JP2009084436A - Fluorine-containing resin composition and cured film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel fluorine-containing resin composition capable of forming a film excellent in surface slipperiness and water- and oil-repellency, and to provide a cured film thereof. <P>SOLUTION: An ultraviolet curing type surface treating agent is formed, which comprises a specific fluorosilicone compound having at one end thereof a polymerizable unsaturated group and at the other end thereof a fluorine-containing group capable of exhibiting orientation on a substrate surface and further a composition having a group polymerizable with the fluorosilicone compound. The cured film excellent in water- and oil-repellency is formed from the surface treating agent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a fluorine-containing resin composition having excellent surface slip properties, a cured film thereof, and a molded body having a cured film.

  Polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, triacetyl cellulose resin, diacetyl cellulose as a substrate for display devices such as liquid crystal display panels and plasma displays, instrument panels, plastic lenses, optical disks, etc. Various plastic resin base materials such as resin, ABS resin, AS resin, norbornene resin are used.

  However, these plastic resin products are easily scratched because of their low surface hardness, especially in the case of transparent resins such as polycarbonate and polyethylene terephthalate, because the original transparency or appearance of the resin is significantly impaired. In addition to antifouling properties, scratch resistance and wear resistance are required. For this reason, it has excellent coating properties, and the surface of various substrates has hardness, scratch resistance, abrasion resistance, surface slipperiness, adhesion, transparency, chemical resistance, and coating surface appearance. In any case, a resin composition capable of forming an excellent cured film is required.

Various compositions have been proposed to meet these requirements.
Examples of a method for imparting surface slipperiness include, for example, an activity comprising an acrylic ester of bisphenol A diglycidyl ether polymer, dipentaerythritol monohydroxypentaacrylate, an active energy ray polymerization initiator, inorganic particles, and terminal reactive polydimethylsiloxane. It has been proposed to use an energy ray curable resin composition as an active energy ray curable resin composition (see, for example, Patent Document 1). However, a cured product using such a composition shows a certain improvement in the surface slipperiness, but the surface slipperiness changes with time, and the hardness and scratch resistance are not always satisfactory. It was.

Moreover, although the curable composition which improved the surface slipperiness by mix | blending the polysiloxane which has a (meth) acryloyl group is proposed (for example, refer patent document 2, patent document 3), antifouling property is proposed. From a point of view, it is not satisfactory.
JP-A-11-124514 JP-A-2005-36018 JP 2006-348196 A

  An object of the present invention is to provide a new fluorine-containing resin composition capable of forming a film excellent in surface slipperiness and water and oil repellency, and a molded body having the cured film and the cured film. And

  In addition, the present invention has excellent coating properties, and has high hardness and scratch resistance on various substrate surfaces, excellent transparency, surface slipperiness, water repellency, oil repellency, and their sustainability. Another object of the present invention is to provide a new fluorine-containing resin composition capable of forming a film having excellent properties, a cured film thereof, and a molded body having the cured film.

  As a result of intensive research from the above viewpoint, the present inventors have fixed a fluorine-based silicon compound that contributes to surface slipperiness, water repellency, and oil repellency on the resin surface, and based on the fluorine alkyl group of the fluorine-based silicon compound. It has been found that by aligning on the surface of the material, slipperiness superior to that of a silicon compound having no fluorine is brought about.

  That is, this invention relates to the fluorine-containing resin composition etc. which are shown below.

[1] A fluorine-containing resin comprising a fluorine-based silicon compound represented by the following formula (I), a curable resin, and a resin material containing at least one selected from monomers constituting the resin Composition.

In the formula (I), R _f is a fluoroalkyl having 1 to 20 carbon atoms in which any methylene may be replaced with oxygen; 6 carbon atoms in which at least one hydrogen is replaced with fluorine or trifluoromethyl. Or a fluoroarylalkyl having 7 to 20 carbon atoms composed of the fluoroaryl and alkylene, n represents an integer of 0 to 1,000, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen; having 1 to 30 carbon atoms, any hydrogen may be replaced by fluorine, and any methylene may be replaced by oxygen or cycloalkylene A good alkyl; a substituted or unsubstituted aryl having 6 to 30 carbon atoms; or the aryl and any hydrogen in which any hydrogen may be replaced by fluorine. Down is constituted by an oxygen or cycloalkylene with replaced may be alkylene, carbon atoms arylalkyl having 7 to 30; represent, A ¹ is the following formula (II), representing the (III) or (IV) .

In Formula (II), Y ¹ represents alkylene having 2 to 10 carbon atoms, R ⁷ represents hydrogen, alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms. In Formula (III), R ⁸ represents hydrogen, alkyl having 1 to 5 carbons, or aryl having 6 to 10 carbons, X ¹ represents alkylene having 2 to 20 carbons, and Y represents — _{OCH 2 CH 2 -, - OCH} (CH 3) CH 2 -, or -OCH ₂ CH (CH ₃₎ - represents, p is an integer of 0 to 3. In Formula (IV), Y ² represents a single bond or alkylene having 1 to 10 carbon atoms.

[2] R _f is 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6,6,6-nona Fluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, hepadecafluoro-1,1,2,2-tetrahydrodecyl, henicosafluoro-1,1,2,2-tetrahydrododecyl, penta Cosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, or α, α, α-trifluoromethylphenyl, R ³ And R ⁴ are independently methyl, phenyl, 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4, 4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, or heptadecafluoro-1,1,2,2-tetrahydrodecyl, R ¹ , R ² , R ⁵ , and R ⁶ are each methyl or phenyl, the fluorine-containing resin composition according to [1].

[3] R _f is 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6,6,6-nona The fluorine-containing resin composition according to [2], which is fluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl or heptadecafluoro-1,1,2,2-tetrahydrodecyl object.

[4] In formula (II), Y ¹ is alkylene having 2 to 6 carbon atoms, R ⁷ is hydrogen or alkyl having 1 to 3 carbon atoms, and in formula (III), X ¹ is —CH ₂ CH ₂ CH ₂ —, Y is —OCH ₂ CH ₂ —, p is 0 or 1, R ⁸ is hydrogen or alkyl having 1 to 3 carbon atoms, and in formula (IV), Y ² is The fluorine-containing resin composition according to [3], which is a single bond, methylene or ethylene.

[5] A surface treatment agent containing the fluorine-containing resin composition according to any one of [1] to [4].

[6] A cured film obtained from the surface treatment agent according to [5].

[7] A molded article having the cured film according to [6].

  The fluorine-containing resin composition containing the fluorine-based silicon compound of the present invention is used for a molded article such as a surface treatment agent having excellent surface slipperiness, water repellency, and oil repellency, a cured film, and a sheet or film having a cured film. Can do.

  The fluorine-containing resin composition of the present invention has a fluorine-containing silicon compound having a polymerizable unsaturated group at one end and a fluorine-containing group capable of expressing orientation on the substrate surface at the other end. Further, it contains a resin material having a group polymerizable with a fluorine-based silicon compound.

  Moreover, in this invention, (meth) acryl is a general term for acryl and methacryl, and means acryl and / or methacryl. Moreover, (meth) acrylate is a general term for acrylate and methacrylate, and means acrylate and / or methacrylate.

  Furthermore, in the present invention, active energy rays are defined as energy rays that can generate active species by decomposing a compound that generates active species. Examples of such active energy rays include optical energy rays such as visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ rays, and electron beams.

<Fluorine-based silicon compound>
The fluorine-based silicon compound contained in the fluorine-containing resin composition of the present invention is represented by the following formula (I).

In the formula (I), R _f is a fluoroalkyl having 1 to 20 carbon atoms in which any methylene may be replaced with oxygen; the number of carbon atoms in which at least one hydrogen is replaced with fluorine or trifluoromethyl 6-20 fluoroaryl; or C7-20 fluoroarylalkyl comprising the above fluoroaryl and alkylene.

R _f preferably has fluorine at the carbon at its tip. Examples of such R _f include trifluoromethyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, , 2,2-trifluoro-1-trifluoromethylethyl, 2,2,3,4,4,4-hexafluorobutyl, 2,2,3,3,4,4,5,5-octafluoropentyl , Nonafluoro-1,1,2,2-tetrahydrohexyl, 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5, 6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, henicosafluoro-1,1,2 , 2-Tetrahi And rhododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, and α, α, α-trifluoromethylphenyl. It is done.

R _f is 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, Tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, henicosafluoro-1,1,2,2-tetrahydrododecyl, pentacosafluoro- It is 1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, or α, α, α-trifluoromethylphenyl. From the viewpoint of liquid repellency and slipperiness in a cured film obtained from a surface treating agent containing a fluorine-containing resin composition, 3,3,3-trifluoro Lopyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2- Tetrahydrooctyl or heptadecafluoro-1,1,2,2-tetrahydrodecyl is more preferable.

In the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently hydrogen; having 1 to 30 carbon atoms, and any hydrogen is replaced with fluorine And any methylene may be replaced by oxygen or cycloalkylene; a substituted or unsubstituted aryl having 6 to 30 carbon atoms; or the aryl and any hydrogen may be replaced by fluorine. Often an arylalkyl having 7 to 30 carbon atoms, which is composed of oxygen or alkylene which may be replaced by oxygen or cycloalkylene.

  Examples of the unsubstituted aryl having 6 to 30 carbon atoms include phenyl and naphthyl. Examples of the substituted aryl having 6 to 30 carbon atoms include pentafluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-butylphenyl, and 4-pentylphenyl. 4-heptylphenyl, 4-octylphenyl, 4-nonylphenyl, 4-decylphenyl, 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 4- (1-methylethyl) phenyl, 4- ( 1,1-dimethylethyl) phenyl, 4- (2-ethylhexyl) phenyl, 2,4,6-tris (1-methylethyl) phenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-propoxyphenyl, 4- Butoxyphenyl, 4-pentyloxyphenyl, 4-heptyloxyphenyl, 4-decyl Xiphenyl, 4-octadecyloxyphenyl, 4- (1-methylethoxy) phenyl, 4- (2-methylpropoxy) phenyl, 4- (1,1-dimethylethoxy) phenyl, 4-ethenylphenyl, 4- (1 -Methylethenyl) phenyl, 4- (3-butenyl) phenyl and the like.

R ¹ , R ² , R ⁵ , and R ⁶ in the formula (I) each have 1 to 20 carbon atoms, and arbitrary hydrogen may be replaced with fluorine; the carbon number is 6 to 20 It is preferable that arbitrary hydrogen is aryl which may be replaced with fluorine, or arylalkyl having 7 to 20 carbon atoms and arbitrary hydrogen may be replaced with fluorine, more preferably methyl or phenyl, respectively. preferable.

R ³ and R ⁴ in the formula (I) are each independently preferably hydrogen, phenyl, or alkyl having 1 to 10 carbon atoms in which arbitrary hydrogen may be replaced by fluorine. Methyl, phenyl, 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6,6,6-nona More preferred is fluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, or heptadecafluoro-1,1,2,2-tetrahydrodecyl.

Furthermore, it is preferable that R ^{1 to} R ⁶ in the formula (I) are all methyl.

In the formula (I), A ¹ represents a group represented by the following formula (II), (III) or (IV). A ¹ is considered to contribute to the stability of the surface properties of the cured film obtained from the fluorine-containing resin composition of the present invention, in particular, the stability over time of the surface slipperiness.

In formula (II), Y ¹ represents alkylene having 2 to 10 carbon atoms, and R ⁷ represents hydrogen, alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms. In Formula (III), R ⁸ represents hydrogen, alkyl having 1 to 5 carbons, or aryl having 6 to 10 carbons, X ¹ represents alkylene having 2 to 20 carbons, and Y represents —OCH _2. CH ₂ —, —OCH (CH ₃ ) CH ₂ —, or —OCH ₂ CH (CH ₃ ) — is represented, and p represents an integer of 0 to 3. Furthermore, in formula (IV), Y
² represents a single bond or alkylene having 1 to 10 carbon atoms.

More specifically, in the group represented by the formula (II), Y ¹ is alkylene having 2 to 6 carbon atoms, and R ⁷ is hydrogen or alkyl having 1 to 3 carbon atoms, particularly methyl. Is mentioned. In the group represented by the formula (III), X ¹ is —CH ₂ CH ₂ CH ₂ —, Y is —OCH ₂ CH ₂ —, p is 0 or 1, and R ⁸ is hydrogen. Or the group which is a C1-C3 alkyl is mentioned. Further, the group represented by the formula (IV) includes a group in which Y ² is a single bond or methylene or ethylene. More specifically, the alkyl of R ⁸ is methyl.

Such A ¹ includes, for example, methacryloxypropyl.

  In the formula (I), n represents an integer of 0 to 1,000. For example, n can be appropriately determined according to the solubility of the fluorine-based silicon compound in a solvent that may be used in the surface treatment agent of the present invention. According to such a viewpoint, n is preferably 0 to 500, and more preferably 0 to 200.

For example, as disclosed in Japanese Patent No. 2655683, the fluorine-based silicon compound reacts chlorosilane having a polymerizable unsaturated group by polymerizing silanol having a fluorine-containing hydrocarbon group and hexamethylcyclotrisiloxane. And the polymerization can be stopped. The fluorine-based silicon compound preferably includes compounds represented by the following formulas (I-1) and (I-2) (both n represents 0 to 500, and R ⁹ represents hydrogen or methyl). It is done.

  The content of the fluorine-based silicon compound in the fluorine-containing resin composition of the present invention is 100% by weight of the entire fluorine-containing resin composition from the viewpoint of expressing the slipperiness, water repellency, and oil repellency of the cured film. Is preferably 0.01% by weight or more. Moreover, it is preferable that content of a fluorine-type silicon compound is 10 weight% or less from a cost-effective viewpoint by the use.

<Resin material>
The resin material contained in the fluorine-containing resin composition of the present invention immobilizes the polymerizable functional group of the fluorine-based silicon compound, and constitutes a cured film obtained from the fluorine-containing resin composition of the present invention. It is a substance. The resin material may be the resin itself that constitutes the film, or may be a substance that constitutes the resin by reacting under conditions for forming a cured film, or a composition containing both of these. There may be.

  Examples of the resin material used in the present invention include a curable resin that undergoes radical curing upon irradiation with heat or active energy rays, a monomer that forms the resin, and an oligomer that forms the resin. As the curable resin, a thermosetting resin or an active energy ray curable resin can be used. One kind of these resin materials may be used, or two or more kinds may be used in combination.

  Resin materials include unsaturated bonds capable of radical polymerization, such as (meth) acrylate monomers, unsaturated polyester resins, polyester (meth) acrylate resins, epoxy (meth) acrylate resins, urethane (meth) acrylate resins, etc. Resin.

  Examples of the (meth) acrylate monomer include compounds obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid. For example, polyalkylene glycol di (meth) acrylate, ethylene glycol (meth) acrylate, propylene glycol (meth) acrylate, polyethylene polytrimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (Meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropanetetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetra Methylolmethane tetra (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate. Moreover, the compound which has a silsesquioxane skeleton and has a (meth) acrylate group in a functional group is also mentioned.

  As the unsaturated polyester resin, a condensation product (unsaturated polyester) resulting from an esterification reaction of a polyhydric alcohol and an unsaturated polybasic acid (and a saturated polybasic acid if necessary) is used for And those dissolved in a polymerizable monomer such as a vinyl monomer that can be crosslinked.

  The unsaturated polyester can be produced by polycondensation of an unsaturated acid such as maleic anhydride and a diol such as ethylene glycol. Specifically, a polybasic acid having a polymerizable unsaturated bond such as fumaric acid, maleic acid, and itaconic acid or an anhydride thereof is used as an acid component, and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, Polyhydric alcohols such as cyclohexane-1,4-dimethanol, ethylene oxide adduct of bisphenol A, and propylene oxide adduct of bisphenol A are reacted as alcohol components, and phthalic acid, isophthalic acid, terephthalic acid as necessary , Tetrahydrophthalic acid, adipic acid, sebacic acid, etc. Polybasic acids or anhydrides thereof do not have a sex unsaturated bonds also include those prepared by adding as an acid component.

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

  Examples of the saturated polybasic acid used as a raw material for the polyester (meth) acrylate resin include polyunsaturated unsaturated bonds such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. Examples thereof include basic acids or anhydrides thereof and polymerizable unsaturated polybasic acids such as fumaric acid, maleic acid and itaconic acid or anhydrides thereof. The polyhydric alcohol component is the same as the unsaturated polyester.

  A typical example of the α, β-unsaturated carboxylic acid ester having a glycidyl group (epoxy group) used for the production of a polyester (meth) acrylate resin is glycidyl methacrylate.

  The epoxy (meth) acrylate resin includes a polymerizable unsaturated bond formed by a ring-opening reaction between a compound having a glycidyl group (epoxy group) and a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid. The compound (vinyl ester) having

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

  Further, various epoxy resins may be reacted with bisphenol (for example, A type) or dibasic acid such as adipic acid, sebacic acid, dimer acid (Haridimer 270S: Harima Kasei Co., Ltd.) to impart flexibility.

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

  As the urethane (meth) acrylate resin, for example, radical polymerization can be obtained by reacting a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol and then further reacting a hydroxyl group-containing (meth) acrylic compound. Examples include unsaturated group-containing oligomers.

  Specific examples of the polyisocyanate include 2,4-tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, Phenylmethane triisocyanate, Bannock D-750, Crisbon NK (trade name; manufactured by Dainippon Ink & Chemicals, Inc.), Desmodur L (trade name; manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate L (trade name; Japan) Polyurethane Industry Co., Ltd.), Takenate D102 (trade name; manufactured by Mitsui Takeda Chemical Co., Ltd.), Isonate 143L (trade name; manufactured by Mitsubishi Chemical Corporation), and the like.

Examples of the polyhydroxy compound include polyester polyol, polyether polyol, and the like. Specifically, glycerin-ethylene oxide adduct, glycerin-propylene oxide adduct, glycerin-tetrahydrofuran adduct, glycerin-ethylene oxide-propylene oxide adduct, Trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct, trimethylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol Tall-propylene oxide adduct, dipentaerythritol-tetrahydrofuran adduct, dipentaerythritol-ethyleneoxy - propylene oxide adduct and the like.

  Specific examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3- Butanediol, adduct of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-butanediol, 1,2-cyclohexane glycol, 1,3 -Cyclohexane glycol, 1,4-cyclohexane glycol, paraxylene glycol, bicyclohexyl-4,4-diol, 2,6-decalin glycol, 2,7-decalin glycol and the like.

  Although it does not specifically limit as said hydroxyl-containing (meth) acryl compound, A hydroxyl-containing (meth) acrylic acid ester is preferable, Specifically, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris (hydroxyethyl) isocyanursannodi (meth) acrylate, pentaesitol tri (meth) ) Acrylate and the like.

  A commercial item can also be used as said (meth) acrylate monomer. Examples of such a resin material include NK Hard B100 manufactured by Shin-Nakamura Chemical Co., Ltd., which is a polyfunctional acrylate-based ultraviolet curable resin composition.

<Surface treatment agent>
The surface treating agent of the present invention contains the above-described fluorine-containing resin composition of the present invention. The surface treatment agent of the present invention is a fluorine-containing resin composition of the present invention from the viewpoint of adjusting the concentration of the fluorine-containing resin composition and various physical properties of the surface treatment agent, and from the viewpoint of curing the fluorine-containing resin composition during subsequent cured film formation. Other components other than the resin composition may be further contained. Examples of such other components include a polymerization initiator and a solvent.

  The polymerization initiator can be used for the purpose of accelerating the curing of the fluorine-containing resin composition when the resin material has a polymerizable unsaturated group. As such a polymerization initiator, an initiator that generates radicals by heat or active energy rays is preferable.

  As initiators for generating radicals by heat, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-butyronitrile) Azo compounds such as dimethyl-2,2′-azobisisobutyrate, 1,1′-azobis (cyclohexane-1-carbonitrile); benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, Peroxides such as di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxyneodecanoate; and And dithiocarbamates such as tetraethylthiuram disulfide; . These compounds may be used alone or in combination of two or more.

As initiators for generating radicals with active energy rays, benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2 -Hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2 , 2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 ON, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butyl) Peroxycarbonyl) benzophenone, 3,4,4′-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4′-methoxystyryl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (3 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ′, 4′-dimethoxystyryl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2- (2′-methoxystyryl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)]-2, 6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4 ′ -Methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3′-carbonylbis (7-diethylamino) Coumarin), 2- (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2-c Lorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5 , 5′-Tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 3- (2-methyl-2-dimethylamino) Propionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (η ⁵ -2,4-cyclopentadien-1-yl) -Screw (2 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butanone-1,3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (t- (Hexylperoxycarbonyl) benzophenone, 3,3′-di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4′-di (methoxycarbonyl) -4,3′-di ( t-butylperoxycarbonyl) benzophenone, 4,4′-di (methoxycarbonyl) -3,3′-di (t-butylperoxycarbonyl) benzopheno , 1,2-octanedione-1- [4- (phenylthio) phenyl]-2-(O-benzoyl oxime), and the like. These compounds may be used alone or in combination of two or more.

  The amount of the polymerization initiator in the surface treatment agent of the present invention is not particularly limited, but is preferably about 0.01 to 30 parts by weight with respect to 100 parts by weight of the entire fluorine-containing resin composition, More preferably, it is 20 parts by weight.

Examples of the solvent include hydrocarbon solvents (benzene, toluene, etc.), ether solvents (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbon solvents (methylene chloride, chloroform, chlorobenzene, etc.), Ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, butyl alcohol, t-butyl alcohol, etc.), nitrile solvents (acetonitrile, propionitrile, benzonitrile, etc.) Ester solvents (ethyl acetate, butyl acetate, etc.), carbonate solvents (ethylene carbonate, propylene carbonate, etc.), amide solvents (N, N-dimethylformamide, N, N-di) Tylacetamide), hydrochlorofluorocarbon solvents (HCFC-141b, HCFC-225), hydrofluorocarbon (HFCs) solvents (HFCs having 2 to 4, 5 and 6 or more carbon atoms), perfluorocarbon solvents (perfluoropentane, Perfluorohexane), alicyclic hydrofluorocarbon solvents (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorine solvents (fluoroethers, fluoropolyethers, fluoroketones, fluoroalcohols), aromatic fluorine solvents (α, α , Α-trifluorotoluene, hexafluorobenzene), and water. These solvents may be used alone or in combination of two or more.

  The content of the solvent in the surface treatment agent of the present invention is not particularly limited, but the content of the fluorine-containing resin composition in the surface treatment agent is preferably about 1 to 50% by weight.

  The surface treatment agent of the present invention includes an active energy ray sensitizer, a polymerization inhibitor, a polymerization initiation aid, and a leveling within a range that does not adversely affect surface slipperiness, water repellency, and oil repellency due to the fluorine-containing resin composition. You may further contain arbitrary components, such as an agent, a wettability improving agent, surfactant, a plasticizer, a ultraviolet absorber, antioxidant, an antistatic agent, a silane coupling agent, a filler.

  When the resin material has a polymerizable unsaturated group, as a curing aid for improving the curability of the fluorine-containing resin composition and improving the adhesion to the substrate, which is contained in the surface treatment agent of the present invention. For example, the compound which has 2 or more of thiols in 1 molecule is mentioned. More specifically, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, Methylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglyconate, trishydroxyethyltristhiopropionate, 1,4-bis (3-mercaptobuti Ryloxy) butane (trade name: Karenz MT BD1, manufactured by Showa Denko KK), pentaerythritol tetrakis (3-mercaptobutyrate) (trade name: Karenz M PE1, manufactured by Showa Denko KK, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (trade name) : Karenz MT NR1, manufactured by Showa Denko KK) and the like.

<Hardened film and molded body>
The cured film of the present invention and the molded body having the cured film are obtained from the surface treatment agent of the present invention described above. More specifically, the cured film of the present invention is obtained by a step of forming the film of the surface treatment agent of the present invention and a step of curing the film. The film can be formed by, for example, coating, and the film can be usually cured by one or more of drying, heating, and active energy ray irradiation.

The method for applying the surface treatment agent of the present invention to the substrate is not particularly limited, and such methods include spin coating, roll coating, slit coating, dipping, spray coating, gravure coating, and reverse coating. Method, rod coating method, bar coating method, die coating method, kiss coating method, reverse kiss coating method, air knife coating method, curtain coating method and the like.

  Examples of substrates to be coated are transparent glass substrates such as white plate glass, blue plate glass, silica coated blue plate glass; polycarbonate, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide, polyimide, triacetate, diacetate Synthetic resin sheet, film, etc .; transparent resin substrate used for optical applications such as cycloolefin resin including norbornene resin, methacrylstyrene, polysulfone, alicyclic acrylic resin, polyarylate; aluminum plate, copper plate, nickel plate, Metal substrates such as stainless steel plates; other ceramic substrates, semiconductor substrates having photoelectric conversion elements; urethane rubber and styrene rubber used in various blades.

  These substrates may be pretreated. Examples of such pretreatment include chemical treatment with a silane coupling agent or the like, sandblast treatment, corona discharge treatment, ultraviolet treatment, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition and the like.

  The surface treatment agent film or the formed cured film can be dried in an environment of 10 to about 200 ° C.

  When the surface treatment agent contains an active energy ray polymerization initiator, the film of the surface treatment agent can be cured by irradiating active energy rays after coating and drying.

  There are no particular restrictions on the active energy ray source, but depending on the nature of the active energy ray polymerization initiator used, for example, low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, carbon arc, xenon arc, gas laser, solid state laser And an electron beam irradiation apparatus.

  The cured film of the present invention is excellent in surface slipperiness, water repellency and oil repellency. Applications of the cured film of the present invention include release paper / peel film coating film, water / oil repellent coating film, antifouling coating film, sliding coating film, antireflection coating film and insulating coating film. Can be mentioned.

  In particular, when the resin material in the fluorine-containing resin composition has a polymerizable unsaturated group, the resin material having a polymerizable unsaturated group is cross-linked when forming a cured film. A cured film excellent in interfacial characteristics and compatibility can be obtained. Such a cured film has a higher surface slipperiness. Moreover, as an example of the molded object which has a cured film, the surface treatment agent of this invention to deformed materials, such as a peeling film, an antifouling film, a metal mold | die, glass, etc. which form the cured film of this invention on various films And the coated product of the surface treatment agent of the present invention on an injection molded plastic product.

[Example 1]
Preparation of coating solution and coating film As a fluorine-based silicon compound, a fluorine-based silicon compound (a-1) (molecular weight of about 6,000) represented by the following formula (I-3) is used. Using NK Hard B100 manufactured by Co., Ltd. and using methyl ethyl ketone as a solvent, the mixture was mixed and dissolved in the following composition to obtain a coating liquid (surface treatment agent). The solid content concentration in the coating solution is 20% by weight.
Compound (a-1) 0.016 g
NK HARD B100 10.0g
Methyl ethyl ketone 30.1g

  The fluorine-based silicon compound (a-1) was obtained by the synthesis method shown below according to Japanese Patent No. 2655683.

Synthesis of silanol having fluorine-containing hydrocarbon group A 500 mL three-necked flask equipped with a reflux condenser and a thermometer was charged with ion-exchanged water (33.33 g), THF (140.52 g), triethylamine (28.07 g). ) And cooled to 0 to 10 ° C. in an ice bath while stirring with a magnetic stirrer under a nitrogen atmosphere. Next, heptadecafluoro-1,1,2,2-tetrahydrodecyldimethylchlorosilane (trade name: SIH580.40.4, manufactured by Gelest) (100.00 g) was slowly added to the dropping funnel over 4 hours while paying attention to heat generation. And dripped. After completion of the dropwise addition, the mixture was further stirred for 1 hour, and then acetic acid (16.66 g) and ion-exchanged water (200 mL) were added to separate the aqueous layer and the organic layer. The aqueous layer was extracted with hexane (600 mL) and washed three times with deionized water. Then, the hexane layer was dehydrated with anhydrous magnesium sulfate, and magnesium sulfate was removed by filtration. The filtrate was distilled off under reduced pressure until a solid was precipitated using a rotary evaporator, and then hexane (430 mL) was added and dissolved by heating, and then left to stand overnight in a refrigerator for recrystallization. The precipitated crystals were separated by filtration and dried in a vacuum dryer at room temperature for 6 hours to obtain 84.61 g of colorless needle crystals. ¹ H-NMR measurement of the obtained crystal was performed, and it was confirmed that it was a compound (A-1) having a structure of the following formula.

Synthesis of fluorinated silicon compound (I-3) In a 300 mL three-necked flask equipped with a reflux condenser, a thermometer, and a septum cap, the above compound (A-1) (8.74 g), dry toluene (8 .74 g) is stirred and stirred with a magnetic stirrer at room temperature under an argon atmosphere. After adding n-butyllithium hexane solution (Kanto Chemical, 1.6 mol / L) (10.5 mL) and N, N-dimethylformamide (6.13 g) in this order with a glass syringe, the mixture was stirred at 35 ° C. for 3 hours. Stir. Thereafter, a mixed solution of hexamethylcyclotrisiloxane (90.00 g) / dry toluene (72.00 g) was added and polymerized at 15 ° C. for 3 hours. Next, triethylamine (0.85 g) and 3-methacryloxypropyldimethylchlorosilane (4.14 g) were added and stirred for 10 hours to stop the polymerization. The synthesized product was transferred to a separatory funnel, and the generated lithium chloride was removed by washing with water, followed by drying over anhydrous magnesium sulfate. The low boiling content of the reaction product thus obtained was distilled off over 2 hours under the condition of 110 ° C./1.3 kPa, and 69.96 g of a colorless transparent liquid was obtained in the residue of the kettle. The obtained transparent liquid was subjected to ¹ H-NMR measurement and found to be compound (I-3) having the structure of the above formula. The weight average molecular weight determined by GPC analysis (gel permeation chromatography method) was 6,000, and the molecular weight distribution was 1.12.

The obtained coating liquid was applied onto a polyethylene terephthalate film (thickness: 125 μm, brand name: Lumirror 125-T60, manufactured by Toray Industries, Inc.) using a coating rod (# 9, manufactured by RD Specialties). did. When the coating rod (# 9) is used, the wet film thickness (as described in the RD Specialties catalog) is 20 μm.

The obtained coating film was dried in a high-temperature chamber at 70 ° C. for 1 minute, and using a conveyor-type UV irradiation apparatus attached with a high-pressure mercury lamp (H08-L41, rated 160 W / cm, manufactured by Iwasaki Electric Co., Ltd.) Ultraviolet rays were irradiated at an illuminance of 80 mW / cm ² and an exposure amount of 500 mJ / cm ² to obtain a transparent coating film (cured film) having a theoretical film thickness of 4 μm. The exposure amount was measured with an illuminometer (UVPF-A1 / PD-365, manufactured by Iwasaki Electric Co., Ltd.). The theoretical film thickness was calculated from the wet film thickness when using the coating rod (# 9) and the resin solid content in the coating liquid according to the following formula.
Theoretical film thickness (μm) = (wet film thickness when a coating rod is used) × (solid content concentration in coating liquid (% by weight)) / 100

[Comparative Example 1]
Preparation of coating solution and coating film Instead of fluorine-based silicon compound (a-1), one-terminal methacryloxypropyl group-modified dimethyl silicone (b-1) represented by the following formula (V) (trade name; Silaplane FM A coating solution was prepared in the same manner as in Example 1 except that −0721 manufactured by Chisso Corporation and a molecular weight of about 6,000 was used.
Compound (b-1) 0.016 g
NK HARD B100 10.0g
Methyl ethyl ketone 30.1g

[Test 1]
The physical properties of the coating films obtained in Example 1 and Comparative Example 1 were measured by the following methods.

Friction resistance test (ASTM flat indenter)
Using a surface property tester HEIDON Type: 14W (manufactured by Shinto Kagaku Co., Ltd.), measurement was performed according to ASTM D1894.

Scratch resistance test (scratching needle)
A sapphire scratch needle (R = 0.3, tip angle 60 °) was attached to the surface property tester HEIDON Type: 14W (manufactured by Shinto Kagaku Co., Ltd.), and pulled at a pulling speed of 120 mm / min with a vertical load of 100 g. The friction coefficient of the coating film surface was calculated from the stress at the time.

  Table 1 shows the physical property values of the coating films obtained.

[Example 2]
Preparation of Coating Liquid and Coating Film Using the obtained fluorine-based silicon compound (a-1) (molecular weight of about 6,000) as the fluorine-based silicon compound, dipentaerythritol hexaacrylate (Shin Nakamura Chemical Industries ( NK ester A-DPH) and pentaerythritol tetrakis (3-mercaptopropionate) (4TP-5 manufactured by Maruzen Petrochemical Co., Ltd.) using methyl ethyl ketone and methyl isobutyl ketone as solvents, radical polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) was mixed and dissolved with the following composition to obtain a coating liquid (surface treatment agent). The solid content concentration in the coating solution is 40% by weight.
Compound (a-1) 0.02 g
NK Ester A-DPH 12.0g
4TP-5 8.0g
Methyl ethyl ketone 6.0g
Methyl isobutyl ketone 24.0g
V-65 2.0g

  The obtained coating solution was applied onto a polyethylene terephthalate film (thickness: 188 μm, brand name: Lumirror 188-T60, manufactured by Toray Industries, Inc.) using a coating rod (# 6, manufactured by RD Specialties). did. When the coating rod (# 6) is used, the wet film thickness (as described in the RD Specialties catalog) is 13.7 μm.

The obtained coating film was dried in a high temperature chamber at 150 ° C. for 1 minute to obtain a transparent coating film (cured film) having a theoretical film thickness of 5.4 μm. The theoretical film thickness was calculated from the wet film thickness when the coating rod (# 6) was used and the resin solid content in the coating liquid according to the following formula.
Theoretical film thickness (μm) = (wet film thickness when a coating rod is used) × (solid content concentration in coating liquid (% by weight)) / 100

[Comparative Example 2]
Preparation of coating solution and coating film Instead of fluorine-based silicon compound (a-1), one-terminal methacryloxypropyl group-modified dimethyl silicone (b-1) represented by formula (V) (molecular weight: about 6,000) A coating solution was prepared in the same manner as in Example 2 except that (trade name; Silaplane FM-0721, manufactured by Chisso Corporation, molecular weight of about 6,000) was used.
Compound (b-1) 0.02 g
NK Ester A-DPH 12.0g
4TP-5 8.0g
Methyl ethyl ketone 6.0g
Methyl isobutyl ketone 24.0g
V-65 2.0g

[Test 2]
Using the coating films obtained in Example 2 and Comparative Example 2, a frictional resistance test was performed in the same manner as in Test 1. Table 2 shows the coefficient of friction of the obtained coating film.

(Consideration of evaluation results of examples)
When a resin film was produced with NK Hard B100 manufactured by Shin-Nakamura Chemical Co., Ltd., which is an ultraviolet curable resin composition, a fluorine-based silicon compound was introduced when Example 1 and Comparative Example 1 were compared in a frictional resistance test. In Example 1, the static friction coefficient and the dynamic friction coefficient are lower. Similarly, in the scratch resistance test in which the change in slipperiness was confirmed, the numerical value of the dynamic friction coefficient was lower in Example 1 in which the fluorine-based silicon compound was introduced. ) Is improved.

  Even when a resin film was prepared with dipentaerythritol hexaacrylate, which is a thermosetting resin composition, when Example 2 and Comparative Example 2 were compared in a frictional resistance test, Example 2 in which a fluorine-based silicon compound was introduced was used. It can be seen that the static friction coefficient and the dynamic friction coefficient are lower, and the slip property (slip property) is improved due to the fluorine-containing effect.

  The surface treatment agent of the present invention is effective in improving the slipping property (sliding property), water repellency and oil repellency on the surface of the cured film, preventing scratches on various substrate surfaces such as plastic, metal and glass, and preventing contamination. It can be used as a surface modifier for In addition, when the surface of the toner particles is coated with a surface treatment agent, it is effective in preventing sticking of the toner particles and strengthening the charging to negatively charge the toner particles. Also, a fixing roller, a mug roller, a rubber roller It can be used as a surface modifier for members of an electronic copying machine, such as imparting a non-adhesive function to a photoconductor drum, a peeling claw, a sliding function on a cleaning blade, and an antifouling function. In addition, the top coat for automobiles for the purpose of preventing dirt, the surface modifier for hard coats, the antifouling treatment agent for optical resins used in lenses, antifogging treatment agents, wall materials, flooring materials, and other building parts. Antifouling treatment agent, mold release treatment agent used in nanoimprinting, resist material modifier, water-repellent / waterproofing treatment agent for printed circuit boards, protective film for display, antifouling treatment agent for protective film It can be used as a surface modifier for preventing contamination of liquid crystal displays, plasma display surfaces and touch panels, preventing fingerprint adhesion, and scratching, and a release treatment for imparting a peeling function to films such as polyester. Is possible.

Claims (7)

A fluorine-based silicon compound represented by the following formula (I):
A fluorine-containing resin composition comprising: a curable resin; and a resin material containing at least one selected from monomers constituting the resin.

(In the formula (I),
R _f is a fluoroalkyl having 1 to 20 carbon atoms in which any methylene may be replaced with oxygen; a fluoroaryl having 6 to 20 carbon atoms in which at least one hydrogen is replaced with fluorine or trifluoromethyl; Or a fluoroarylalkyl having 7 to 20 carbon atoms composed of the fluoroaryl and alkylene,
n represents an integer of 0 to 1,000,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently hydrogen; having 1 to 30 carbon atoms, any hydrogen may be replaced with fluorine, and any Alkyl in which methylene may be replaced by oxygen or cycloalkylene; substituted or unsubstituted aryl having 6 to 30 carbon atoms; or aryl and any hydrogen may be replaced by fluorine, and any methylene is oxygen or An arylalkyl having 7 to 30 carbon atoms composed of alkylene which may be substituted with cycloalkylene;
A ¹ represents the following formula (II), (III) or (IV).

In Formula (II), Y ¹ represents alkylene having 2 to 10 carbon atoms, R ⁷ represents hydrogen, alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms,
In the formula (III), R ⁸ represents hydrogen, alkyl having 1 to 5 carbons, or aryl having 6 to 10 carbons, X ¹ represents alkylene having 2 to 20 carbons, and Y represents —OCH ₂ CH _{2 -, - OCH (CH 3} ) CH 2 -, or -OCH ₂ CH (CH ₃₎ - represents, p represents an integer of 0 to 3,
In formula (IV), Y ² represents a single bond or alkylene having 1 to 10 carbon atoms. ) R _f is 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, Tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, henicosafluoro-1,1,2,2-tetrahydrododecyl, pentacosafluoro- 1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, or α, α, α-trifluoromethylphenyl,
R ³ and R ⁴ are each independently methyl, phenyl, 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5 , 6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, or heptadecafluoro-1,1,2,2-tetrahydrodecyl,
The fluorine-containing resin composition according to claim ¹ , wherein R ¹ , R ² , R ⁵ , and R ⁶ are each methyl or phenyl. R _f is 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, The fluorine-containing resin composition according to claim 2, which is tridecafluoro-1,1,2,2-tetrahydrooctyl or heptadecafluoro-1,1,2,2-tetrahydrodecyl. In the formula (II), Y ¹ is alkylene having 2 to 6 carbon atoms, R ⁷ is hydrogen or alkyl having 1 to 3 carbon atoms,
In the formula (III), X ¹ is —CH ₂ CH ₂ CH ₂ —, Y is —OCH ₂ CH ₂ —, p is 0 or 1, and R ⁸ is hydrogen or 1 to 3 carbon atoms. Alkyl,
The fluorine-containing resin composition according to claim 3, wherein Y ² in formula (IV) is a single bond, methylene or ethylene.   The surface treating agent containing the fluorine-containing resin composition as described in any one of Claims 1-4.   A cured film obtained from the surface treatment agent according to claim 5.   The molded object which has a cured film of Claim 6.