JP6067938B2 - Polyester resin composition - Google Patents

Description

  The present invention relates to a polyester resin composition excellent in transparency, adhesion and antifouling property, which is useful as a surface coating material for top coat materials, clothing, fibers and the like in the field of automobile members, electronic equipment, building materials, and the like. The present invention relates to a polyester resin composition having excellent adhesion, antifouling properties, antibacterial properties and antiviral properties.

  Various decorative films and various synthetic resin sheets are used as topcoat materials because they are excellent in moldability, inexpensive, and lightweight in decoration applications such as automobile parts, electronic devices, and building materials.

  However, there is a problem such as a decrease in transparency, non-fouling due to fingerprint adhesion, and adhesion such as easy peeling, and in order to solve these various problems, an antifouling film imparted with an antifouling function is also used. It has been proposed (see, for example, Patent Documents 1 and 2 below).

  In particular, it adhered to the surface of optical members such as antireflection films, optical filters, optical lenses, liquid crystal displays, CRT displays, projection televisions, plasma displays, EL displays, etc. used as parts of optical products, and the surfaces of wallpaper, signs, etc. Dirt degrades optical performance and appearance.

  In recent years, various types of touch-panel electronic devices have attracted attention, but in general, the display screen of a touch panel operated with a fingertip is often difficult to see due to adhesion of finger grease, fingerprints, and other dirt. is there.

  For this reason, in a top coat material such as a transparent film having excellent antifouling property, such as a film or sheet, further improvement in the antifouling property is desired.

  In addition, these films and sheets are used in everyday living spaces of ordinary households, and there are many cases where they are directly touched by human hands, and antibacterial properties have been imparted to top coat materials such as these films and sheets. Things are also desired.

  Further, the present applicants can obtain an ionic liquid such as a fluoroalkyl group-containing oligomer having an alkoxysilyl group and a borophonium salt having an alkoxysilyl group by hydrolyzing the alkoxysilyl group in an alcohol solution. Various nanocomposite particles have been proposed (see, for example, Patent Documents 3 to 5).

JP 2009-216750 A JP 2011-74105 A JP 2007-270124 A JP 2009-209349 A JP 2010-77383 A

  However, when the nanocomposite particles are contained in a resin, it is difficult to obtain a product with excellent transparency.

  Therefore, the first object of the present invention is to provide a polyester resin composition excellent in transparency, adhesion and antifouling property. The second object of the present invention is to provide a polyester resin composition excellent in transparency, adhesion, antifouling properties, antibacterial properties and antiviral properties.

  In view of the above-mentioned problems, the present inventors have conducted extensive research. As a result, the polyester resin (A), the (meth) acrylic polymer (B), the monomer (C) having a (meth) acryloyl group, and organic The polyester resin composition containing the metal compound (D) and the solvent (E) contains at least one kind selected from a fluoroalkyl group-containing oligomer represented by the following general formula (1) and a hydrolysis product thereof. The compound containing the fluorine compound (F) has excellent antifouling properties while maintaining excellent transparency and adhesion, and further, an onium salt represented by the following general formula (2) and the onium What contains at least one compound (G) selected from salt hydrolysis products maintains excellent antibacterial and antiviral properties while maintaining excellent transparency, adhesion and antifouling properties. What you have It found that, which resulted in the completion of the present invention.

  That is, the present invention (1) includes a polyester resin (A), a (meth) acrylic polymer (B), a monomer (C) having a (meth) acryloyl group, an organometallic compound (D), a solvent ( E) and at least one fluorine-containing compound (F) selected from a fluoroalkyl group-containing oligomer represented by the following general formula (1) and a hydrolysis product thereof: A composition is provided.

Wherein R ¹ and R ² represent a — (CF ₂ ) p—Y group or a —CF (CF ₃ ) — [OCF ₂ CF (CF ₃ )] q—OC ₃ F ₇ group, and R ¹ And R ² may be the same group or different groups, Y in R ¹ and R ² represents a hydrogen atom, a fluorine atom or a chlorine atom, and p and q are integers of 0 to 10. R ³ , R ⁴ and R ⁵ may be the same or different groups, and R ³ , R ⁴ and R ⁵ are linear or branched alkyl groups having 1 to ⁵ carbon atoms. M is an integer of 2 to 3.)

  Further, the present invention (2) further includes the polyester resin according to (1), further comprising at least one compound (G) selected from an onium salt represented by the following general formula (2) and a hydrolysis product thereof. A composition is provided.

(In the formula, A represents a phosphorus atom or a nitrogen atom. R ⁶ , R ⁷ and R ⁸ represent a linear or branched alkyl group having 1 to 18 carbon atoms. R ⁹ has 1 to 5 carbon atoms. .n which a straight or branched alkyl group is an integer of 1 to 8 .X ^- represents an anion group).

  ADVANTAGE OF THE INVENTION According to this invention, the polyester resin composition excellent in transparency, adhesiveness, and antifouling property can be provided. Moreover, according to this invention, the polyester resin composition excellent in transparency, adhesiveness, antifouling property, antibacterial property, and antiviral property can be provided.

In Example 1, it is an electron micrograph of the polyester fiber before processing. In Example 1, it is an electron micrograph of the polyester fiber after spin-coating with the polyester resin composition sample.

  The polyester resin composition of the present invention comprises a polyester resin (A), a (meth) acrylic polymer (B), a monomer (C) having a (meth) acryloyl group, an organometallic compound (D), a solvent ( E) and at least one fluorine-containing compound (F) selected from a fluoroalkyl group-containing oligomer represented by the following general formula (1) and a hydrolysis product thereof: It is a composition.

Wherein R ¹ and R ² represent a — (CF ₂ ) p—Y group or a —CF (CF ₃ ) — [OCF ₂ CF (CF ₃ )] q—OC ₃ F ₇ group, and R ¹ And R ² may be the same group or different groups, Y in R ¹ and R ² represents a hydrogen atom, a fluorine atom or a chlorine atom, and p and q are integers of 0 to 10. R ³ , R ⁴ and R ⁵ may be the same or different groups, and R ³ , R ⁴ and R ⁵ are linear or branched alkyl groups having 1 to ⁵ carbon atoms. M is an integer of 2 to 3.)

  In the present invention, “(meth) acrylate” and “acrylic” and “methacrylic” or both of “acrylate” and “methacrylate” and “(meth) acrylate” ) Acrylic ”and“ acryloyl ”and / or“ methacryloyl ”may be described as“ (meth) acryloyl ”, respectively.

  The polyester resin (A) according to the polyester resin composition of the present invention is produced by a polymerization reaction of a reactive raw material composed of a compound having an ester-forming functional group. An ester-forming functional group refers to a functional group that can react with a carboxyl group or a hydroxyl group to form an ester bond. The ester-forming functional group includes a carboxyl group, a hydroxyl group, an ester-forming derivative group of a carboxyl group, and an ester-forming derivative group of a hydroxyl group. The ester-forming derivative group of a carboxyl group is a group derived from a carboxyl group that has been made anhydride, acid chloride, or halogenated, and reacts with a hydroxyl group to form an ester bond. The ester-forming derivative group of a hydroxyl group is a group that is derived, for example, by acetylation of a hydroxyl group and reacts with other carboxyl groups to form an ester bond. In particular, it is preferable that the ester-forming functional group is a carboxyl group or a hydroxyl group from the viewpoint of good reactivity during production of the polyester resin.

  The reactive raw material includes, for example, a polyvalent carboxylic acid component and a glycol component.

  The polyvalent carboxylic acid component is composed of a divalent or higher polyvalent carboxylic acid and an ester-forming derivative in which a carboxyl group in the polyvalent carboxylic acid is substituted with an ester-forming derivative derived from the carboxyl group. One or more selected.

  Examples of the polyvalent carboxylic acid component include aromatic dicarboxylic acids and aliphatic dicarboxylic acids. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, diphenic acid, naphthalic acid, 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2, Examples of the aliphatic dicarboxylic acid include linear, branched or alicyclic oxalic acid, malonic acid, succinic acid, maleic acid, itaconic acid, glutaric acid, and adipic acid. , Pimelic acid, 2,2-dimethylglutaric acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, diglycolic acid, thiodipropion An acid etc. are mentioned.

  Examples of the polyvalent carboxylic acid component include dicarboxylic acids having a metal sulfonate group, tribasic acid anhydrides such as tribasic acid anhydrides and tetrabasic acid anhydrides, and ester-forming derivatives thereof. It is done. Examples of the dicarboxylic acid having a metal sulfonate group and an ester-forming derivative thereof (hereinafter collectively referred to as a dicarboxylic acid having a metal sulfonate group) include 5-sulfoisophthalic acid, 2-sulfoisophthalic acid, 4-sulfo Examples include alkali metal salts such as isophthalic acid, sulfoterephthalic acid, 4-sulfonaphthalene-2,6-dicarboxylic acid, and ester-forming derivatives thereof. Examples of trivalent or higher valent carboxylic acids and ester-forming derivatives thereof include hemimellitic acid, trimellitic acid, trimedic acid, merophanic acid, pyromellitic acid, benzenepentacarboxylic acid, meritic acid, cyclopropane- Examples include 1,2,3-tricarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, ethanetetracarboxylic acid, and ester-forming derivatives thereof.

  The polyvalent carboxylic acid component is used alone or in combination of two or more. Among these polyvalent carboxylic acid components, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid, and aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedioic acid, This is preferable in terms of easy reaction, excellent adhesion of the resulting resin, weather resistance, durability, and the like. In particular, it is preferable that only an aromatic dicarboxylic acid is used as the polyvalent carboxylic acid component, or that the aromatic dicarboxylic acid is the main component of the polyvalent carboxylic acid component.

  Examples of the glycol component include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, and other polyethylene glycols, propylene glycol, dipropylene glycol, and tripropylene glycol. , Polypropylene glycol such as tetrapropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl- 1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 2,2,4 Trimethyl-1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol 4,4′-dihydroxybiphenol, 4,4′-methylenediphenol, 4,4′-isopropylidenediphenol, 1,5-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,2-bis (4- Hydroxyphenyl) propane (bisphenol A), bisphenol S and the like. A glycol component is used individually by 1 type or in combination of 2 or more types. In particular, as the glycol component, ethylene glycol, diethylene glycol, butanediol such as 1,4-butanediol, hexanediol such as 1,6-hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, bisphenol A and the like Glycols and acetates of their hydroxyl groups are preferred because they are easy to react and have excellent durability of the resulting resin.

  The amount of the dicarboxylic acid component and the diol component contained in the reaction raw material is preferably adjusted so that the ratio of the total mole of the diol component to the total number of moles of the dicarboxylic acid component is in the range of 1 to 2.5.

  The reaction raw material is preferably a compound having a hydroxyl group introduced in the molecule in terms of high adhesion and reactivity. Examples of such a compound include pentaerythritol, trimethylolpropane, and dimethylolbutane. An acid etc. are mentioned.

  When the polyvalent carboxylic acid component contains an ester-forming derivative of polyvalent carboxylic acid and the glycol component contains glycol, the polyester resin (A) is an ester of an ester-forming derivative of polyvalent carboxylic acid and glycol. It may be produced through a first-stage reaction that is an exchange reaction and a second-stage reaction in which a reaction product of the first-stage reaction is polycondensed. In the first stage reaction, all of the reaction raw materials may be contained in the reaction system from the beginning, or a part may be added to the reaction system during the ester polycondensation reaction. In the case of batch charging, for example, the reaction system is gradually heated to 150 to 260 ° C. under normal pressure under an inert gas atmosphere such as nitrogen gas, whereby the transesterification reaction proceeds. The second stage reaction proceeds, for example, within a temperature range of 160 to 280 ° C. under a reduced pressure of 6.7 hPa (5 mmHg) or less. In the first stage reaction and the second stage reaction, conventionally known titanium, antimony, lead, zinc, magnesium, calcium, manganese, alkali metal compounds and the like may be added to the reaction system at any time as a catalyst.

  Although content of the polyester resin (A) in the polyester resin composition of this invention is selected suitably, Preferably it is 10-99 mass%, Most preferably, it is 25-90 mass%. More preferably, it is 30-80 mass%.

  The (meth) acrylic polymer (B) according to the polyester resin composition of the present invention is a component that improves the adhesion to the substrate, and a polymerization raw material consisting only of a polymerization monomer having a (meth) acrylic structure. It is a polymer obtained by polymerizing a polymerization raw material mainly comprising a polymer obtained by polymerization or a polymerization monomer having a (meth) acrylic structure. Examples of the monomer having a (meth) acrylic structure that is a polymerization raw material for the (meth) acrylic polymer (B) include acrylic acid, methacrylic acid, (meth) acrylic acid ester, (meth) acrylamide monomers, and the like. More specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, n-decyl (meth) acrylate, glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, Hexane (Meth) acrylic acid esters such as aldi (meth) acrylate; alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl ( Hydroxyalkyl (meth) acrylates such as meth) acrylate and 2-hydroxypropyl (meth) acrylate; N, N dimethylaminoethyl (meth) acrylate, N, N diethylaminoethyl (meth) acrylate, N, N dimethylaminopropyl (meth) ) Acrylates, nitrogen-containing (meth) acrylic esters such as N, N diethylaminopropyl (meth) acrylate; N, N dimethylaminoethyl (meth) acrylamide, N, N diethylaminoethyl (meth) acrylate Ruamido, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylamino propyl (meth) acrylamide, N-isopropyl (meth) (meth) acrylamide monomer such as acrylamide; and glycidyl (meth) acrylate.

  (Meth) acrylic polymer (B) is (meth) acrylic acid ester, (meth) acrylamide, more specifically alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, nitrogen-containing (meth) acrylic acid Even if it is only one kind of polymerization monomer having a (meth) acrylic structure such as ester, (meth) acrylamide, glycidyl (meth) acrylate, etc., a polymerization monomer having two or more (meth) acrylic structures Or a copolymer of a monomer for polymerization having one or more (meth) acrylic structures and an ethylenically unsaturated monomer.

  Examples of the ethylenically unsaturated monomer used for copolymerization with a polymerization monomer having a (meth) acrylic structure include carboxylic acid-containing ethylenically unsaturated monomers such as itaconic acid and ethylenic functional groups such as (meth) acrylonitrile. Examples include unsaturated monomers, vinyl acetate, vinyl propionate, styrene, α-methylstyrene, allylamine, and ethyleneimine.

  The (meth) acrylic polymer (B) may be one type or a combination of two or more types.

  The (meth) acrylic polymer (B) is preferably a polymer obtained by polymerizing a polymerization raw material in which part or all of the monomer as a polymerization raw material is a monomer containing nitrogen. As monomers for nitrogen-containing (meth) acrylic polymer (B), N, N dimethylaminoethyl (meth) acrylate, N, N diethylaminoethyl (meth) acrylate, N, N dimethylaminopropyl (meth) acrylate N, N diethylaminopropyl (meth) acrylate and other nitrogen-containing (meth) acrylic acid esters, N, N dimethylaminoethyl (meth) acrylamide, N, N diethylaminoethyl (meth) acrylamide, N, N dimethylaminopropyl (meth) ) Acrylamide, N, N diethylaminopropyl (meth) acrylamide, (meth) acrylamide such as N isopropyl (meth) acrylamide, allylamine, and ethyleneimine. Among these, N, N dimethylaminoethyl (meth) acrylate, N, N diethylaminoethyl (meth) acrylate, N, N dimethylaminopropyl) (meth) acrylate, N, N diethylaminopropyl (meth) acrylate, N isopropyl ( Meth) acrylamide is preferred.

  Although the usage-amount of the monomer for (meth) acrylic polymer (B) containing nitrogen is not specifically limited, (meth) acrylic heavy containing nitrogen with respect to the whole quantity of the polymerization raw material of (meth) acrylic polymer (B). The mass ratio of the monomer for coalescence (B) is 0.5 to 100 mass%, preferably 1 to 60 mass%.

  The polymerization method for obtaining the (meth) acrylic polymer (B) by polymerizing the monomer as the polymerization raw material is not particularly limited, and known methods such as solution polymerization, suspension polymerization, and emulsion polymerization are appropriately used. Specifically, taking the case of solution polymerization using an organic solvent as an example, a suitable organic solvent can be used as the polymerization solvent for the (meth) acrylic polymer, for example, methyl alcohol, ethyl alcohol, n Alcohols such as -propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol; cellosolves such as cellosolve acetate, methyl cellosolve, ethyl cellosolve, n-butyl cellosolve, i-butyl cellosolve, n-propyl cellosolve; propylene Propylene glycol ethers such as glycol n-butyl ether, propylene glycol methyl ether, propylene glycol phenyl ether, dipropylene glycol methyl ether, propylene glycol methyl ether acetate; Ene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, aromatic (petroleum fraction) solvents, phthalate ester plasticizers, alkyl phosphate esters, etc., but (meth) acrylic polymers dissolve or disperse If it is a possible solvent, it is not restricted to these solvents. Considering the ease of reaction, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, acetone, methyl ethyl ketone, toluene, and ethyl acetate are preferable as the polymerization solvent.

  The content of the (meth) acrylic polymer (B) in the polyester resin composition of the present invention is appropriately selected, but in many cases, it is preferably 0.1 to 100 parts by mass of the polyester resin (A). 250 parts by mass, particularly preferably 0.5 to 200 parts by mass, and still more preferably 1 to 150 parts by mass.

  The monomer (C) having a (meth) acryloyl group according to the polyester resin composition of the present invention is a component that further improves the adhesion and adhesion to the substrate by a synergistic effect with the (meth) acrylic polymer (B). It is. The monomer (C) having a (meth) acryloyl group is a monomer that is polymerized by heating or irradiation with active energy rays. And as a monomer (C) which has a (meth) acryloyl group, an active energy ray hardening monomer is preferable. Examples of the active energy ray-curable monomer having a (meth) acryloyl group according to the monomer (C) having a (meth) acryloyl group include ethylene glycol, dipropylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, and tripropylene. Ester of (meth) acrylic acid in alcohol such as glycol, trimethylolpropane, pentaerythritol; Ester of allylic alcohol in phthalic acid, maleic acid, isocyanuric acid, etc .; Phthalic acid, maleic acid, isocyanuric Examples include those obtained by esterifying glycidyl (meth) acrylate with an acid or the like. The monomer (C) having a (meth) acryloyl group may be one type or a combination of two or more types.

  Although content of the monomer (C) which has a (meth) acryloyl group in the polyester resin composition of this invention is selected suitably, Preferably it is 0.1-40 with respect to 100 mass parts of polyester resins (A). Part by mass, particularly preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass.

  The organometallic compound (D) according to the polyester resin composition of the present invention is a component that increases the compatibility between the polyester resin (A) and the (meth) acrylic resin (B) in the polyester resin composition of the present invention. . Therefore, when the polyester resin composition of the present invention contains the organometallic compound (D), the polyester resin composition of the present invention can uniformly disperse the polyester resin (A) and the (meth) acrylic polymer (B). It becomes possible.

  Examples of the organometallic compound (D) include metal alkoxides, metal acylates, metal chelates, and the like, and those having metal atoms such as zirconium, titanium, aluminum, and silicon are preferable. Examples of the organometallic compound (D) include zirconium tetranormal propoxide, zirconium tetranormal butoxide, zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetonate), zirconium. Dibutoxybis (ethylacetonate), zirconium tributoxymonostearate, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium butoxide dimer, titanium tetra-2-ethylhexoxide, titanium diisopropoxybis (acetylacetonate) ), Titanium tetraacetylacetonate, titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethi) Acetoacetate), aluminum acetylacetonate, monomethyltriisocyanate silane, tetraisocyanate silane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, propyltrimethoxysilane, phenyltrimethoxy Examples include silane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane. The organometallic compound (D) may be one type or a combination of two or more types.

  Although content of the organometallic compound (D) in the polyester resin composition of this invention is suitably selected, Preferably it is 1-60 mass parts with respect to 100 mass parts of polyester resins (A), Most preferably, it is 3- 50 parts by mass, more preferably 5 to 40 parts by mass.

  As long as the solvent (E) according to the polyester resin composition of the present invention can dissolve the polyester resin (A) and the (meth) acrylic polymer (B) and can dissolve or uniformly disperse other components, There is no particular limitation, for example, alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol; cellosolve acetate, methyl cellosolve, ethyl cellosolve, n-butyl cellosolve, Cellosolves such as i-butyl cellosolve and n-propyl cellosolve; propylene glycol n-butyl ether, propylene glycol methyl ether, propylene glycol phenyl ether, dipropylene glycol methyl ether, propylene glycol methyl ether Propylene glycol ethers such as acetate; toluene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, aromatic (petroleum fraction) solvents, phthalate ester plasticizers, alkyl phosphate esters, etc. Or it may be a combination of two or more. Further, the solvent (E) may be a reaction solvent used for the production of the (meth) acrylic polymer (B). That is, the solvent (E) is used as a reaction solvent for the production of the (meth) acrylic polymer (B), and the (meth) acrylic polymer (B) is dissolved in the resulting reaction solution, that is, the solvent (E). The polyester resin composition of the present invention can be produced by mixing other components into the solution.

  Content of the solvent (E) in the polyester resin composition of this invention is suitably selected, Preferably it is 10-99 mass%, Most preferably, it is 20-95 mass%.

  At least one fluorine-containing compound (F) selected from the fluoroalkyl group-containing oligomer represented by the general formula (1) and the hydrolysis product thereof according to the polyester resin composition of the present invention is a polyester resin composition. It is a component that imparts excellent antifouling properties while maintaining excellent transparency and adhesiveness.

  The fluoroalkyl group-containing oligomer according to the polyester resin composition of the present invention is represented by the following general formula (1).

Wherein R ¹ and R ² represent a — (CF ₂ ) p—Y group or a —CF (CF ₃ ) — [OCF ₂ CF (CF ₃ )] q—OC ₃ F ₇ group, and R ¹ And R ² may be the same group or different groups, Y in R ¹ and R ² represents a hydrogen atom, a fluorine atom or a chlorine atom, and p and q are integers of 0 to 10. R ³ , R ⁴ and R ⁵ may be the same or different groups, and R ³ , R ⁴ and R ⁵ are linear or branched alkyl groups having 1 to ⁵ carbon atoms. M is an integer of 2 to 3.)

Examples of the linear or branched alkyl group having 1 to 5 carbon atoms represented by R ³ , R ⁴ and R ⁵ in the general formula (1) include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Etc.

  The fluoroalkyl group-containing oligomer represented by the general formula (1) is produced, for example, by reacting a trialkoxyvinylsilane such as trimethoxyvinylsilane with a fluoroalkanoyl peroxide (for example, JP-A-2002-338691, JP, 2010-77383, A).

  The hydrolysis product of the fluoroalkyl group-containing oligomer represented by the general formula (1) according to the polyester resin composition of the present invention is such that the fluoroalkyl group-containing oligomer represented by the general formula (1) is hydrolyzed. However, the hydrolyzing method of the fluoroalkyl group-containing oligomer represented by the general formula (1) is not particularly limited, and even if it is a method using an alkali or acid catalyst, no catalyst is used. It may be the method performed in Examples of the alkali catalyst used for the hydrolysis include alkalis such as aqueous ammonia, sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and potassium carbonate. Examples of the acid catalyst used for hydrolysis include acids such as hydrochloric acid and acetic acid.

  When the polyester resin composition of the present invention contains a hydrolysis product of a fluoroalkyl group-containing oligomer represented by the general formula (1), the fluoroalkyl group-containing oligomer represented by the general formula (1) May be hydrolyzed in the presence of only other components, or may be hydrolyzed in the presence of other components. Specifically, for example, (i) First, a solution in which only the fluoroalkyl group-containing oligomer represented by the general formula (1) is dissolved in the solvent (E) is prepared. Hydrolyzing the fluoroalkyl group-containing oligomer represented by (1), and then mixing the resulting hydrolysis solution and other components to produce a polyester resin composition, (ii) A solution in which the polyester resin (A) is dissolved in the solvent (E) is prepared together with the fluoroalkyl group-containing oligomer represented by the general formula (1), and then the solution represented by the general formula (1) in the solution is prepared. Hydrolyzing the fluoroalkyl group-containing oligomer, and then mixing the resulting hydrolysis solution with other components to produce a polyester resin composition. Among these, it is preferable to hydrolyze the fluoroalkyl group-containing oligomer represented by the general formula (1) in a solution containing the polyester resin (A) as in the above method (ii).

  The content of at least one fluorine-containing compound (F) selected from the fluoroalkyl group-containing oligomer represented by the general formula (1) and the hydrolysis product thereof in the polyester resin composition of the present invention is appropriately selected. However, it is preferably 0.1 to 10% by mass, particularly preferably 0.5 to 5% by mass. In addition, when the polyester resin composition of this invention contains both the fluoroalkyl group containing oligomer represented by General formula (1), and its hydrolysis product, the said content is total content of both. It is. The content of the hydrolysis product of the fluoroalkyl group-containing oligomer represented by the general formula (1) is the fluoroalkyl group-containing oligomer represented by the general formula (1) before being hydrolyzed. In this case, the content of the fluoroalkyl group-containing oligomer represented by the general formula (1) before hydrolysis is used. That is, the content of the hydrolysis product of the fluoroalkyl group-containing oligomer represented by the general formula (1) is converted into the fluoroalkyl group-containing oligomer represented by the general formula (1) before being hydrolyzed. Value.

  The polyester resin composition of the present invention can further contain at least one compound (G) selected from an onium salt represented by the general formula (2) and a hydrolysis product thereof. The polyester resin composition of the present invention further contains at least one compound (G) selected from an onium salt represented by the general formula (2) and a hydrolysis product thereof, thereby providing excellent transparency. It has excellent antibacterial and antiviral properties while maintaining its properties, adhesion and antifouling properties.

  The compound (G) selected from the onium salt represented by the general formula (2) and the hydrolysis product thereof according to the polyester resin composition of the present invention is excellent in transparency, adhesion and prevention of polyester resin compositions. It is a component that imparts excellent antibacterial and antiviral properties while maintaining dirtiness.

  Examples of the bacteria having an antibacterial effect by the polyester resin composition of the present invention include Escherichia coli, Bacillus subtilis, Staphylococcus aureus, and Pseudomonas aeruginosa. Examples of viruses having an antiviral effect by the polyester resin composition of the present invention include influenza A virus (human, bird, swine), influenza B virus, parainfluenza virus, A to E hepatitis viruses, measles Examples include viruses having envelopes such as viruses, herpes viruses, mumps viruses, and rabies viruses, and non-enveloped viruses such as noroviruses.

  The onium salt according to the polyester resin composition of the present invention is represented by the following general formula (2).

(In the formula, A represents a phosphorus atom or a nitrogen atom. R ⁶ , R ⁷ and R ⁸ represent a linear or branched alkyl group having 1 to 18 carbon atoms. R ⁹ has 1 to 5 carbon atoms. .n which a straight or branched alkyl group is an integer of 1 to 8 .X ^- represents an anion group).

R ⁶ , R ⁷ and R ⁸ in the general formula (2) are linear or branched alkyl groups having 1 to 18 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl Group, pentyl group, octyl group, dodecyl group, octadecyl and the like. R ⁶ , R ⁷ and R ⁸ may be the same group or different groups. R ⁹ in the general formula (2) is a linear or branched alkyl group having 1 to 5 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group. Among them, a methyl group is particularly preferable. Moreover, n in General formula (2) is an integer of 1-8, Preferably it is 3. Moreover, X < ^- > in General formula (2) shows an anion group. Examples of the anion group of X ⁻ include benzotriazole ion, fluorine ion, chlorine ion, bromine ion, iodine ion, BF ₄ ⁻ , PF ₆ ⁻ , N (SO ₂ CF ₃ ) ₂ ⁻ , PO ₂ (OMe) ₃ ⁻ , Anionic groups such as PS ₂ (OEt) ₂ ⁻ and (CO ₂ Me) ₂ PhSO ₃ ^— can be mentioned, and among these, chlorine ions are preferred.

  In the compound (G) selected from the onium salt represented by the general formula (2) and the hydrolysis product thereof according to the polyester resin composition of the present invention, the phosphonium salt has a higher antiviral activity than the ammonium salt. It is preferable from the viewpoint of improvement.

  The hydrolysis product of the onium salt represented by the general formula (2) according to the polyester resin composition of the present invention is a product produced by hydrolysis of the onium salt represented by the general formula (2). However, the method for hydrolyzing the onium salt represented by the general formula (2) is not particularly limited, and a method using an alkali or acid catalyst or a method using no catalyst may be used. Examples of the alkali catalyst used for the hydrolysis include alkalis such as aqueous ammonia, sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and potassium carbonate. Examples of the acid catalyst used for the hydrolysis include acids such as hydrochloric acid and acetic acid.

  When the polyester resin composition of the present invention contains a hydrolysis product of an onium salt represented by the general formula (2), the onium salt represented by the general formula (2) is in a state where only the onium salt is present. It may be hydrolyzed or may be hydrolyzed in the presence of other components. Specifically, for example, (iii) First, a solution in which only the onium salt represented by the general formula (2) is dissolved in the solvent (E) is prepared, and then the general formula (2) in the solution is prepared. Hydrolyzing the onium salt represented by the following, and then mixing the resulting hydrolysis solution and other components to produce a polyester resin composition, (iv) First, in general formula (2) A solution in which the polyester resin (A) and the fluoroalkyl group-containing oligomer represented by the general formula (1) are dissolved in the solvent (E) is prepared together with the onium salt represented, and then the general formula in the solution is prepared. The onium salt represented by the general formula (2) is hydrolyzed together with the fluoroalkyl group-containing oligomer represented by (1), and then the resulting hydrolyzed solution and other components are mixed to obtain a polyester. Manufacture resin composition Rukoto, and the like. Among these, the onium represented by the general formula (2) in the solution containing the polyester resin (A) and the fluoroalkyl group-containing oligomer represented by the general formula (1) as in the method (iv) above. It is preferred to carry out the hydrolysis of the salt.

  The content of at least one compound (G) selected from the onium salt represented by the general formula (2) and the hydrolysis product thereof in the polyester resin composition of the present invention is appropriately selected, but preferably It is 0.1-50 mass%, Most preferably, it is 0.5-30 mass%. In addition, when the polyester resin composition of this invention contains both the onium salt represented by General formula (2), and its hydrolysis product, the said content is both total content. Further, the content of the hydrolysis product of the onium salt represented by the general formula (2) is hydrolyzed when it is the onium salt represented by the general formula (2) before being hydrolyzed. The content of the onium salt represented by the general formula (2) is used. That is, the content of the hydrolysis product of the onium salt represented by the general formula (2) is a converted value converted into the content of the onium salt represented by the general formula (2) before being hydrolyzed. .

  The method for producing the polyester resin composition of the present invention is not particularly limited, and the monomer (C) having a polyester resin (A), a (meth) acrylic polymer (B), and a (meth) acryloyl group in the solvent (E). The order and method of mixing the organometallic compound (D), the fluorine-containing compound (F) and the compound (G) are appropriately selected.

  The polyester resin composition according to the present invention comprises a polyester resin (A), a liquid A containing a solvent (E) and a fluorine-containing compound (F), or a polyester resin (A), a solvent (E), a fluorine-containing compound (F ) And A liquid containing compound (G), (meth) acrylic polymer (B), monomer (C) having (meth) acryloyl group, B containing organometallic compound (D) and solvent (E) It is preferable that the polyester resin composition has a high stability because it is obtained by mixing the liquid.

  The total content (A + F + G) of the polyester resin (A), the fluoropolymer (F) and the compound (G) mixed as necessary in the liquid A is 40 to 100% by mass, preferably 60 to 100% by mass. It is preferable that it is excellent in the workability of the liquid A. Further, the total content (B + C + D) of the (meth) acrylic polymer (B), the monomer (C) having a (meth) acryloyl group and the organometallic compound (D) in the liquid B is 2 to 40% by mass, preferably Is preferably 5 to 20% by mass in terms of excellent workability of the B liquid.

  As the liquid A, in the liquid containing the polyester resin (A), the solvent (E) and the fluoroalkyl group-containing oligomer represented by the general formula (1), the fluoroalkyl group-containing compound represented by the general formula (1) It is preferably obtained by hydrolyzing the oligomer. Moreover, as A liquid, in the liquid containing polyester resin (A), solvent (E), the fluoroalkyl group containing oligomer represented by General formula (1), and the onium salt represented by General formula (2) The fluoroalkyl group-containing oligomer represented by the general formula (1) and the onium salt represented by the general formula (2) are preferably obtained by hydrolysis.

  The mixing amount of the B liquid with respect to the A liquid is 0.1 to 2.5, preferably 1.0 to 2.0 in mass ratio (B liquid / A liquid).

  The fluoroalkyl group-containing oligomer represented by the general formula (1) and the onium salt represented by the general formula (2) have a trialkoxysilyl group as a hydrolyzable site. Therefore, by hydrolyzing the fluoroalkyl group-containing oligomer represented by the general formula (1), the reaction residues of the fluoroalkyl group-containing oligomer are connected by a siloxane bond to form a three-dimensional network, The reaction residue of the fluoroalkyl group-containing oligomer and the polyester resin (A) form a chemical bond or an intermolecular hydrogen bond, and the reaction residue of the fluoroalkyl group-containing oligomer is immobilized in the polyester resin (A). The In addition, by simultaneously hydrolyzing the fluoroalkyl group-containing oligomer represented by the general formula (1) and the onium salt represented by the general formula (2) in the same solution, the reaction residue of the fluoroalkyl group-containing oligomer and The reaction residue of the onium salt is linked by a siloxane bond to form a three-dimensional network. On the other hand, the reaction residue of the fluoroalkyl group-containing oligomer and the reaction residue of the onium salt and the polyester resin (A) are chemically treated. A bond or an intermolecular hydrogen bond is formed, and the reaction residue of the fluoroalkyl group-containing oligomer and the reaction residue of the onium salt are immobilized in the polyester resin (A). And when the polyester resin composition of this invention contains the polyester resin (A) by which the reaction residue of the fluoroalkyl group containing oligomer or the fluoroalkyl group containing oligomer and onium salt was fix | immobilized, such polyester The hardened | cured material formed using the resin composition can maintain antifouling property and the antibacterial property and anti-wistle property provided as needed over a long period of time. In particular, when the polyester resin composition of the present invention contains the polyester resin (A) in which the reaction residue of the fluoroalkyl group-containing oligomer and the onium salt is immobilized, the reaction residue of the fluoroalkyl group-containing oligomer As a result, the reaction residue of the onium salt can be more selectively present on the surface of the cured product, so that antibacterial and antiviral effects can be efficiently expressed.

  As a specific method for immobilizing the reaction residue of the fluoroalkyl group-containing oligomer or onium salt on the polyester resin (A), a solution containing the polyelter resin (A) and the solvent (E) is added to the general formula (1). ) Or a fluoroalkyl group-containing oligomer represented by the general formula (1) and an onium salt represented by the general formula (2), and then aqueous ammonia if necessary. Is added, and the trialkoxysilyl group is hydrolyzed. The resulting hydrolyzate and other components can be mixed to produce the polyester resin composition of the present invention. At this time, the addition amount of the ammonia water is an addition amount when converted with 25% by mass of ammonia water, and is 1 to 30 ml, preferably 5 to 15 ml per 1 g of the total of the fluoroalkyl group-containing oligomer and the onium salt. Moreover, reaction temperature when performing a hydrolysis is -5-50 degreeC, Preferably it is 0-30 degreeC, and reaction time is 0.1 to 5 hours.

  The polyester resin composition according to the present invention can be added with additives such as a sensitizer, a photopolymerization initiator, a leveling agent, a wax, an antifoaming agent, a mold release agent, and an antiwear agent as necessary. It can contain in the range which is not impaired.

  The method of using the polyester resin composition of the present invention, first, impregnation method, curtain coating method, gravure coating method, wire bar method, spray coating method, reverse coating method, die coating method, etc. on the surface of the substrate The polyester resin composition of the present invention is applied, then dried to remove the solvent (E), and a film made of a non-volatile component is formed on the surface of the substrate. Next, the film is formed by heating the formed film, irradiating the formed film with active energy rays, or irradiating the film with inert energy rays while heating the formed film. The formed film is cured to form a cured product on the surface of the substrate.

  When ultraviolet rays are used as active energy rays when the formed film is cured with active energy rays, the polyester resin composition of the present invention contains a photopolymerization initiator in order to promote the reaction by ultraviolet irradiation. It is preferable to contain. As photopolymerization initiators, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, 2-allyl benzoin, 2-chlorobenzoin and other benzoin-based compounds, benzophenone, p-methylbenzophenone, p-chlorobenzophenone, p-chlorobenzophenone Benzophenone series such as diethoxyacetophenone, hydroxyacetophenone (1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, etc.), and acetophenone series such as α-aminoacetophenone Thioxanthones such as 2-methylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, azos such as azobisisobutyronitrile, anthraquinone, 2-chloro Anthraquinone, and a quinone such as phenanthrene. Various photopolymerization initiators are used alone or in combination of two or more.

  When the polyester resin composition of the present invention contains a photopolymerization initiator, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-dimethylaminoethylbenzoate, N, N-dimethylaminoethyl methacrylate N -It is preferable to contain a sensitizer such as methyldiethanolamine in that the sensitivity to ultraviolet rays can be increased.

  When the polyester resin composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is appropriately selected, but preferably the total amount of monomers (C) having a (meth) acryloyl group is 100. It is 0.5-30 mass parts with respect to a mass part.

  The active energy ray is not particularly limited as long as it generates a radical active species and induces a polymerization reaction according to the composition of the polyester resin composition of the present invention. Examples thereof include a low pressure to high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge lamp, and a carbon arc lamp. When irradiating an electron beam, various irradiation apparatuses are used, for example, a scanning type, an electro curtain type, etc. are mentioned.

  The cured product of the present invention is a cured product obtained by heating the polyester resin composition of the present invention or irradiating active energy rays. The cured product of the present invention is formed on the surface of the substrate.

  The material of the substrate is not particularly limited, and examples thereof include polyethylene terephthalate (PET), polyethylene naphthalate, polyester, paper, polycarbonate, and acrylic resin. The shape of the substrate is not particularly limited, and may be a fill shape, a sheet shape, a filter shape, or a fiber shape. The base material may be an indeterminate type.

  The cured product of the present invention is obtained by applying the polyester resin composition of the present invention to the surface of a substrate by impregnation method, curtain coating method, gravure coating method, wire bar method, spray coating method, reverse coating method, die coating method, etc. Then, drying is performed to remove the solvent (E), and a film made of the non-volatile content of the polyester resin composition of the present invention is formed on the surface of the substrate, and then the non-volatile content in the polyester resin composition of the present invention It is obtained by curing the nonvolatile content in the polyester resin composition of the present invention by heating the film consisting of the component or irradiating the nonvolatile energy in the polyester resin composition of the present invention with active energy rays. The non-volatile content in the polyester resin composition of the present invention is the component remaining after the solvent (E) is removed from the polyester resin composition of the present invention by drying the polyester resin composition of the present invention. Point to.

  When the polyester resin composition of the present invention contains a polyester resin (A) in which a reaction residue of a fluoroalkyl group-containing oligomer or a fluoroalkyl group-containing oligomer and an onium salt is immobilized, such a polyester resin composition In the cured product formed using, the reaction residue of the fluoroalkyl group-containing oligomer represented by the general formula (1) and the reaction residue of the onium salt represented by the general formula (2) are cured like corona. The shape extends radially from the surface of the object. Therefore, even when the content of fluoroalkyl group oligomer and onium salt is small, while maintaining excellent transparency and adhesion, it has excellent antifouling properties, and also has excellent antibacterial and antiviral properties. Can be imparted to the cured product.

  The polyester resin composition of the present invention is suitably used for the formation of surface-treated materials such as top coat materials, clothing, fibers and the like in the field of automobile members, electronic equipment, building materials and the like.

  The structure of the present invention comprises a substrate and the cured product of the present invention formed on the surface thereof.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.

<Fluoroalkyl group-containing oligomer (F)>
As the fluoroalkyl group-containing oligomer (F) (hereinafter sometimes referred to as “VM”), those shown in Table 1 below were used.

<Onium salt (G)>
As the onium salt, those shown in Table 2 below were used.

<Preparation of A 'solution>
According to the reaction raw material composition shown in Table 3 below, various reaction raw materials for the production of a polyester resin were prepared.
Next, a reaction vessel having a capacity of 1000 ml equipped with a stirrer, a nitrogen gas inlet, a thermometer, a rectifying column, and a cooling condenser was prepared, and reaction raw materials shown in Table 3 below were prepared in the reactor. These were heated to 200 ° C. while stirring and mixing in a normal pressure and nitrogen atmosphere, and then the reaction temperature was gradually raised to 260 ° C. over 4 hours to complete the transesterification reaction. Next, this solution was gradually depressurized at a temperature of 260 ° C., and the polycondensation reaction was advanced by maintaining for 2 hours under the conditions of 260 ° C. and 0.67 hPa (0.5 mmHg) to obtain a polyester resin. .
Next, 100 parts of the obtained polyester resin and 270 parts of ethyl acetate were placed in a container and kept at a temperature of 80 to 95 ° C. for 2 hours while stirring them, whereby A having a polyester resin content of 27% by mass was obtained. 'I got the liquid.

１）全ジカルボン酸成分に対する各ジカルボン酸成分のモル％
２）全ジオール成分に対する各ジオール成分のモル％

1) mol% of each dicarboxylic acid component relative to the total dicarboxylic acid component
2) mol% of each diol component relative to the total diol component

<Preparation of liquid B>
In accordance with the polymerization raw material composition shown in Table 4, various raw materials for the (meth) acrylic polymer (B) (polymer raw material monomer) for the production of the (meth) acrylic copolymer (B) were prepared.
Next, a 1000 ml reaction vessel equipped with a stirrer, a nitrogen gas inlet, a thermometer, and a reflux condenser was prepared, and a total of 200 parts of the polymer raw material monomers shown in Table 4 below were used as a polymerization solvent, and 380 parts of ethyl acetate. , 10 parts of toluene, 10 parts of MEK, and 4 parts of 2,2′-azobisisobutyronitrile as a polymerization initiator were added and polymerized in a nitrogen gas stream at 80 ° C. for 6 hours to be transparent and viscous ( A resin solution of the (meth) acrylic polymer (B) was obtained.
To the resin solution of the obtained (meth) acrylic polymer (B), a monomer (C) (monomer (C)) having a (meth) acryloyl group shown in Table 4 and an organometallic compound (D) are added. Further, ethyl acetate was added, and the total content (B + C + D) of the (meth) acrylic polymer (B), the monomer (C) having a (meth) acryloyl group and the organometallic compound (D) was 13% by mass. B liquid was obtained.

１）（メタ）アクリル体重合（Ｂ）の重合原料となるモノマー
２）（メタ）アクリロイル基を有するモノマー（Ｃ）

1) Monomer (C) that has a (meth) acryloyl group 2) A monomer that is a polymerization raw material for (meth) acrylic polymerization (B)

Example 1
Each of the fluoroalkyl group-containing oligomers is individually added to the A ′ solution so as to have the composition shown in Table 5, and then 25% by mass of ammonia water is added so as to have the composition shown in Table 5 at room temperature (25 ° C.). A liquid was prepared by stirring for a minute. Subsequently, the B liquid was added to this A liquid, and it stirred for 3 minutes, and prepared the polyester resin composition sample.

(Example 2)
A polyester resin composition sample was prepared in the same manner as in Example 1 except that ammonia water was not added.

１）Ｂ液と混合するＡ液の量
２）Ａ液と混合するＢ液の量

1) Volume of liquid A mixed with liquid B 2) Volume of liquid B mixed with liquid A

<Evaluation to PET film>
The polyester resin composition sample obtained above is spin-coated on a PET film (length 1.8 cm × width 1.8 cm), dried at room temperature, and then heated and cured at 120 ° C. to have a film thickness of 105 μm. Was prepared.
The contact angle between dodecane and water on the surface of the film, turbidity and adhesion of the film sample were evaluated. The results are shown in Table 6. In addition, the unprocessed ones were blanked and are shown in Table 6.
As for the contact angle, the contact angle was measured using Drop Master 300 manufactured by Kyowa Interface Science. As for turbidity, the light transmittance at 500 nm was measured, and the absorbance of the film sample was measured using a VM-free film sample (blank) as a reference. It shows that it is transparent, so that this value is small.
For adhesion, in accordance with JIS K 5600-5-6, cut a 25-mass cut into the film sample, and after firmly sticking the adhesive tape on it, peel off the tape within 5 minutes and visually check for peeling of the thin film. By checking, the adhesion was evaluated. The evaluation criteria are as follows.
○: 20 or more remained per 25 squares.
X: Less than 20 remained per 25 squares.

<Evaluation to PET fiber>
The polyester resin composition sample prepared in Example 1 was coated on a PET cloth by a spin coating method and a dip method, dried, dried at room temperature, and then heated and cured at 120 ° C. to prepare a fiber sample. The contact angle of dodecane and water on the surface of the fiber was measured in the same manner as described above, and the results are shown in Table 7.
Moreover, the electron micrograph of the fiber sample (after thermosetting) processed by the spin coat method before a process was shown in FIG.1 and FIG.2, respectively.

(Examples 3-5 and Comparative Examples 1-2)
Fluoroalkyl group-containing oligomer, onium salt, and tetraethyl silicate (TEOS) were individually added to the A ′ solution so as to have the composition shown in Table 8, and then 25% by mass of ammonia water was added to the composition shown in Table 8. The solution A was prepared by stirring at room temperature (25 ° C.) for 5 minutes. Subsequently, the B liquid was added to this A liquid, and it stirred for 3 minutes, and prepared the polyester resin composition sample.

The polyester resin composition sample obtained above was spin-coated on a PET film (length 1.8 cm × width 1.8 cm), dried at room temperature, and then heated and cured at 120 ° C. to prepare a film sample. .
The contact angle of dodecane and water on the surface of this film and the turbidity and adhesion of the film sample were measured in the same manner as in Example 1, and the results are shown in Table 9. In addition, the non-treated ones were blanked and are shown in Table 9.

１）Ｂ液と混合するＡ液の量
２）Ａ液と混合するＢ液の量

1) Volume of liquid A mixed with liquid B 2) Volume of liquid B mixed with liquid A

(Antimicrobial activity test)
Example 4 using Escherichia coli NBRC 3972 as a representative of Gram-negative bacteria, Staphylococcus aureus NBRC12732 as Staphylococcus aureus NBRC12732, and Staphylococcus aureus NBRC12732 as representatives of Gram-negative bacteria. The film sample obtained in Example 5 was tested for antibacterial properties.
A square test piece having a size of 50 mm × 50 mm was prepared from the film sample. Place the test piece in a sterile petri dish, and add 0.5 ml of the test bacteria solution of E. coli to 2.3 x 10 ⁴ cells / ml and Staphylococcus aureus to 2.2 x 10 ⁴ cells / ml on the surface of each test piece. Vaccinated.
After the lid was covered and cultured at 25 ° C. for 24 hours, each test piece was thoroughly washed with 10 ml of bouillon medium. After culturing in NA medium at 37 ° C. for 24 hours, the number of viable bacteria in this medium was measured, and the number of colonies ( cfu / ml). The results are shown in Table 10. In addition, an untreated one was similarly subjected to an antibacterial test and used as a blank.

(Evaluation of anti-influenza virus)
A square test piece having a size of 50 mm × 50 mm was prepared from the film sample.
A filter paper was laid in the deep petri dish, and a small amount of sterilized water was added. A glass stand of about 5 mm was placed on the filter paper, and the test piece was placed thereon. 0.1 ml of a QB phage (NBRC20012) solution of influenza virus substitute virus that has been acclimated and clarified in advance is dropped on this, and a polyethylene film (KOYUYO, 40 mm × 40 mm) is used to bring the material surface into contact with the phage. ). The petri dish was covered with a glass plate. The same number of sets for measurement was prepared for the number of times the number of phages was scheduled to be measured, and was left to stand in a dark place at 25 ° C. for 4 hours.
Next, based on JIS R 1706, the host bacteriophage infectivity titer was evaluated using host E. coli (NBRC106373), and the antibacterial activity was determined based on the calculation formula of the effect in the dark of the hybrid photocatalytic antiviral processing material of the following formula (1). the virus activity was evaluated as V _D. The results are shown in Table 11. Further, in Examples 4 and 5, it carried out VM, TBSP-Cl, similarly antiviral tested for those obtained by curing without adding ODTSA-Cl and 25 wt% NH _3, which blank 1 The results are also shown in Table 11.
Incidentally, indicating that the antiviral activity, the higher the value of V _D is larger.
V _D = log (B _D / C _D ) (1)
V _D : dark effect of anti-virus processed material B _D : average value (pfu) of bacteriophage infectivity of 3 test pieces after storing non-anti-virus processed test pieces in the dark for 4 hours
C _D : Average value (pfu) of bacteriophage infectivity of 3 test pieces after storing the anti-virus processed test pieces in the dark for 4 hours

(Evaluation of anti-norovirus)
Example 1 and Comparative Example 1 and Comparative Example 1 except that instead of QB phage (NBRC20012), Norovirus-replaced ф6 phage (NBRC105899) was used, and host Pseudomonas aeruginosa (NBRC105640) was used instead of host E. coli (NBRC106373). Similarly, to evaluate the antiviral activity as V _D. The results are shown in Table 12. Further, in Examples 4 and 5, it carried out VM, TBSP-Cl, similarly antiviral tested for those obtained by curing without adding ODTSA-Cl and 25 wt% NH _3, which blank 2 The results are also shown in Table 12.

(Examples 6 to 7)
Fluoroalkyl group-containing oligomer and onium salt are individually added to the A ′ solution so as to have the composition shown in Table 13, and then 25% by mass of ammonia water is added so as to have the composition shown in Table 13. A liquid A was prepared by stirring at (25 ° C.) for 5 minutes. Subsequently, the B liquid was added to this A liquid, and it stirred for 3 minutes, and prepared the polyester resin composition sample.

１）Ｂ液と混合するＡ液の量
２）Ａ液と混合するＢ液の量

1) Volume of liquid A mixed with liquid B 2) Volume of liquid B mixed with liquid A

The polyester resin composition sample obtained above was spin-coated on a PET film (length 1.8 cm × width 1.8 cm), dried at room temperature, and then thermally cured at 120 ° C. to prepare a film sample.
The contact angle, turbidity, and adhesion of dodecane and water on the surface of this film were measured in the same manner as in Example 1, and the results are shown in Table 14. In addition, the unprocessed material was blanked and shown in Table 14.

  Although the comparison example when the VM in Examples 6 and 7 was not used was not carried out, Examples 6 and 7 had the same contact angle values with dodecane and water as those of Example 1. Therefore, Examples 6 and 7 also have the same effect as Example 1. When the VMs in Examples 6 and 7 were not used, their turbidity was as in Examples 6 and 7. Is estimated to be worse than

(Example 8)
A polyester resin composition sample was prepared in the same manner as in Example 4 except that 25% by mass NH ₃ was not added to the liquid A.
Next, the polyester resin composition sample obtained above is spin-coated on a PET film (length 1.8 cm × width 1.8 cm), dried at room temperature, then heated at 120 ° C. and thermally cured to prepare a film sample. did.
The contact angle of dodecane and water on the surface of the film and the turbidity and adhesion of the film sample were measured in the same manner as in Example 1, and the results are shown in Table 15. In addition, the unprocessed ones were blanked and are shown in Table 15.

(Antimicrobial / antiviral test)
About the film sample obtained above, an antibacterial test and an antiviral test were carried out in the same manner as in Example 4 and Example 5. In addition, in order to confirm whether VM and TBSP-Cl were chemically immobilized in the polyester, antibacterial tests and antiviral tests were also conducted on the film samples washed with ethanol. The results are shown in Table 16 and Table 17, respectively.
Washing with ethanol was performed by immersing the film sample in 99% ethanol for 5 minutes, and the film sample dried for 1 day at room temperature was used as the washed film sample.

Claims (13)

Polyester resin (A), (meth) acrylic polymer (B), monomer (C) having a (meth) acryloyl group, organometallic compound (D), solvent (E), and the following general formula (1) And at least one fluorine-containing compound (F) selected from a fluoroalkyl group-containing oligomer represented by (1) and a hydrolysis product thereof.

Wherein R ¹ and R ² represent a — (CF ₂ ) p—Y group or a —CF (CF ₃ ) — [OCF ₂ CF (CF ₃ )] q—OC ₃ F ₇ group, and R ¹ And R ² may be the same group or different groups, Y in R ¹ and R ² represents a hydrogen atom, a fluorine atom or a chlorine atom, and p and q are integers of 0 to 10. R ³ , R ⁴ and R ⁵ may be the same or different groups, and R ³ , R ⁴ and R ⁵ are linear or branched alkyl groups having 1 to ⁵ carbon atoms. M is an integer of 2 to 3.)   2. The (meth) acrylic polymer (B) is a (meth) acrylic polymer obtained by polymerizing a monomer for (meth) acrylic polymer (B) containing nitrogen. Polyester resin composition.   The polyester resin composition according to claim 1 or 2, wherein the monomer (C) having the (meth) acryloyl group is an active energy ray-curable monomer having a (meth) acryloyl group.   The polyester resin composition according to claim 1, wherein the organometallic compound (D) is at least one selected from metal alkoxides, metal acylates, and metal chelates.   Content of the said fluorine-containing compound (F) is 0.1-10 mass%, The polyester resin composition of any one of Claims 1 thru | or 4 characterized by the above-mentioned. Furthermore, at least 1 sort (s) of compounds (G) chosen from the onium salt represented by following General formula (2), and its hydrolysis product are contained, The any one of Claim 1 thru | or 5 characterized by the above-mentioned. The polyester resin composition as described.

(In the formula, A represents a phosphorus atom or a nitrogen atom. R ⁶ , R ⁷ and R ⁸ represent a linear or branched alkyl group having 1 to 18 carbon atoms. R ⁹ has 1 to 5 carbon atoms. .n which a straight or branched alkyl group is an integer of 1 to 8 .X ^- represents an anion group). The content of the compound (G) is, polyether scan ether resin composition according to claim 6, wherein the 0.1 to 50 mass%.   A liquid containing the polyester resin (A), the solvent (E) and the fluorine-containing compound (F), the (meth) acrylic polymer (B), and the monomer (C) having the (meth) acryloyl group The polyester according to any one of claims 1 to 7, wherein the polyester is obtained by mixing the organometallic compound (D) and the liquid B containing the solvent (E). Resin composition.   The polyester resin composition according to claim 8, wherein the liquid A further contains the compound (G). A method for producing a polyester resin composition according to claim 8,
In submerged containing the polyether scan ether resin (A) and the solvent (E), by a row Ukoto hydrolysis of the fluorinated compound (F), to obtain a solution A, then the resulting solution A , The (meth) acrylic polymer (B), the monomer (C) having the (meth) acryloyl group, the organometallic compound (D) and the liquid B containing the solvent (E), method of manufacturing features and to Lupo Riesuteru resin composition to obtain a polyester resin composition. The A liquid, a liquid in containing the polyether scan ether resin (A) and the solvent (E), characterized in that could perform the hydrolysis of the fluorinated compound (F) and the compound (G) The manufacturing method of the polyester resin composition of Claim 10 . The polyester resin composition of any one of claims 1 to 9, the cured product obtained by curing by irradiation with heat or active energy rays.   The structure which has the hardened | cured material of Claim 12 on the surface.

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