebum, sweat, fingerprints, and the like are easily adhered, and when they become marks, the appearance or the visibility is deteriorated. In particular, in a capacitive touch panel, it is necessary to input by direct contact with a finger, and this problem cannot be avoided. Therefore, for such hard coat materials, an improvement in antifouling properties such as fingerprint resistance is strongly required.

As a countermeasure against this, there are various reviews at present, which are roughly classified into the following two methods. One method is to use a polyoxymethylene compound or a fluorine compound to form water with low surface energy on the surface of the hard coat layer. The oily surface is oily, and the dirt such as fingerprints is not easily attached, and the processor which is easy to remove is applied.

For example, Japanese Laid-Open Patent Publication No. 2004-250474, the entire surface of the hard coat layer is treated with a perfluoropolyether group-containing decane compound, Japanese Patent Laid-Open No. 3963169: Patent Document 2 As shown, by adding a perfluoropolyether urethane acrylate composition to the hard coat composition, the surface is crosslinked to form a water repellent. Oil-repellent surface for anti-fouling performance.

Although this method makes the attached dirt easy to be wiped off, but because of its high water. The oil-repellent property, the attached fingerprint, etc. form fine droplets, and the transmittance or visibility is lowered due to diffuse reflection of light, and the refractive index difference between the sebum or sweat of the component of the fingerprint due to the low refractive index of the fluorine compound Large, even a slight trace of adhesion will be eye-catching.

In addition, the attached fingerprint contains inorganic components such as water or salt, and proteins. An organic component such as a substance or a fat or oil has a complicated composition, and it is difficult to completely prevent such adhesion.

Another method is to form a hydrophilic ‧ lipophilic surface having a high affinity for a dirty component such as a fingerprint on the outermost surface of the hard coat layer, and to make the thin wetting spread by being intimate with the adhered dirt Eye-catching.

For example, Japanese Laid-Open Patent Publication No. 2001-353808: As shown in Patent Document 3, the outermost surface of a hard coat layer is treated with a decane compound having a long-chain alkyl ester group, or International Publication No. 2009/44912: As shown in Patent Document 4, by adding a colloidal vermiculite to the acrylic polymer composition, a hydrophilic ‧ lipophilic surface is formed on the surface, and the visibility of the stain is lowered.

In this method, even if the surface of the hard coat layer is contaminated, the whole is wetted and spread and is not easily seen. Further, by making the refractive index of the hard coat layer close to a dirty component such as a fingerprint, it is possible to further prevent a decrease in visibility. However, since the affinity for the soiled components is high, they are slowly deposited or difficult to wipe off, so that the light transmittance of the display or the like is lowered.

Japanese Patent No. 4873666: Patent Document 5 describes an acrylate compound having a perfluoropolyether group. When the compound is added alone, the fingerprint wiping off system is greatly improved, but the fingerprint is not conspicuous. .

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2004-250474

[Patent Document 2] Japanese Invention Patent No. 3963169

[Patent Document 3] JP-A-2001-353808

[Patent Document 4] International Publication No. 2009/44912

[Patent Document 5] Japanese Invention Patent No. 4873666

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a surface of a hard coat layer which can be imparted to human fats, cosmetics, and the like which adhere to fingerprints, sebum, sweat, and the like, or which is excellent in wiping property even when stains are adhered. Antifouling hard coating composition.

In order to achieve the above object, the present inventors have repeated the intensive review, and found that a fluorine-containing acrylate compound represented by the following formula (1) is added to the hard coat material, and the following formula is used. (2) A hard coat composition for imparting antifouling properties to two types of antifouling additives of a perfluoropolyether group-containing acrylate compound, the surface of the hard coat layer obtained is improved in fingerprints, and the fingerprint is wiped off. The de-sexability is also good, and the present invention has been completed.

Accordingly, the present invention provides the following hard coat composition for imparting antifouling properties.

[1] A hard coat composition for imparting antifouling properties, the main component of which is: (A) a hard coat material, (B) a fluorine-containing acrylate compound represented by the following formula (1), [wherein, Rf is a fluoroalkyl group having 2 to 16 carbon atoms, Q is independently a single bond or a divalent organic group having 1 to 12 carbon atoms, and R is independently a carbon atom having 6 to 20 carbon atoms. alkyl group or aralkyl group having a carbon number of 7 to 20, R & lt based carbon ¹ independently of each other alkyl, C6-14 aryl group or an aralkyl group having 7 to carbon atoms, 1 to 6 10 6 to 10, R ² lines Hydrogen atom or methyl group, X system is of the following formula (wherein R ¹² is a divalent hydrocarbon group having 1 to 12 carbon atoms)

The group shown, m is an integer of 2-8, n is independently 1 or 2], (C) an acrylate compound X ¹ -[Z) having a perfluoropolyether group represented by the following formula (2) -Rf'-ZX ² ] _v -Z-Rf'-ZX ¹ (2) [wherein, Rf' is independently a divalent polystyrene group having a molecular weight of 500 to 30,000, and may also include a branch on the way, X ¹ Independent of each other, the following formula (3) [In the formula (3), a and c are each an integer of 0 or 1 to 3, and b is an integer of 1 to 4, except that a+b+c is 2, 3 or 4, and the arrangement of each repeating unit may be random. R ^{3 is} independently of the following formula (4)-(C ₄ H ₈ O) _d (C ₃ H ₆ O) _e (C ₂ H ₄ O) _f (CH ₂ O) _g R ⁵ (4) (formula In (4), d, e, f, and g are in the range of 45 to 600 in the molecular weight of R ³ , and are independently 0 or 1 to 20 integers, and the arrangement of each repeating unit may be random, R ⁵ a group represented by a saturated or unsaturated monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁴ is represented by the following formula (5) (In the formula (5), R ^{6 is} independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and R ⁷ is a divalent or trivalent linking group having an ether bond or an ester bond having 1 to 18 carbon atoms; , u is 1 or 2)

The acrylic group or the group containing an α-substituted acrylate group, Q ¹ and Q ^{2 are} each independently a carbon number of 3 to 20 which may contain an ether bond, an ester bond, a guanamine bond or a urethane bond. The linking group may include a cyclic structure or a branched structure in the middle, each of which may be the same or different, and X ^{2 is} independently the following formula (6) (In the formula (6), R ³ , R ⁴ , Q ¹ , and Q ² are as described above, h and k are each an integer of 0 or 1 to 3, j is an integer of 1 to 3, and h+j+k is Any value of 1 to 3, the arrangement of each repeating unit may be a random group represented by a random group, and Z may independently contain an oxygen atom, a nitrogen atom, a germanium atom, and may have a cyclic structure and an unsaturated bond. The divalent organic group, v is 0 or an integer of 1 to 5].

[2] The hard coat composition which imparts antifouling property according to [1], wherein the hard coat material of the component (A) is an ultraviolet curable acrylic hard coat material.

[3] The hard coat composition for imparting antifouling properties according to [2], wherein the ultraviolet curable acrylic hard coat material is composed of a (meth)acrylic compound and a photopolymerization initiator.

By the hard coat composition which imparts antifouling property of the present invention, it is possible to impart a hard coat layer which is excellent in the wiping property even if it adheres to human fat such as fingerprints, sebum, sweat, etc., cosmetics, or the like. surface.

[Formation of the Invention]

Hereinafter, the present invention will be described in detail.

The hard coat composition for imparting antifouling property of the present invention contains the following components as a main component: (A) a hard coat material, (B) a fluorine-containing acrylate compound represented by the formula (1), C) An acrylate compound having a perfluoropolyether group represented by the formula (2).

(A) hard coating material

The hard coat material of the component (A) of the present invention is not particularly limited, but is preferably a balance between solubility and surface elution properties of the antifouling agent for the components (B) and (C) to be described later. An excellent resin (active energy ray-curable resin composition) which is cured by irradiation with an active energy ray, and particularly preferably an ultraviolet ray-curable acrylic hardened by a (meth)acrylic compound and a photopolymerization initiator. Coating material.

In the ultraviolet curable acrylic hard coat material, as the (meth)acrylic compound, for example, pentaerythritol di(meth)acrylate, diethylene glycol di(meth)acrylate, or trimethylolpropane can be used. Tris(meth)acrylate, tetramethylol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, tris(meth)acryloxyethyl phosphate Ester, hydrogen phthalate-(2,2,2-tris(meth)acryloxymethyl)ethyl, glycerol tri(meth) acrylate, pentaerythritol tetra(meth) acrylate, ditrihydroxy Methylpropane tetra(meth)acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, sorbitol hexa(meth) acrylate 2~6-functional (meth)acrylic compounds, such (meth)acrylic compounds modified with ethylene oxide, propylene oxide, epichlorohydrin, fatty acid, alkyl, urethane Epoxy acrylate obtained by adding acrylic acid to epoxy resin, the (meth) acrylate compound in ethylene oxide, propylene oxide, epichlorohydrin, fatty acid, alkane, ethyl urethane Modified product, epoxy resin obtained by adding acrylic acid to epoxy acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3- propylene methoxy propyl methacrylate and pentaerythritol triacrylate The selected (meth) acrylate having a hydroxyl group, and the amino isocyanate reacted with a polyisocyanate selected from hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate a acrylate acrylate or a polyfunctional (meth) acrylate mixture in which a copolymer of (meth) acrylonitrile group is introduced into a side chain of an acrylate copolymer, and a benzoin, benzoin A is blended therein. Ether, diphenyl ketone, 1-hydroxycyclohexyl phenyl ketone The photopolymerization initiator is used.

Further, as the ultraviolet curable acrylic hard coat material, a commercially available product can be used, and as the (meth)acrylic compound, for example, EBECRYL 40 (4-functional acrylate, manufactured by DAICEL Scientific Co., Ltd.), PETIA (3 functional group) can be used. Acrylate, manufactured by DAICEL Scientific Co., Ltd., A-TMPT (3-functional acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), A-DPH (6-functional acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H (6-functional acrylate, Co., Ltd. Chemical Co., Ltd.), UN-952 (15-functional acrylate, manufactured by K.K.). Further, as the photopolymerization initiator, for example, Irgacure 184, Irgacure 127, Irgacure 651, Darocure can be used. 1173 (BASF system) and the like.

Here, the amount of the photopolymerization initiator to be used is preferably 1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the (meth)acrylic compound. When the amount is too small, the hardenability is insufficient, and the cured product may become soft. If the amount is too large, impurities which do not participate in crosslinking in the cured product may increase, and the physical properties may be lowered.

(B) fluorine-containing acrylate compound

The fluorine-containing acrylate compound of the component (B) of the present invention functions as an antifouling agent according to the following formula (1).

In the formula (1), Rf is a linear or branched fluorine alkyl group having 2 to 16 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, which is used for water withdrawal. The oil-repellent property, the anti-fouling property, and the elution property on the surface of the hard coat layer are imparted to the compound. When the carbon number in Rf exceeds the above upper limit value, the compatibility with the hard coat material is impaired, and whitening or hardening failure occurs.

As an example of such a fluorine-containing group Rf, the following can be illustrated as an example.

-C _p F _2p -, -(CF ₂ ) _r -CH ₂ -(CF ₂ ) _s - (wherein p is an integer from 2 to 10, preferably an integer from 4 to 8, and r is from 1 to 8, Preferably, it is an integer of 2 to 6, and s is 1 to 8, preferably an integer of 2 to 6.

Among these, the following ones can be suitably used.

-C _p F _2p - (wherein p is the same as above).

In the formula (1), Q is independently a single bond or a divalent organic group having 1 to 12 carbon atoms and preferably 3 to 8 carbon atoms. The divalent organic group may specifically be a methylene group, an exoethyl group, a propyl group (trimethylene group, a methyl group ethyl group), a butyl group (tetramethylene group, a methyl group propyl group), and a hexamethyl group. a combination of an alkylene group such as a methylene group or an octamethylene group, an extended aryl group such as a phenyl group, or a combination of two or more groups (such as an alkyl group, an aryl group, etc.), or may be One or two or more kinds of structures selected from the group consisting of an ether bond, a guanamine bond, an ester bond, and a diorganenylalkenyl group are inserted into the base of the above, and in addition to the above, A divalent hydrocarbon group of one or more selected from the group consisting of an atom, a nitrogen atom and a ruthenium atom.

Examples of the divalent organic group of Q include a group represented by the following formula.

-CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ -O-(CH ₂ ) _t -, -CH ₂ CH ₂ -O-(CH ₂ ) _t -,- OCH ₂ -, -CO-NH-CH ₂ -, -CO-N(Ph)-CH ₂ -, -CO-NH-CH ₂ CH ₂ -, -CO-N(Ph)-CH ₂ CH ₂ CH ₂ -, -CO-N(CH ₃ )-CH ₂ CH ₂ CH ₂ -, -CO-O-CH ₂ -, -CO-N(CH ₃ )-Ph'-, -CO-NR ¹¹ -Y'- -CO-NR ¹¹ -Y'-CH ₂ CH ₂ - (wherein Ph is a phenyl group, Ph' is a phenylene group, and t is an integer of 1 to 10.

Y'--CH ₂ - or the following formula The divalent group shown, R ¹¹ is a hydrogen atom or unsubstituted or substituted, preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms.

Here, the unsubstituted or substituted R ¹¹ is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. An alkyl group such as a third butyl group, a pentyl group, a neopentyl group, a hexyl group or an octyl group; a cycloalkyl group such as a cyclohexyl group; an alkenyl group such as a vinyl group, an allyl group or a propenyl group; a phenyl group; a tolyl group; An aryl group such as a tolyl group or a naphthyl group, an aralkyl group such as a benzyl group, a phenylethyl group or a phenylpropyl group, or a part or all of the hydrogen atoms of the groups may be a halogen atom such as fluorine, bromine or chlorine. A cyano group (N≡C-) or the like is substituted, for example, a chloromethyl group, a chloropropyl group, a bromoethyl group, a trifluoropropyl group, a cyanoethyl group or the like.

In the formula (1), R is independently an alkyl group having 6 to 20 carbon atoms, preferably 8 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, preferably 8 to 14 carbon atoms. The base has affinity with the oil component of the stain or the fingerprint, and is introduced in order to make the stain or the fingerprint unobtrusive. For example, examples of the alkyl group include a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group (lauryl group), a tetradecyl group (myristyl group), and a hexadecyl group (palmityl group). And an octadecyl (stearyl), a decyl group, etc., and an aralkyl group, a benzyl group, a phenylethyl group, a tolylethyl group, etc. are mentioned. In addition, one or more types of an oxygen-bonded oxygen atom (-O-), a carbonyl bond (-CO-), and an ester bond (-COO-) may be inserted in the above-mentioned, for example, Ethyl undecanoate, ethyl octylate, ethoxypentyl, and the like. The plural R can be the same base or a heterologous base.

In the formula (1), R ^{1 is} independently an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, or a carbon number of 7 ～10, preferably an aralkyl group having 7 to 8 carbon atoms, which is introduced in order to impart lipophilicity to a compound, compatibility with a hard coat material, and the like. For example, an alkyl group such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a hexyl group or a cyclohexyl group, an aryl group such as a phenyl group, or a benzyl group may be mentioned. Etc. aralkyl and the like. Among them, a methyl group, a n-butyl group, and a phenyl group are preferred, and a methyl group is particularly preferred. Each of the R ¹ systems may be the same or a heterogeneous group.

Further, R ² is a hydrogen atom or a methyl group.

In the formula (1), X is represented by the following formula.

(wherein R ¹² is a divalent hydrocarbon group having 1 to 12 carbon atoms such as an alkylene group such as a methylene group, an ethyl group or a propyl group; and an extended aryl group such as a phenyl group or a phenylene group;

Further, in the formula (1), n is independently 1 or 2, preferably 2; m is an integer of 2 to 8, preferably an integer of 2 to 6.

Specific examples of the fluorine-containing acrylate compound represented by the above formula (1) include the following.

(However, x+y (average) = 5).

The fluorine-containing acrylate compound represented by the above formula (1) can be easily produced by a known method. For example, the following general formula (i) can be obtained (wherein, Rf, Q, and R ¹ are the same as described above)

a fluorine-containing compound containing a hydroquinolyl group, and an α-olefin compound having 6 to 20 carbon atoms and an enol corresponding to a residue obtained by removing one hydrogen atom from the R group of the formula (1). Preferably, in the presence of a platinum-based catalyst, the hydroxylation addition reaction is carried out by a conventional method to form a fluorine-containing organic modified siloxane, and the oxirane and the (meth)acrylic group are contained. The isocyanate compound is produced by reaction.

Here, the α-olefin compound is an olefin obtained by removing one hydrogen atom from R in the formula (1), and preferably an olefin having a vinyl group at one terminal. When an olefin having a vinyl group at both ends is used, a cross-linking reaction occurs between the molecules during the hydroquinone addition reaction, and the product is gelated, or the solubility of the hard coat material is Reduce the embarrassment. As carbon number 6~ Specific examples of the 20-α-olefin compound include 1-hexadecene, 1-dodecene, 10-undecenoic acid ethyl ester, and ethoxy-1-pentene.

Further, examples of the enol include those represented by the following formulas.

_{^{HO-R 13 -CH = CH 2}} ( wherein, R ¹³ based single bond or a methylene group having a carbon number 1 to 6, extending ethyl, propyl stretching, stretching alkylene butyl, etc.).

The fluorine-containing compound containing a hydroquinolyl group and the α-olefin compound having 6 to 20 carbon atoms are reacted so that at least one of the SiH groups of the fluorine-containing compound containing a hydroquinolyl group remains. Preferably, the molar ratio (Vi/SiH ratio) of the terminal vinyl group of the SiH group containing the hydrofluorenyloxy group-containing fluorine compound and the α-olefin compound is 0.167 to 0.833, more preferably 0.333 to 0.667. The reaction is carried out to obtain a fluorine-containing organic group-modified rhodium oxide having at least one, preferably 1 to 3, SiH groups. When the α-olefin compound is more than the above, when it is added to the hard coat material, turbidity may occur.

Next, the remaining SiH groups are reacted with the enol. The fluorine-containing organic group-modified siloxane having at least one SiH group after the reaction of the fluoroalkoxy group-containing fluorine-containing compound with the α-olefin compound and the enol are preferably modified by the fluorine-containing organic group The molar ratio of the SiH group of the azoxy alkane to the vinyl group of the enol (Vi/SiH ratio) is 0.2 to 1.5, particularly preferably 0.333 to 1.2, and the reaction is carried out to obtain a fluorine-containing organic group having no SiH group. Sexual alkane.

In the above reaction, as the platinum-based catalyst, a conventional platinum group metal catalyst used in the hydroquinone addition reaction can be used. Generally, due to the high price of the noble metal compound, it is preferred to use a platinum or platinum compound which is relatively easy to obtain. As such a platinum compound, a complex of chloroplatinic acid or chloroplatinic acid with an olefin such as ethylene, a complex with an alcohol or a vinyl siloxane, and a ruthenium, alumina, carbon, or the like can be used. Metal platinum. As the platinum group metal catalyst other than the platinum compound, ruthenium, rhodium, iridium, and palladium compounds can be used. For example, RhCl(PPh ₃ ) ₃ , RhCl(CO)(PPh ₃ ) ₂ , Ru ₃ (CO) ₁₂ , IrCl(CO)(PPh ₃ ) ₂ , Pd(PPh ₃ ) ₄ or the like (wherein, Ph is a phenyl group).

The amount of the platinum-based catalyst used may be a catalytic amount, and is preferably 0.1 to 500 ppm, preferably 0.1 to 500 ppm, based on 100 parts by mass of the total of the hydrofluorinated alkoxy group-containing fluorine-containing compound and the α-olefin compound or the enol. The amount.

The reaction temperature is appropriately determined depending on the amount or type of the solvent, and it is usually from room temperature to 200 ° C, preferably from 40 to 100 ° C. The reaction time is not particularly limited as long as the reaction is sufficiently carried out according to individual reaction conditions.

When performing the hydrohaloalkylation addition reaction in each of the above stages, a solvent may be used as needed. The solvent is preferably one in which a hydrofluorinated alkoxy group-containing fluorine-containing compound, an α-olefin compound, and an enol are dissolved. However, if only one of them is dissolved, as long as it does not inhibit the hydroquinone addition reaction, There are no special restrictions. The amount of the solvent to be used is appropriately selected according to the viscosity or the amount of the fluorine-containing compound containing a hydrofluorenyloxy group, the α-olefin compound, and the enol or the resulting fluorine-containing organic modified rhodium oxide, but is relative to the hydrogen-containing compound. The total amount of the fluorinated compound of the decyloxy group, the α-olefin compound, and the enol is preferably 10 to 200 parts by mass, particularly preferably 20 to 100 parts by mass.

Examples of such a solvent include aliphatic hydrocarbon compounds such as n-hexane, n-heptane, isooctane, and isodecane, and aromatic hydrocarbon compounds such as toluene and xylene, and trifluorotoluene and hexafluoro-di Fluorinated aromatic hydrocarbons such as toluene Compound, perfluorobutyl methyl ether, perfluorobutyl ethyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(three a hydrofluoroether compound such as fluoromethyl)pentane or a chlorofluorocarbon compound such as Daiproyl (manufactured by DAIKIN Co., Ltd.), hexamethyldioxane, octamethyltrioxane or decamethyltetraoxane Chain-like oxime of alkane, dodecamethylpentaoxane, 2-(trimethylphosphonium oxyalkyl)-1,1,1,2,3,3,3-heptamethyltrioxane a cyclic oxirane such as an alkane, an octamethylcyclopentaoxane or a decamethylcyclopentaoxane, a Fomblin, a Galden (manufactured by SOLVAY SOLEXIS), a Demnum (manufactured by DAIKIN Industries), or a Krytox (manufactured by DuPont). Perfluoropolyether compound or the like. Among them, toluene, xylene, hexafluorom-xylene-based hydrofluoroalkyloxy group-containing fluorine-containing compound, α-olefin compound, enol, and produced fluorine-containing organic modified rhodium oxide are excellent in solubility. .

The obtained fluorine-containing organic modified azide is reacted with an isocyanate compound containing a (meth)acryl group. In this case, the amount of the alcohol in the fluorine-containing organic modified rhodium oxide is quantified, preferably in an amount of 1.2 to 3 times the molar amount, preferably 1.5 to 2 times the molar amount of the (meth)acrylic group. The isocyanate compound reacts.

Here, the isocyanate compound containing a (meth)acryl group can be exemplified by the following formula.

(wherein R ² and R ¹² are the same as described above).

The reaction of the fluorine-containing organic modified alkane with the (meth)acrylic acid-containing isocyanate compound can be carried out at 0 to 120 ° C, preferably 25 Under the condition of ~80 ° C, the two were mixed and carried out.

Further, in order to increase the reaction rate, an appropriate catalyst may be added. Examples of the catalyst include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctoate, stannous dioctoate, and the like. Alkyl tin ester compound, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetrakis(2-ethylhexyloxy), titanium dipropoxy bis(acetonitrile), titanium isopropoxy A titanate or titanium chelate compound such as octanediol, zirconium tetraethoxide acetonide, zirconium tributoxy acetoacetate acetonide, zirconium monobutoxyacetam acetonide bis(ethyl acetamidine acetate) , zirconium dibutoxy bis(ethyl acetamidine acetate), zirconium tetraethyl acetonide, zirconium chelate compound, etc., but these are not limited to one type, and may be two or more types. The mixture is used. The reaction rate can be increased by adding these catalysts in an amount of 0.01 to 2% by mass, preferably 0.05 to 1% by mass, based on the total mass of the reactants.

Further, the reaction may be carried out by diluting with a suitable solvent as needed. The solvent is not particularly limited as long as it is a solvent which does not react with an isocyanate or a hydroxyl group, and specific examples thereof include ethers such as tetrahydrofuran, diisopropyl ether and dibutyl ether, acetone and methyl ethyl. A ketone such as a ketone or a methyl isobutyl ketone; an ester such as ethyl acetate or butyl acetate; an aromatic hydrocarbon solvent such as toluene or xylene; and the like.

The component (B) of the present invention can be prepared into a solution which is uniformly dissolved in an organic solvent. In this case, the concentration of the fluorine-containing acrylate compound in the solution is not particularly limited as long as the range of the homogeneous solution is obtained, and it is usually 1 to 50% by mass, preferably 5 to 30% by mass, more preferably For 5 ~20% by mass or so.

The organic solvent in which the fluorine-containing acrylate compound is dissolved is selected from those which do not react with the hard coat material of the component (A), and examples thereof include aliphatic hydrocarbon solvents such as hexane, heptane, isooctane, and isodecane. An aromatic hydrocarbon solvent such as toluene or xylene; an alcohol solvent such as methanol, ethanol or isopropyl alcohol; a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; A glycol ether solvent such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether or propylene glycol monomethyl ether, or an ester system such as ethyl acetate, butyl acetate or propylene glycol monomethyl ether acetate. Solvents, etc. Among them, isodecane, isopropanol, methyl isobutyl ketone and the like are preferably used.

The amount of the fluorine-containing acrylate compound to be added as the component (B) is 0.1 to 3 parts by mass, more preferably 0.2 to 100 parts by mass of the hard coat material of the component (A). When the ratio of 2 parts by mass is added, good surface characteristics are obtained. When the lower limit is not reached, the elution of the surface of the hard coat layer is difficult, and the appropriate characteristics are not obtained. Moreover, when it exceeds the above-mentioned upper limit, the affinity for the resin may be impaired, and whitening of the appearance or a decrease in hardness may occur.

(C) an acrylate compound having a perfluoropolyether group

The acrylate compound having a perfluoropolyether group of the component (C) of the present invention is an antifouling property imparting agent as shown by the following formula (2).

X ¹ -[Z-Rf'-ZX ² ] _v -Z-Rf'-ZX ¹ (2)

In the formula (2), Rf' is independently a divalent polyfluoropolyether group having a molecular weight of 500 to 30,000, and may also be branched in the middle.

Rf' is a divalent perfluoropolyether residue having 1 to 500 repeating units of the formula -C _i F _2i O- (i is an integer of from 1 to 6 per unit independently), preferably lower The perfluoropolyether residue represented by the formulas (7) to (9).

In the formula (7), Y is each independently F or a CF ₃ group, and A is an integer of 2 to 6, preferably an integer of 1 to 3, and B and C are each an integer of 0 or 1 to 200, preferably An integer from 2 to 100, but B+C is 2 to 200, preferably 4 to 100. D is an integer of 0 or 1 to 6, preferably an integer of 1 to 4, and each repeating unit may be randomly bonded.

[Chem. 17]-C _E F _2E (OCF ₂ CF ₂ CF ₂ ) _G OC _E F _2E - (8)

In the formula, E is an integer of 1 to 3, and G is an integer of 1 to 200, preferably an integer of 1 to 100.

Wherein Y is an F or CF ₃ group, E is an integer from 1 to 3, and H and J are each an integer of 0 or 1 to 200, preferably an integer of 1 to 100, except that H+J is 2 to 200. It is preferably 4 to 100. Each repeating unit can also be randomly bonded.

In the formula (2), X ^{1 is} each independently a group represented by the following formula (3).

In the formula (3), a and c are each an integer of 0 or 1 to 3, and b is an integer of 1 to 4, preferably 2 or 3, except that a+b+c is any of 2, 3, and 4. Preferably, it is 3 or 4, and the arrangement of each repeating unit may also be random.

In the formula (3), R ^{3 is} independently a group represented by the following formula (4).

-(C ₄ H ₈ O) _d (C ₃ H ₆ O) _e (C ₂ H ₄ O) _f (CH ₂ O) _g R ⁵ (4)

Formula (4), d, e, f, and g based on the molecular weight of R ³ is 45 to 600, preferably be in the range of 60 to 300, are each independently an integer of 0 or 1 to 20, preferably 1 An integer of ~10, d+e+f+g is preferably from 1 to 20, more preferably from 2 to 15. Further, the propyl group and the butyl group in the formula (4) may be branched, and the arrangement of each repeating unit may be random.

Formula (4), R ⁵ based saturated carbon atoms of 1 to 10 or an unsaturated monovalent hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, 2-B An alkyl group such as a hexyl group or a cyclohexyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; and the like. Particularly preferred are methyl and ethyl.

As such R ³ , a group represented by the following formula is preferred.

-(C ₂ H ₄ O) _{f '} (C ₃ H ₆ O) _{e '} CH ₃ (wherein f', e' is 0 or an integer from 1 to 20, and f'+e' is from 1 to 40. The propyl group in the middle can also be a branch, and each repeating unit can also be randomly bonded)

R ⁴ is preferably a monovalent organic group having 1 to 21 carbon atoms, which is one of at least one of an acryl group and an α-substituted acryl group represented by the following formula (5).

In the formula (5), R ^{6 is} independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group. R ⁷ is a carbon number of 1 to 18, preferably a divalent or trivalent linking group having 2 to 10 carbon atoms, and may have an etheric oxygen atom or an ester structure, and preferably exemplified below.

Also, u is 1 or 2.

The group represented by the formula (5) is preferably a group represented by the following formula, and particularly preferably a group containing an ethyl group as R ⁷ .

In the formula (3), Q ¹ and Q ^{2 are} each independently a two-valent linking group having an ether bond, an ester bond, a guanamine bond or a urethane bond having a carbon number of 3 to 20, which may be included in the middle. The annular structure or the branched structure may each be the same or different. As Q ¹ and Q ² , a group represented by the following formula is preferable.

In the formula (2), X ^{2 is} independently a divalent group represented by the following formula (6).

In the formula (6), R ³ , R ⁴ , Q ¹ , and Q ² are the same as described above, and h and k are each an integer of 0 or 1 to 3, j is an integer of 1 to 3, and h+j+k is For any value of 1, 2, and 3, the arrangement of each repeating unit may also be random.

In the formula (2), each of Z is independently a divalent organic group which may contain a halogen atom such as an oxygen atom, a nitrogen atom or a diorganenylenyl group, and Z may be a group having a cyclic structure or an unsaturated bond. The structural system is not particularly limited as long as it does not hinder the polymerization of the acrylic group. Examples of Z include a group represented by the following formula.

Among them, a group represented by the following formula is preferred.

v is an integer of 0 or 1 to 5, preferably 0, 1 or 2, more preferably 0 or 1.

Specific examples of the fluoroacrylate group-containing acrylate compound represented by the above formula (2) include the following.

(wherein Rf' is the same as above).

The component (C) of the present invention can be prepared into a solution which is uniformly dissolved in an organic solvent. In this case, the concentration of the perfluoropolyether group-containing acrylate compound in the solution is not particularly limited as long as the range of the homogeneous solution is obtained, and it is usually 1 to 50% by mass, preferably 5 to 30% by mass. %, more preferably about 5 to 20% by mass.

As the organic solvent for dissolving the perfluoropolyether group-containing acrylate compound, those which do not react with the (A) component for the hard coat material are selected, and examples thereof include hexane, heptane, isooctane, isodecane, and the like. An aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent such as toluene or xylene; an alcohol solvent such as methanol, ethanol or isopropyl alcohol; acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; a ketone solvent, a glycol ether solvent such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether or propylene glycol monomethyl ether, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate An ester solvent such as an ester. Among them, methyl ethyl ketone, methyl isobutyl ketone, isopropyl alcohol and the like are preferably used.

The amount of the perfluoropolyether group-containing acrylate compound to be added to the component (C) is 0.1 to 3 parts by mass based on 100 parts by mass of the hard coat material of the component (A). More preferably, it is added in a ratio of 0.2 to 2 parts by mass to obtain good surface characteristics. Not up When the lower limit is described, the elution of the surface of the hard coat layer is difficult, and the appropriate characteristics are not obtained. Moreover, when it exceeds the above-mentioned upper limit, the affinity for the resin may be impaired, and whitening of the appearance or a decrease in hardness may occur.

The hard coat composition of the present invention is suitably diluted with a solvent exemplified by a solvent capable of dissolving the above components (B) and (C) in order to uniformly disperse the components. Further, an additive such as a leveling agent or a tackifier may be blended insofar as the object of the present invention is not impaired.

The hard coat composition of the present invention can impart antifouling properties to the surface of the hard coat layer by blending the above two types of antifouling imparting agents (components (B) and (C)) into the hard coat material. , fingerprint resistance, etc. Thereby, it is possible to impart a surface of the hard coat layer which is excellent in the wiping property even when the human fat, the cosmetics, and the like which adhere to fingerprints, sebum, sweat, and the like are not conspicuous, or even if the stain is adhered. Therefore, the hard coat composition of the present invention can be applied to the surface of an article which is likely to be contaminated by human fat, cosmetics or the like due to human contact, and can be used for forming a coating film or a protective film, and is useful as a hardening component. Things. Examples of such an article include optical recording media such as optical disks, CDs, CDs, DVDs, Blu-ray disks, and the like, and holograms, lenses, lenses, films, and polarizers. Optical components such as optical filters, lenticular lenses, Fresnel lenses, anti-reflection films, optical fibers or optical couplers, optical devices, CRTs, liquid displays, plasma displays, electroluminescent displays, rear projection displays, and fluorescent devices. Various display devices such as light display tubes (VFDs), electroluminescent displays, and toner-based displays, especially PCs, mobile phones, portable information terminals, game consoles, digital cameras, digital cameras, automatic cash withdrawal devices, Automatic teller machines, vending machines, automobiles, etc. Video display device for navigation device, security system terminal, etc., and touch panel (touch sensor, touch screen) image display input device for the operation; mobile phone, portable information terminal, portable music player Input device such as a portable game machine, a remote controller, a controller, a keyboard, a panel switch for an in-vehicle device, a mobile phone, a portable information terminal, a camera, a portable music player, a portable game machine, and the like Surface; exterior and exterior of automobile, piano, high-grade furniture, marble, etc.; protective glass for art display, display window, display box, advertising cover, photo cover, watch, front glass for cars, train Transparent glass or transparent plastic (acrylic, polycarbonate, etc.) components such as window glass, automobile headlights, and taillights, and various mirror members.

The hard coat layer (cured film) is formed by applying the hard coat composition of the present invention to the outer surface of the article and ultraviolet curing.

As a coating method, spin coating, dip coating, brush coating, etc. are illustrated.

Further, as the ultraviolet curing condition, the ultraviolet light can be hardened by irradiation with an ultraviolet ray having a wavelength of 100 to 400 nm, preferably about 200 to 400 nm, with an irradiation amount of 200 to 2,000 mJ/cm ² , preferably about 400 to 1,600 mJ/cm ² . .

Further, the thickness of the hard coat cured film may be usually from 0.1 to 30 μm, preferably from about 1 to 10 μm.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited by the following examples.

[Examples 1 to 4, Comparative Example 1] Modification of antifouling agent

In a 10 ml glass sample vial, 2.0 g of any of the following antifouling additives (B) and (C) and 8.0 g of methyl isobutyl ketone (MIBK) were weighed and sealed, and shaken for 30 minutes. It was confirmed that the antifouling additive was completely dissolved, and it was filtered with a membrane filter made of PTFE (polytetrafluoroethylene) having a pore size of 0.45 μm to prepare 20% by mass of the component (B) or the component (C) as an antifouling imparting component. Antifouling imparting agent.

(B) component of antifouling additive B-1

B-2

B-3

(C) component antifouling additive C-1

Rf': -CF ₂ (OCF ₂ CF ₂ ) _G1 (OCF ₂ ) _H1 OCF ₂ - (G1/H1=0.9, G1+H1≒45)

C-2

Rf': -CF ₂ (OCF ₂ CF ₂ ) _G1 (OCF ₂ ) _H1 OCF ₂ - (G1/H1=0.9, G1+H1≒45)

Modification of hard coating composition

The hard coat composition was prepared by blending as shown in Table 1 below.

EBECRYL 40: 4-functional acrylate, manufactured by DAICEL Scientific

Irgacure 184: 1-hydroxycyclohexyl phenyl ketone, manufactured by CIBA Japan

Modification of hard coating material

Each solution (hard coat composition) blended with the antifouling agent was spin-coated on a black polymethyl methacrylate plate (5 × 5 × 0.2 cm), and a transport type ultraviolet irradiation device (PANASONIC electrician) As a company, ultraviolet rays of 1.6 J/cm ^{2 were} irradiated in a nitrogen atmosphere to form a cured film. The film thickness of the hardened coating film after hardening was 7 μm. The material coated with this hard coat film was used as a test piece for the following test.

Appearance test

The appearance (hue, transparency, smoothness) of the hard coat film was visually evaluated. The results are shown in Table 2.

2. Contact angle measurement test

A contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the contact angle of the surface of the hard coat film with water and oleic acid. The results are shown in Table 2.

3. Fingerprint resistance test

The fingerprint resistance test (fingerprint visibility, fingerprint wiping property) was carried out by the following method. The trial was conducted by five panelists. As a result of the evaluation, the most evaluation value among the five evaluation values was taken as the evaluation result. When two or more evaluation values are the same, the evaluation value is determined by a protocol of five. The results are shown in Table 2.

. Fingerprint visibility

The surface of the hard coating film was pressed with the index finger, and after holding for 3 seconds, the finger was quietly left. Under the wavelength-emitting fluorescent lamp, the visibility of the attached fingerprint was visually observed from directly above the coating film, and evaluated by the following four grades.

◎... I can't see the fingerprint.

○...I can hardly see the fingerprint.

△...You can see several fingerprints.

×...The fingerprint can be clearly seen.

. Fingerprint wiping

The non-woven fabric (Bemcot M-3II [made by Asahi Kasei Fiber Co., Ltd.]) was used to wipe back the fingerprint attached to the surface of the hard coat film. Under the three-wavelength luminescent fluorescent lamp, the angle of the self-coated film is inclined above 45°, and the shape after wiping is visually observed. State, the following three levels are used to evaluate the number of round trips until the fingerprint is not visible.

◎... The fingerprint can be wiped off after 3 round trips.

○... 3 times back and forth and less than 5 round trips can be wiped off.

×... Even if you wipe it back and forth 5 times, you cannot wipe the fingerprint.

[Examples 5 and 6, Comparative Examples 2 to 4]

The hard coat composition was prepared in the same manner as in the above Example 1 by the combination of the following Table 3.

The hard coat coating material was prepared in the same manner as in the above Example 1, and the properties were measured in the same manner, and the results are shown in Table 4 below.

The synthesis examples of the components B-1 to B-3 are shown below.

[Synthesis Example 1] Modulation of component B-1

In the flask equipped with a reflux cooling tube and a thermometer, the following formula (I) is added. The indicated fluorine-containing hydrooxane 43.1 g (0.050 mol), toluene 21.1 g, and platinum/vinyl alkane complex toluene solution 0.04 g (containing 0.2 mg of platinum). After the internal temperature was heated to 60 ° C, the dropping rate was adjusted so that the internal temperature did not become 70 ° C or higher, and 44.9 g (0.20 mol) of 1-hexadecene was dropped. After heating at 60 to 70 ° C for 1 hour, the dropping rate was adjusted so that the internal temperature did not become 70 ° C or higher, and 17.2 g (0.20 mol) of 4-pentenol was dropped. After confirming the disappearance of the absorption of the SiH group derived from the fluorine-containing hydroquinone (I) by the measurement of the IR spectrum, the hexafluorom-xylene and the excess cyclotetraoxane were distilled off under reduced pressure to obtain the following. 93.8 g of a fluorine-containing oxirane represented by the formula (II).

Next, in the flask equipped with the reflux cooling tube and the thermometer, 44.8 g (0.030 mol) of the fluorine-containing fluorinated alkane (II) obtained above and 8.9 g (0.063 mol) of acryloxyethyl isocyanate and A were added. Isobutyl ketone 53.7 g. After heating the internal temperature to 50 ° C, dibutyltin dilaurate was added. 0.02 g, reacted at 50 to 60 ° C for 2 hours. After the reaction, 0.90 g of ethanol was added, and it was confirmed by IR spectrum measurement that the absorption of NCO had disappeared, and the solvent was distilled off at 25 ° C to obtain 49.9 g of a transparent paste product.

The product obtained above was analyzed by measurement of ¹ H-NMR and IR spectrum, and found to be a fluorine-containing acrylate compound represented by the following formula.

[Synthesis Example 2] Modulation of component B-2

To the flask equipped with the reflux cooling tube and the thermometer, 43.1 g (0.050 mol) of fluorine-containing hydrooxane represented by the above formula (I), 18.8 g of toluene, and platinum/vinyl azide complex toluene were added. The solution was 0.04 g (containing 0.2 mg of platinum). After the internal temperature was heated to 60 ° C, the dropping rate was adjusted so that the internal temperature did not become 70 ° C or more, and 33.6 g (0.20 mol) of 1-dodecene was dropped. After heating at 60 to 70 ° C for 1 hour, the dropping rate was adjusted so that the internal temperature did not become 70 ° C or higher, and 17.2 g (0.20 mol) of 4-pentenol was dropped. After confirming the disappearance of the absorption of the SiH group derived from the fluorine-containing hydroquinone (I) by the measurement of the IR spectrum, the hexafluorom-xylene and the excess cyclotetraoxane were distilled off under reduced pressure to obtain the following. 80.4 g of a fluorine-containing oxirane represented by the formula (III).

Next, in the flask equipped with the reflux cooling tube and the thermometer, 31.4 g (0.030 mol) of the fluorine-containing fluorinated alkane (III) obtained above and 8.9 g (0.063 mol) of acryloxyethyl isocyanate and a Isobutyl ketone 40.3 g. After heating the internal temperature to 50 ° C, 0.02 g of dibutyltin dilaurate was added, and the reaction was carried out at 50 to 60 ° C for 2 hours. After the reaction, 1.55 g of ethanol was added, and it was confirmed by IR spectrum measurement that the absorption of NCO had disappeared, and the solvent was distilled off at 25 ° C to obtain 36.4 g of a transparent paste product.

The product obtained above was analyzed by measurement of ¹ H-NMR and IR spectrum, and found to be a fluorine-containing acrylate compound represented by the following formula.

[Synthesis Example 3] Modulation of B-3 ingredients

To the flask equipped with the reflux cooling tube and the thermometer, 43.1 g (0.050 mol) of the fluorine-containing hydrooxane represented by the above formula (I), 20.6 g of toluene, and platinum/vinyl azide complex toluene were added. Solution 0.04g (containing 0.2 mg of platinum). After the internal temperature was heated to 60 ° C, the dropping rate was adjusted so that the internal temperature did not become 70 ° C or higher, and 42.5 g (0.20 mol) of ethyl 10-undecenoate was added dropwise. After heating at 60 to 70 ° C for 1 hour, the dropping rate was adjusted so that the internal temperature did not become 70 ° C or higher, and 17.2 g (0.20 mol) of 4-pentenol was dropped. After confirming the disappearance of the absorption of the SiH group derived from the fluorine-containing hydroquinone (I) by the measurement of the IR spectrum, the hexafluorom-xylene and the excess cyclotetraoxane were distilled off under reduced pressure to obtain a formula. 93.4 g of fluorine-containing oxane as shown in (IV).

Next, in the flask equipped with the reflux cooling tube and the thermometer, 30.9 g (0.030 mol) of the fluorine-containing fluorinated alkane (IV) obtained above and 8.9 g (0.063 mol) of acryloxyethyl isocyanate and A were added. Isobutyl ketone 39.8 g. After heating the internal temperature to 50 ° C, 0.02 g of dibutyltin dilaurate was added, and the reaction was carried out at 50 to 60 ° C for 2 hours. After the reaction, 1.58 g of ethanol was added, and it was confirmed by IR spectrum measurement that the absorption of NCO had disappeared, and the solvent was distilled off at 25 ° C to obtain 34.2 g of a transparent paste product.

The product obtained above was analyzed by measurement of ¹ H-NMR and IR spectrum, and found to be a fluorine-containing acrylate compound represented by the following formula.

Claims (1)

A hard coat composition for imparting antifouling properties, the main component of which is: (A) an ultraviolet curable acrylic hard coat material composed of a (meth)acrylic compound and a photopolymerization initiator, (B) a fluorine-containing acrylate compound represented by the following formula (1), [wherein, Rf is a fluoroalkyl group having 2 to 16 carbon atoms, Q is independently a single bond or a divalent organic group having 1 to 12 carbon atoms, and R is independently a carbon atom having 6 to 20 carbon atoms. An alkyl group or an aralkyl group having 7 to 20 carbon atoms, and R ^{1 is} independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and R ² is an alkyl group. Hydrogen atom or methyl group, X system is of the following formula (Wherein, R ¹² divalent hydrocarbon-based carbon number 1 to 12) shown in the group, m is an integer of from 2 to 8, n is independently 1 2], (C) or the following formula (2) The perfluoropolyether group-containing acrylate compound X ¹ -[Z-Rf'-ZX ² ] _v -Z-Rf'-ZX ¹ (2) wherein Rf' is independently the following formula (7) a perfluoropolyether residue as shown in ~(9), (wherein Y is independently F or CF ₃ groups, A is an integer of 2-6, and B and C are each 0 or an integer of 1 to 200, but B+C is 2 to 200, preferably 4~ 100, D is 0 or an integer of 1~6, and each repeating unit can also be randomly bonded.) [Chem. 17]-C _E F _2E (OCF ₂ CF ₂ CF ₂ ) _G OC _E F _2E - (8)( Where E is an integer from 1 to 3, and G is an integer from 1 to 200) (wherein Y is F or CF ₃ group, E is an integer of 1 to 3, H and J are each 0 or an integer of 1 to 200, but H+J is 2 to 200, and each repeating unit can also be randomly Bonding) X ^{1 is} independent of each other (3) [In the formula (3), a and c are each an integer of 0 or 1 to 3, and b is an integer of 1 to 4, except that a+b+c is 2, 3 or 4, and the arrangement of each repeating unit may be random. R ^{3 is} independently of the following formula (4)-(C ₄ H ₈ O) _d (C ₃ H ₆ O) _e (C ₂ H ₄ O) _f (CH ₂ O) _g R ⁵ (4) (formula In (4), d, e, f, and g are in the range of 45 to 600 in the molecular weight of R ³ , and are independently 0 or 1 to 20 integers, and the arrangement of each repeating unit may be random, R ⁵ a group represented by a saturated or unsaturated monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁴ is represented by the following formula (5) (In the formula (5), R ^{6 is} independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and R ⁷ is a divalent or trivalent linking group having an ether bond or an ester bond having 1 to 18 carbon atoms; , group, Q ¹ and Q ² group represented by the following formula are each independently of the line u 1 or 2 containing an acrylic group or an acrylic group as the substituent α) shown in , each of which may be the same or different, and X ^{2 is} independently the following formula (6) (In the formula (6), R ³ , R ⁴ , Q ¹ , and Q ² are as described above, h and k are each an integer of 0 or 1 to 3, j is an integer of 1 to 3, and h+j+k is Any value of 1 to 3, the arrangement of each repeating unit may be a binary group represented by a random), and Z is independently a base represented by the following formula , v is 0 or an integer from 1 to 5].