阅读说明：本技术 拒液剂、拒液组合物、固化树脂及物品 (Liquid repellent, liquid repellent composition, cured resin, and article ) 是由 市原丰 于 2021-05-18 设计创作，主要内容包括：本发明提供一种使表面自由能稳定地降低的拒液剂。一种拒液剂,其由使含羟基的氟系聚合物和至少一种含异氰酸酯基的(甲基)丙烯酸酯系单体反应而成的氨基甲酸酯系反应产物构成,所述含羟基的氟系聚合物是将下述(A)单体～(C)单体进行共聚而得到的：(A)含有全氟醚部分的至少一种(甲基)丙烯酸酯系单体；(B)至少一种含羟基的(甲基)丙烯酸酯系单体；(C)至少一种(甲基)丙烯酸酯系单体。(The invention provides a liquid repellent which stably reduces surface free energy. A liquid repellent comprising a urethane-based reaction product obtained by reacting a hydroxyl group-containing fluorine-based polymer and at least one isocyanate group-containing (meth) acrylate-based monomer, wherein the hydroxyl group-containing fluorine-based polymer is obtained by copolymerizing the following monomers (A) to (C): (A) at least one (meth) acrylate-based monomer containing a perfluoroether moiety; (B) at least one hydroxyl group-containing (meth) acrylate monomer; (C) at least one (meth) acrylate-based monomer.)

1. A liquid repellent comprising a urethane-based reaction product obtained by reacting a hydroxyl group-containing fluorine-based polymer and at least one isocyanate group-containing (meth) acrylate-based monomer, wherein the hydroxyl group-containing fluorine-based polymer is obtained by copolymerizing the following monomers (A) to (C):

(A) at least one (meth) acrylate-based monomer containing a perfluoroether moiety;

(B) at least one hydroxyl group-containing (meth) acrylate monomer;

(C) at least one (meth) acrylate-based monomer.

2. The liquid repellent of claim 1 wherein,

(A) comprising a (meth) acrylate monomer containing one perfluoroether moiety and a (meth) acrylate monomer containing a plurality of perfluoroether moieties.

3. The liquid repellent of claim 2 wherein,

the (meth) acrylate monomer having one perfluoroether moiety is represented by the following formula (A1), the (meth) acrylate monomer having a plurality of perfluoroether moieties is represented by the following formula (A2),

in the formula, R¹Represents a hydrogen atom or a methyl group,

R²a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms; the saturated aliphatic hydrocarbon group is straight-chain or branched-chain type, and is saturated aliphatic hydrocarbon group, saturated aliphatic hydrocarbon group with ether bond (-O-), saturated aliphatic hydrocarbon group with ester bond (-COO-or-O-CO-), or saturated aliphatic hydrocarbon group with amido bond (-CONH-or-NHCO-),

R³represents a hydrogen atom or a methyl group,

R⁴a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms; the saturated aliphatic hydrocarbon group is straight-chain or branched-chain type, and is saturated aliphatic hydrocarbon group, saturated aliphatic hydrocarbon group with ether bond (-O-), saturated aliphatic hydrocarbon group with ester bond (-COO-or-O-CO-), or saturated aliphatic hydrocarbon group with amido bond (-CONH-or-NHCO-),

n is an integer of 1 to 10.

4. The liquid repellent of claim 1 wherein,

the fluorine content of the hydroxyl group-containing fluorine-containing polymer is 20 to 35% by mass.

5. The liquid repellent of claim 1, wherein the liquid repellent is dissolved in a solvent.

6. The liquid repellent according to claim 1, wherein the liquid repellent is used by being added to a UV-curable resin.

7. A liquid repellent composition comprising a UV curable resin and the liquid repellent of claim 1.

8. A liquid-repellent cured resin obtained by irradiating the liquid-repellent composition according to claim 7 with ultraviolet rays.

9. An article comprising the liquid repellent cured resin of claim 8.

Technical Field

The invention relates to a liquid repellent, a liquid repellent composition, a cured resin and an article.

Background

In order to manufacture devices such as pixels, wirings, color filters, biochips, and the like for displays by printing techniques typified by inkjet, it is required to pattern a substrate on the order of micrometers in a liquid repellent region and a liquid hydrophilic region by photolithography. In order to obtain a liquid repellent region, a liquid repellent agent is added to, for example, a UV curable resin composition, a color resist, or the like.

However, there are the following disadvantages: when a high-performance liquid repellent is added to a cured resin composition, a color resist, or the like, the color resist generates turbidity or craters are generated on the surface of the resist.

When the fluorine-containing oligomer disclosed in patent document 1 is added to a UV curable resin composition, a color resist, or the like, the above-described cloudiness and craters (ハジキ) do not occur, but the liquid repellency is insufficient.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 5997998

Disclosure of Invention

Problems to be solved by the invention

The invention aims to provide a liquid repellent agent, a liquid repellent composition, a cured resin and an article, wherein the surface free energy of the liquid repellent agent is stably reduced.

Means for solving the problems

The invention provides a liquid repellent, a liquid repellent composition, a cured resin and an article.

Item 1. a liquid repellent comprising a urethane-based reaction product obtained by reacting a hydroxyl group-containing fluorine-based polymer obtained by copolymerizing the following monomers (a) to (C):

(A) at least one (meth) acrylate-based monomer containing a perfluoroether moiety;

(B) at least one hydroxyl group-containing (meth) acrylate monomer;

(C) at least one (meth) acrylate-based monomer.

Item 2 the liquid repellent according to item 1, wherein (a) comprises a (meth) acrylate-based monomer containing one perfluoroether moiety and a (meth) acrylate-based monomer containing a plurality of perfluoroether moieties.

Item 3 the liquid repellent according to item 2, wherein the (meth) acrylate monomer having one perfluoroether moiety is represented by the following formula (A1), and the (meth) acrylate monomer having a plurality of perfluoroether moieties is represented by the following formula (A2),

[ chemical formula 1 ]

(in the formula, R¹Represents H or methyl.

R²Represents a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may be linear or branched, and may have an ether bond (-O-), an ester bond (-COO-or-O-CO-), or an amide bond (-CONH-or-NHCO-) as required).

R³Represents H or methyl.

R⁴Represents a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may be linear or branched, and may have an ether bond (-O-), an ester bond (-COO-or-O-CO-), or an amide bond (-CONH-or-NHCO-) as required).

n is an integer of 1 to 10. )

The liquid repellent according to any one of claims 1 to 3, wherein the fluorine content of the fluorine-containing polymer having a hydroxyl group is 20 to 35% by mass.

The liquid repellent according to any one of claims 1 to 4, wherein the liquid repellent is dissolved in a solvent.

The liquid repellent according to any one of claims 1 to 5, wherein the liquid repellent is used by being added to a UV curable resin.

An item 7. a liquid repellent composition comprising a UV curable resin and the liquid repellent of any one of items 1 to 5.

An item 8. a liquid-repellent curable resin obtained by irradiating the liquid-repellent composition described in item 7 with ultraviolet rays.

Item 9. an article comprising the liquid-repellent cured resin of item 8.

Effects of the invention

By adding the liquid repellent of the present invention to a UV curable resin composition, a color resist, or the like and curing the obtained composition, a cured surface having a greatly reduced free energy can be formed, and the change with time in the free energy of the obtained cured surface is small.

Detailed Description

When a composition in which the liquid repellent agent of the present invention is added to a UV curable resin or a color resist is applied and cured on a substrate or the like, a liquid repellent property can be imparted to a curable resin such as a cured film obtained by reacting a curing component contained in the UV curable resin or the color resist with the liquid repellent agent of the present invention.

Component (A)

Examples of the perfluoroether moiety of the (meth) acrylate monomer include: o- (perfluoroalkyl), -O- (perfluoroalkylene), (perfluoroalkylene) -O- (perfluoroalkyl), and the like.

Specific examples of the perfluoroalkyl group include: -CF₃、-CF₂CF₃、-CF₂CF₂CF₃、-CF(CF₃)₂、-CF₂CF₂CF₂CF₃Etc. having straight or branched chain C₁～C₈Preferably C₁～C₄A perfluoroalkyl group of (a).

Specific examples of the perfluoroalkylene group include: -CF₂-、-CF₂CF₂-、-CF(CF₃)-、-CF₂CF₂CF₂-、-CF₂CF(CF₃)-、-CF(CF₃)CF₂-、-CF₂CF₂CF₂CF₃Equal or branched 2-valent C₂～C₈Preferably C₂～C₄A perfluoroalkylene group of (a).

The (meth) acrylate monomer having a perfluoroether moiety is preferably represented by the following formula (A1) or (A2).

[ chemical formula 2 ]

(in the formula, R¹Represents H or methyl.

R²Represents a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may be linear or branched, and may have an ether bond (-O-), an ester bond (-COO-or-O-CO-), or an amide bond (-CONH-or-NHCO-) as required).

R³Represents H or methyl.

R⁴Represents 1 to 10 carbon atomsA divalent saturated aliphatic hydrocarbon group (the saturated aliphatic hydrocarbon group may be linear or branched, and may have an ether bond (-O-), an ester bond (-COO-or-O-CO-), or an amide bond (-CONH-or-NHCO-) as required).

n is an integer of 1 to 10. )

n is preferably 2 to 10, more preferably 3 to 9, further preferably 4 to 8, and particularly preferably 5 to 7.

Examples of the divalent saturated aliphatic hydrocarbon group include: -CH₂-、-CH₂CH₂-、-CH(CH₃)-、-CH₂CH₂CH₂-、-CH₂CH(CH₃)-、-CH(CH₃)CH₂-、-CH₂CH₂CH₂CH₃-equal C₁～C₁₀Preferably C₁～C₆More preferably C₁～C₄A divalent saturated aliphatic hydrocarbon group of (1).

Further, as the divalent saturated aliphatic hydrocarbon group having an ether bond, there may be mentioned-CH₂-O-CH₂CH₂-、-CH₂CH₂-O-CH₂-、-(CH₂CH₂-O)₁- (l is an integer of 1 to 5), and the like. As a divalent saturated aliphatic hydrocarbon group having an ester bond, there may be mentioned-CH₂CH₂-COO-、-CH₂CH₂-OCO-、-CH₂CH₂CH₂-COO-、-CH₂CH₂CH₂-OCO-、-CH₂CH₂-COO-CH₂-、-CH₂CH₂-OCO-CH₂-and the like. Examples of the divalent saturated aliphatic hydrocarbon group having an amide bond include-CH₂CH₂-NHCO-、-CH₂CH₂-CONH-、-CH₂-NHCO-CH₂-、-CH₂-CONH-CH₂-and the like.

The (meth) acrylate monomer containing a perfluoroether moiety may be used alone in 1 kind or in combination with 2 or more kinds.

Component (B)

The hydroxyl group-containing (meth) acrylate monomer has 1 or 2, preferably 1, hydroxyl group. Preferred examples of the hydroxyl group-containing (meth) acrylate monomer include compounds represented by the following formula (B1), and these may be used alone in 1 kind or in combination in 2 or more kinds.

[ chemical formula 3 ]

(in the formula, R⁵Represents H or methyl.

R⁶Represents an alkylene group having a straight chain or a branched chain.

m represents an integer of 1 to 20. )

Examples of the alkylene group having a straight chain or a branched chain include: -CH₂-、-CH₂CH₂-、-CH(CH₃)-、-CH₂CH₂CH₂-、-CH₂CH(CH₃)-、-CH(CH₃)CH₂-、-CH₂CH₂CH₂CH₃-equal C₁～C₄An alkylene group.

Component (C)

Examples of the (meth) acrylate monomer include: methyl Acrylate (MA), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate (4-HBMA), isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, Methyl Methacrylate (MMA), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, these substances can be used alone 1, can also be used in combination of 2 or more.

Fluorine-containing Polymer having hydroxyl group

The hydroxyl group-containing fluorine-based polymer can be obtained by copolymerizing the component (a), the component B, and the component (C). The copolymerization reaction is advantageously carried out by reacting at 70 to 90 ℃ for 4 to 12 hours in the presence of a radical initiator. The polymerization is preferably carried out in the presence of a radical polymerization initiator as a radical initiator. Examples of the radical polymerization initiator that can be used in the production method of the present invention include: t-butyl hydroperoxide, cumene hydroperoxide, 2, 5-dimethylhexane-2, 5-dihydroperoxide, diisopropylphenyl peroxide, di-t-butyl peroxide, t-butyl peroxyisobutyrate, t-butyl- α -cumyl peroxide, di- α -cumyl peroxide, α' -bis (t-butylperoxy) -p-diisopropylbenzene, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di (t-butylperoxy) -hexyne-3-acetyl peroxide, succinic peroxide, diisobutyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, di-isopropyl butyryl peroxide, di-t-butyl peroxyacetate, di-t-butyl peroxyisobutyrate, di-isopropyl butyryl peroxide, di-t-butyl peroxide, di-butyl peroxyl, di-isopropyl peroxyl, di-3-isopropyl peroxyl, di-butyl peroxyl, di-isopropyl peroxyl, di-2, di-butyl peroxyl, di-isopropyl peroxyl, di-2, di-3-isopropyl peroxyl, di-tert-butyl peroxyl, tert-isopropyl peroxyl, tert-butyl peroxyl, tert-2, tert-butyl peroxyl, tert-isobutyl isobutyryl peroxide, tert-butyl peroxyl, tert-isobutyl isobutyryl peroxide, tert-butyl peroxyl, tert-isobutyryl peroxide, tert-butyl peroxyl, tert-isobutyryl peroxide, tert-butyl peroxyl, tert-isobutyryl peroxide, and tert-butyl peroxyl peroxide, and tert-butyl peroxy, Azo compounds such as di-isobutyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, methyl ethyl ketone peroxide, cyclohexanone peroxide, 2 '-azobisisobutyronitrile, dimethyl 2, 2' -azobisisobutyrate, dimethyl azobisisobutyrate (V-601), 2 '-azobis (2-methylbutyronitrile), 2' -azobis (isobutylamidine) dihydrochloride, 2 '-azobis [2- (2-imidazolin-2-yl) propane ] and its disulfate, and 2, 2' -azobis (2-methylamidoxime) dihydrochloride; potassium persulfate, sodium persulfate, ammonium persulfate, tert-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, and the like. These radical polymerization initiators may be used alone in 1 kind, or may be used in combination in 2 or more kinds. The copolymerization reaction can be carried out by using a chain transfer agent such as lauryl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid, thioglycerol, etc., to adjust the molecular weight.

The proportions of the component (a), the component (B) and the component (C) for obtaining the hydroxyl group-containing fluorine-based polymer are as follows, assuming that the total of them is 100% by mass.

Component (A): preferably 40 to 70% by mass, more preferably 50 to 60% by mass,

Component (B): preferably 10 to 40% by mass, more preferably 20 to 30% by mass,

Component (C): preferably 10 to 40 mass%, more preferably 20 to 30 mass%.

In the component (a) for obtaining the hydroxyl group-containing fluorine-based polymer, a preferred mass ratio of the monomer represented by formula (a1) to the monomer represented by formula (a2) is the monomer (a 1): monomer (a2) ═ 1: 0-1: 0.4. if the amount of the (A2) component is too large relative to the (A1) component, turbidity occurs in the liquid and the appearance of the liquid becomes poor.

The fluorine content of the hydroxyl group-containing fluorine-based polymer is preferably 15 to 40% by mass, more preferably 20 to 35% by mass, and still more preferably 22 to 32% by mass. If the fluorine content is too high, shrinkage cavities are generated on the surface of the cured resin obtained by mixing and curing the UV curable resin, which is not preferable. If the fluorine content is too small, the liquid repellency is undesirably reduced.

The weight average molecular weight of the hydroxyl group-containing fluorine-based polymer is preferably 3000 to 50000, more preferably 10000 to 20000. The weight average molecular weight can be calculated as a value converted into a molecular weight of standard polystyrene by a Gel Permeation Chromatography (GPC) method.

Isocyanate group-containing (meth) acrylate monomer

Examples of the isocyanate group-containing (meth) acrylate monomer include: 2-isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 2-isocyanato-1-methylethyl (meth) acrylate, 2-isocyanato-1, 1-dimethylethyl (meth) acrylate, 4-isocyanatocyclohexyl (meth) acrylate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1- (bis (meth) acryloyloxymethyl) ethyl isocyanate, 2- (2-isocyanatoethoxy) ethyl (meth) acrylate, 2-isocyanato-ethyl (meth) acrylate, 4-isocyanato-ethyl (meth) acrylate, 2-isocyanato-acetoxy (meth) acrylate, 2-isocyanato-ethyl (meth) acrylate, 2-isocyanato-ethyl (meth) isocyanate, 2-isocyanato, 2-isocyanato (meth) isocyanate, 2-isocyanato, 2-isocyanato (meth) isocyanate, 2, and (meth) isocyanate, 2-2, or, 2- (2-isocyanatoethoxy) (meth) acrylate and the like, preferably 2-isocyanatoethyl (meth) acrylate. The isocyanate group-containing (meth) acrylate monomer may be used alone in 1 kind or in combination with 2 or more kinds.

Urethane-based reaction products

The urethane reaction product can be obtained by reacting a hydroxyl group-containing fluorine-based polymer with an isocyanate group-containing (meth) acrylate monomer in the presence of an amine catalyst, if necessary. Examples of the amine-based catalyst include: triethylamine, N-methylmorpholine, N-ethylmorpholine, N' -dimethylpiperazine, benzyldimethylamine, N-dimethylethanolamine, bis (dimethylaminoethyl) ether, and the like. The reaction is advantageously carried out by using 0.3 to 1.0 equivalent of the isocyanate group-containing (meth) acrylate monomer per 1 equivalent of the hydroxyl group-containing fluorine-based polymer and reacting at 50 to 80 ℃ for 4 to 8 hours.

Liquid-repellent agent, liquid-repellent composition, liquid-repellent cured resin, and article

The liquid repellent of the present invention preferably contains a urethane-based reaction product and further contains a solvent. Examples of the solvent include: dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, 1,1,2, 2-tetrachloroethane, 1,1, 1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, methyl acetate, ethyl acetate, butyl acetate, amyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, 1, 3-dioxolane, 1, 4-dioxane, cyclohexanone, ethyl formate, 2,2, 2-trifluoroethanol, 2,2,3, 3-hexafluoro-1-propanol, 1, 3-difluoro-2-propanol, 1,1, 1, 3,3, 3-hexafluoro-2-methyl-2-propanol, nitroethane, Propylene Glycol Monomethyl Ether Acetate (PGMEA), Dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol diacetate, tripropylene glycol, 3-methoxybutyl acetate (MBA), 1, 3-butanediol diacetate, cyclohexanol acetate, dimethylformamide, dimethyl sulfoxide, methyl cellosolve, cellosolve acetate, butyl cellosolve, butyl carbitol, carbitol acetate, ethyl lactate, isopropyl alcohol, methanol, ethanol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, anisole, tetrahydronaphthalene, cyclohexylbenzene, mesitylene, petroleum ether, tetrahydrofuran, 1, 4-dioxane, and the like.

The liquid repellent of the present invention can be prepared into a liquid repellent composition by adding it to a UV curable resin. The UV curable resin and the liquid repellent composition are preferably liquid substances. By curing the liquid-repellent composition, liquid repellency can be imparted to the cured resin. The urethane-based reaction product of the present invention can impart liquid repellency to a cured product thereof by adding the urethane-based reaction product to a UV curable resin, and therefore is useful as a liquid-repellent additive for a UV curable resin.

The liquid repellent of the present invention is a liquid repellent having sustained liquid repellency, and for example, when a liquid repellent composition is produced by mixing with a cured resin and the liquid repellent composition is cured to obtain a cured resin (cured film), the initial Surface Free Energy (SFE) of the cured resin₀) And surface energy after 3 days (SFE)₃) The absolute value of the rate of change (represented by the formula X) of (2) is 10% or less, preferably 5% or less, more preferably 4% or less, and particularly 3% or less.

[ mathematical formula 1 ]

|(100×(SFE₃-SFE₀)/SFE₀Formula X

As the UV curable resin, an acrylic resin, an epoxy resin, a melamine resin, or the like can be used. The UV curable resin of a preferred embodiment is used for the manufacture of color filters, color photoresists, and the like. The color photoresist includes a photoresist for black matrix production (black photoresist). The UV curable resin may be a 2-functional or higher curable resin in order to satisfy physical properties such as heat resistance, hot water resistance, and chemical resistance. In order to obtain a low-viscosity, liquid-repellent composition, the UV-curable resin is preferably a resin exhibiting low molecular weight and non-crystallinity.

The liquid repellent composition of the present invention preferably contains 20 to 40% by mass of a UV-curable resin (solid content) and 0.05 to 2.0% by mass of a solid content of a liquid repellent, more preferably 25 to 35% by mass of a UV-curable resin (solid content) and 0.2 to 0.7% by mass of a solid content of a liquid repellent, based on 100% by mass of the total solid content.

The liquid-repellent curable resin can be obtained by curing the liquid-repellent composition of the present invention by UV (ultraviolet) irradiation. The curing may be performed under the curing conditions of the UV curable resin. In a preferred embodiment, an article having a cured film as a cured resin can be obtained by applying the liquid-repellent composition of the present invention to a substrate and UV-curing the composition. The cured film has a liquid repellent surface. Examples of the substrate include: silicon sheet, synthetic resin, glass, metal, ceramic, and the like. The synthetic resin may be any of a thermoplastic resin and a thermosetting resin. Examples of the glass include: silicate glass, alkali silicate glass, soda lime glass, potassium lime glass, lead glass, barium glass, borosilicate glass, and the like. Examples of the metal include: gold, silver, copper, iron, nickel, aluminum, platinum, and the like. Examples of the ceramics include: oxides (e.g., aluminum oxide, zinc oxide, titanium oxide, silicon oxide, zirconium oxide, barium titanate), nitrides (e.g., silicon nitride, boron nitride), sulfides (e.g., cadmium sulfide), carbides (e.g., silicon carbide), and the like.

The liquid-repellent composition can be applied to the substrate by, for example, roll coating, gravure coating, microgravure coating, flow coating, bar coating, spray coating, die coating, spin coating, dip coating, or the like, and can be selected in consideration of the type, shape, productivity, controllability of film thickness, and the like of the substrate.

[ examples ] A method for producing a compound

The present invention will be described in detail below with reference to examples.

Using materials

AC-500: 2-Propenoic acid-2-methyl-2- [2,3,3,3-tetrafluoro-2- (1,1,2,2,3,3,3-heptafluoropropoxy) -1-oxopropoxy ] ethyl ester (2-Propenoic acid,2-methyl-,2- [2,3,3, 3-tetrafluorofluoro-2- (1,1,2,2,3,3,3-heptafluoropropoxy) -1-oxopropoxy ] ethyl ester

[ chemical formula 4 ]

AC-1000: poly [ oxy [ trifluoro (trifluoromethyl) -1,2-ethanediyl ] ] - α - (1,1,2,2,3,3, 3-heptafluoropropyl) - ω - [1,2,2, 2-tetrafluoro-1- [ [2- [ (2-methyl-1-oxy-2-propen-1-yl) oxy ] ethoxy ] carbonyl ] ethoxy ] ester (Poly [ oxy [ trifluoromethyl (trifluoromethyl) -1,2-ethanediyl ] ], α - (1,1,2,2,3,3, 3-heptafluoropyryl) - ω - [1,2,2, 2-tetrafluoro-1- [ [2- [ (2-methyl-1-oxo-2-propen-1-yl) oxy ] ethenyl ] carbonyl ] ethoxy ] ester.

[ chemical formula 5 ]

PE-90: poly (oxy-1,2-ethanediyl) alpha- (2-methyl-1-oxy-2-propen-1-yl) -omega-hydroxy ester (Poly (oxy-1,2-ethanediyl), alpha- (2-methyl-1-oxo-2-propen-1-yl) -omega-hydroxy-)

[ chemical formula 6 ]

4-HBMA: 2-Propenoic acid-2-methyl-4-hydroxybutyl ester (2-Propenoic acid,2-methyl-,4-hydroxybutyl ester)

[ chemical formula 7 ]

MMA: 2-methyl-2-Propenoic acid methyl ester (2-Propenoic acid,2-methyl-, methyl ester)

[ chemical formula 8 ]

PME-200: poly (oxy-1,2-ethanediyl) alpha- (2-methyl-1-oxy-2-propen-1-yl) -omega-methoxy ester (Poly (oxy-1,2-ethanediyl), alpha- (2-methyl-1-oxo-2-propen-1-yl) -omega-methoxy-)

[ chemical formula 9 ]

CALENDS AOI: 2-Isocyanatoethyl acrylate (2-Isocyanoethyl acrylate)

[ chemical formula 10 ]

FTERGENT 601ADH 2: (manufactured by Neos corporation)

Synthesis example 1

Into a three-necked flask (500ml) having a cooling tube were charged AC-500(50g), PE-90(20g), MMA (20g), butyl acetate (200g), lauryl mercaptan (1.48g) and V-601(0.84 g). Nitrogen gas was introduced into the reaction solution to replace the reaction vessel with nitrogen. After the substitution with nitrogen, the reaction solution was heated to 80 ℃ while stirring the reaction solution, and the reaction was started. Thereafter, stirring was continued at 80 ℃ for 8 hours. By passing¹The completion of the reaction was confirmed by the disappearance of peaks specific to the respective acrylates in H-NMR. The target fluorine-containing oligomer was quantitatively obtained. 50 mol% of CALENDS AOI and 1 mol% of triethylamine were added to PE-90, and the reaction solution was stirred at 50 ℃ for 8 hours. The completion of the reaction was confirmed by the disappearance of the absorption of-N ═ C ═ O using FT-IR. The target urethane-based reaction product, namely, the reactive fluorine-containing oligomer 1, was quantitatively obtained.

Synthesis examples 2 to 9

Reactive fluorine-containing oligomers 2 to 9 were synthesized by changing the same operations as in synthesis example 1 to the monomer weights shown in Table 1.

Synthesis example 10

FTERGENT 601ADH2 was set as reactive fluorine-containing oligomer 10.

[ TABLE 1 ]

Examples 1 to 5 and comparative examples 1 to 5

Reactive fluorine-containing oligomers 1 to 9 synthesized in Synthesis examples 1 to 9 were added so that the concentration of the active ingredient in the liquid repellent became 0.5 wt% based on the active ingredient in the resist coating liquid. The coating liquid was applied to a glass substrate by spin coating, dried by heating, and then irradiated with UV to prepare a coating film, and the following evaluation was performed. The results are shown in Table 2.

Examples 6 to 10 and comparative examples 6 to 9

Reactive fluorine-containing oligomers 1 to 9 synthesized in synthesis examples 1 to 9 were added so that the concentration of the active ingredient in the liquid repellent was 0.5 wt% with respect to the active ingredient in the UV curing bar coating liquid containing dipentaerythritol hexaacrylate. The bar coating liquid was applied to a PET substrate by bar coating, and after heating and drying, a coating film was formed by UV irradiation, and the following evaluation was performed. The results are shown in Table 3.

Evaluation of

Film appearance

The film appearance of each coating film was visually observed, and the film was evaluated as good when no craters were present on the film, and as good as or good when craters were present on the film, the film was evaluated as poor.

Surface free energy determination

The contact angle of the resulting coating film was measured, and the surface free energy was calculated. The calculation formula is Kaelble-Uy.

The performance is good if the initial surface free E is 17mN/m or less.

Stability of film Properties

The obtained coating film was stored at 25 ℃ for 3 days in a 30% atmosphere. The contact angle after storage was measured to calculate the surface free E.

The initial and stored surface free energies were compared.

If the change amount of the surface free E after 3 days is 1mN/m or less, it is good.

When the change amount of the surface free E after 3 days was 1mN/m or more, it was X.

[ TABLE 2 ]

[ TABLE 3 ]

As shown in table 2, it can be seen that: the FTERGENT 601ADH2 used in comparative example 5 is not only high in initial SFE but also changes by 10% or more after 3 days with respect to initial SFE, and is not preferable, but the initial SFE of the liquid repellent of the present invention is very low, and the change rate of SFE after 3 days with respect to initial SFE is less than 5%, and is preferable as a liquid repellent for imparting liquid repellency to a coating material for a photoresist.

As shown in Table 3, in the case of the UV curing bar coating solutions, the film appearance was good and the initial SFE was also good in examples 6 to 10. In the case of comparative examples 6 to 9, shrinkage cavities occurred in the film appearance. The liquid repellent of the present invention is preferable as a liquid repellent that imparts liquid repellency to a UV curing bar coating liquid.