KR20030045191A - Water-Repellent, Oil-Repellent and Soil Resistant Coating Composition - Google Patents

Abstract

The present invention provides a coating composition capable of obtaining a coating film having high adhesion to a substrate by having sufficiently high water / oil repellency and stain resistance. The present invention also provides a coating composition comprising a copolymer obtained by copolymerizing a monomer comprising a fluoroaliphatic group-containing unsaturated ester monomer and an unsaturated silane monomer.

Description

Water-Repellent, Oil-Repellent and Soil Resistant Coating Composition

Conventionally, coatings containing compounds containing long-chain fluoroaliphatic groups have lower critical surface tensions than other materials and have been widely used as surface modifiers for water repellency, oil repellency and contamination prevention. As such surface modifiers, homopolymers or copolymers obtained by radical polymerization of an α, β-unsaturated ester monomer containing a fluoroaliphatic group are used. However, these polymers have a low surface hardness and are not sufficient for wear resistance and durability. In addition, such polymers tend to have insufficient film forming ability and adhesion to a substrate. Therefore, the polymer has a problem that the coating film is peeled off even if lightly rubbed. In addition, since the bonding with the substrate is due to hydrogen bonding, the bonding strength is weak and there is a problem in that the coating film is peeled off when water is applied to the end surface of the coating film.

U.S. Patent Application Nos. 3,931,454 and 4,849,291 disclose coating compositions comprising a fluoroalkyl (meth) acrylate / (meth) acrylic acid copolymer in which a portion of the fluoroalkyl (meth) acrylate is substituted with (meth) acrylic acid. It is described. These documents describe that the adhesion to the substrate is improved by introducing (meth) acrylic acid into the copolymer. However, such improvement did not completely solve the above problems.

Japanese Unexamined Patent Publication (Kokai) No. 58-172245 is a treatment agent for imparting water repellency, oil repellency, fouling resistance and low reflectivity to a glass surface, and (a) a polyfluoroalkyl group-containing silane compound represented by the following formula (I) or A glass surface treating agent comprising a partially hydrolyzed condensate and (b) a silane compound represented by the following general formula (Ia) is disclosed.

{Rf (X) _n CON (R ¹ ) -A} _a Si (Z) _b Y ¹ _4-ab

SiR ² _c Y ² _4-c

Wherein Rf is a polyfluoroalkyl group having 1 to 20 carbon atoms and may include one or more ether bonds, R ¹ and R ² are each a hydrogen atom or a lower alkyl group, and X is -CON (R ² ) -Q -Or -SO ₂ N (R ² ) -Q- (R ² is as defined above, Q is a divalent organic group), A is an alkylene group, Z is a lower alkyl group, and Y ¹ and Y ² are Each is a halogen, alkoxy group or R ³ COO— (R ³ is a hydrogen atom or a lower alkyl group), n is an integer of 0 or 1, a is an integer of 1 to 3, b is an integer of 0, 1 or 2 C is an integer of 0, 1 or 2.

It is described that the use of the above-mentioned polyfluoroalkyl group-containing silane compound and alkoxy or halogenosilane increases the degree of crosslinking in terms of adhesion with glass to improve adhesion, water repellency and oil repellency. However, this treatment agent has a Rf: Si ratio of 1: 1 in component (a), and also contains Si in component (b) so that the composition as a whole has a low density of Rf groups and contains a large amount of silicon. If the amount of silicon is too large, it is not preferable because it tends to inhibit the oil repellency of the composition. In addition, since the component (a) contained in the treatment agent has a low molecular weight, it is difficult to obtain a homogeneous coating film, and it is considered that the permeability of the membrane against oil is low.

Coating compositions comprising fluorine-containing polymers rather than the above low molecular weight fluoro-containing compounds are also known. Japanese Patent Laid-Open No. 11-349888 discloses a coating composition comprising a fluororesin having an aliphatic ring structure in the main chain, a partial hydrolysis condensate of alkoxysilanes, and a solvent. The partial hydrolysis condensation products of the alkoxysilanes in this composition are intended to act so that the fluorine resin overcomes the shortcomings in terms of physical properties such as low glass transition temperature, low elastic modulus in high temperature region and high linear expansion coefficient. When attaching such a composition to a base material, since a fluororesin generally has low adhesiveness with a base material, it is thought that it adheres to a base material through the partial hydrolysis-condensation product of alkoxysilanes. This document also describes that a compound having a site capable of reacting with a hydrolyzable group capable of reacting with a partial hydrolysis condensate of alkoxysilanes and a functional group of a fluorine resin can be used as a coupling agent in order to improve adhesion to the substrate. However, in such a composition, there is no direct adhesion between the fluorine resin and the substrate, making it difficult to form a homogeneous coating film having sufficiently high water repellency, oil repellency and stain resistance.

Accordingly, it is an object of the present invention to provide a coating composition capable of obtaining a coating film having high adhesion to a substrate by having sufficiently high water repellency, oil repellency and stain resistance.

<Overview of invention>

According to the present invention, there is provided a coating composition comprising a copolymer obtained by copolymerizing a monomer comprising a fluoroaliphatic group-containing unsaturated ester monomer and an unsaturated silane monomer.

By using this coating composition, a coating having high adhesion to the substrate can be obtained by having sufficiently high water repellency, oil repellency and stain resistance.

<Detailed Description of Exemplary Embodiments>

The fluoroaliphatic group containing unsaturated ester monomers for the copolymers in the compositions of the present invention act to impart water and oil and oil resistance to the resulting coatings. The ester monomer is a compound containing an aliphatic group at least partially substituted by fluorine, in particular an alkyl group at least partially substituted by fluorine, and also having a polymerizable ethylenically unsaturated carbon-carbon double bond. More specifically, examples of the fluoroaliphatic group-containing unsaturated ester monomer include compounds having the following formula.

Wherein R _f is a straight, branched or cyclic at least partially fluorinated aliphatic group having from 2 to 12 carbon atoms, for example at least partially fluorinated alkyl group, preferably fully fluorinated alkyl group, R ¹ is H Or CH ₃ , Q is a lower alkylene group, for example -CH _2- , -CH ₂ CH ₂ -or -SO ₂ NR ² -lower alkylene group, for example -SO ₂ NR ² -CH ₂ -or- SO ₂ NR ² -CH ₂ CH _2- , R ² is hydrogen or a lower alkyl group, for example -CH ₃ or -C ₂ H ₅ .

The higher the number of carbon atoms or fluorine substituents of R _f, the higher the water / oil repellency and the fouling resistance. However, it is considered that when the number of carbon atoms is too large, the tendency for the copolymer to accumulate in living tissue increases. Therefore, R _f is preferably a fluoroaliphatic group having 3 to 7 carbon atoms, more preferably a fluoroaliphatic group having 3 to 6 carbon atoms. In addition, the terminal group of R _f is preferable because it exhibits high water / oil repellency and fouling resistance when the group is completely fluorinated -CF ₃ .

Q is a lower alkylene group has not to inhibit water repellency, etc. of the copolymer, preferably -CH ₂ - or -CH ₂ CH ₂ - is. Specific examples of the monomer include F (CF ₂ ) ₆ CH ₂ OC (═O) C (CH ₃ ) = CH ₂ , C ₇ F ₁₅ SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ OC (= O) C (CH ₃ ) = CH ₂ , cC ₆ F ₁₁ CH ₂ OC (= O) C (CH ₃ ) = CH ₂ , C ₆ F ₁₃ C ₂ H ₄ OC (= O) CH = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₂ C ₂ H ₄ OC (= O) CH = CH ₂ , H (CF ₂ ) ₄ CH ₂ OC (= O) CH = CH ₂ , F (CF ₂ ) ₄ C ₂ H ₄ OC (= O) CH = CH ₂ and F (CF ₂ ) ₃ CH ₂ OC (= 0) CH = CH ₂ . Such monomers may be prepared by conventional methods such as those described in US Pat. Nos. 2,803,615 and 2,841,573.

The fluoroaliphatic group-containing unsaturated ester monomer is usually included in an amount of at least 50% by weight, preferably at least 70% by weight based on the total weight of the unsaturated ester monomer and the unsaturated silane monomer. Within this range, it is possible to give the coating sufficiently high water and oil repellency and fouling resistance.

The unsaturated silane monomer portion in the copolymer serves to promote adhesion of the resulting coating to the substrate. An unsaturated silane monomer is a silane compound which contains the silicon atom which can improve adhesiveness with a base material, and has a polymerizable ethylenically unsaturated carbon-carbon double bond. More specifically, the unsaturated silane monomers include compounds having the following formula.

Wherein R ¹ is H or CH ₃ , R ³ is hydrogen or lower alkyl group such as methyl or ethyl group, X is alkoxy, halogen or RCOO- and R is hydrogen or lower alkyl group such as methyl or Is an ethyl group, Y is a single bond or -CH _2- , n is an integer of 0, 1 or 2;

Specific examples of the compound where X is an alkoxy group include vinyltrialkoxysilanes such as (CH ₃ O) ₃ SiCH = CH ₂ and (C ₂ H ₅ O) ₃ SiCH = CH ₂ , and allyltrialkoxysilanes, such as (CH ₃ O) ₃ SiCH ₂ CH = CH ₂ . Specific examples of the compound where X is halogen include CH ₂ = CHSiCl ₃ . Specific examples of the compound wherein X is RCOO- include (CH ₃ COO) ₃ SiCH = CH ₂ .

Unsaturated silane monomers are usually included in amounts of 1 to 50% by weight, based on the total weight of fluoroaliphatic group-containing unsaturated ester monomers and unsaturated silane monomers. If the unsaturated silane monomer is included in less than 1.0% by weight does not appear to significantly improve the adhesion of the coating to the substrate, when exceeding 50% by weight may lower the water and oil repellency. The amount of unsaturated silane monomer is preferably 1 to 30% by weight, more preferably 1 to 10% by weight, still more preferably 1.5 to 4% by weight in terms of balance of performance such as adhesion to the substrate and water repellency of the coating.

In addition, the copolymers in the compositions of the present invention, in addition to the above-mentioned fluoroaliphatic group-containing unsaturated ester monomers and unsaturated silane monomers, so long as they do not impair the desirable properties of the coating of the present invention such as water repellency, oil repellency, fouling resistance and adhesion to the substrate. Monomers copolymerizable with these monomers may be included, for example (meth) acrylic acid, ethylene, olefins and styrene. However, the copolymer usually consists of the two monomers preferably.

The preparation of the copolymer can be carried out using conventional radical polymerization methods. Specifically, in the presence of a radical polymerization initiator such as azobisisobutyronitrile, the fluoroaliphatic group-containing unsaturated ester monomer and the unsaturated silane monomer are dissolved in a suitable solvent such as hydrofluorocarbon ether, and then, at 10 to 60 ° C. The copolymer can be obtained by heating to polymerize for 20 hours.

The molecular weight of the copolymer in the coating composition is preferably 100 to 50,000, more preferably 500 to 5,000. If the molecular weight is too small, the film forming ability is bad, and if the molecular weight is too large, the viscosity of the coating composition rises, making the resulting coating more difficult to apply.

The coating composition preferably contains a solvent in order to improve applicability. Preferably, the solvent used in the present invention is a fluorinated solvent. Examples of suitable fluorinated solvents include solvents that are non-ozone depletable and non-flammable, for example, highly fluorinated hydrofluorocarbons (HFC) and hydrofluorocarbon ethers (HFE). The term "hydrofluorocarbons" "When used herein, means a compound that contains carbon, hydrogen, and fluorine, but does not contain other atoms. The term "hydrofluorocarbon ether" as used herein refers to carbon, hydrogen, fluorine and one or more ether oxygen atoms, and optionally one or more other hetero atoms, such as trivalent nitrogen or sulfur, inserted in the carbon backbone. And compounds containing no chlorine, bromine and iodine atoms.

HFC and HFE have lower surface tension and viscosity than other organic solvents. Therefore, even if the base material to be covered has a complicated shape, it is possible to apply it continuously and uniformly, that is, without a gap. As a result, it can apply | coat to a small gap and a small hole in a composition. In addition, the composition can be coated with a thin coating film. HFCs and HFEs are less attacked by organic substances than conventional ketone or ester solvents, and therefore can be effectively used even if the substrate is a resin without being degraded by the solvent. In addition, since HFC and HFE have very low water solubility, the coating composition obtained can be prevented from being gelled by hydrolysis of the silane monomer units of the copolymer to obtain a coating composition having high storage stability. On the other hand, the use of a solvent which is easy to contain water such as alcohol is generally not preferable because condensation proceeds by partial hydrolysis of the silane monomer unit, causing gelation. HFCs and HFE are preferably liquid at room temperature (about 20 ° C.) and atmospheric pressure (1 atm) and are nonflammable.

Examples of useful HFCs include those having a carbon backbone having 3 to 8 carbon atoms, with carbon backbone having 4 to 9 carbon atoms being preferred. The carbon backbone may be straight chain, branched chain, cyclic, or mixtures thereof. Examples of useful HFCs include compounds having greater than about 5 mol% fluorine substitution and compounds having less than 95 mol% fluorine substitution based on the total number of hydrogen atoms and fluorine atoms bonded to the carbon backbone. Preferably, HFC is CF ₃ CFHCFHCF ₂ CF ₃ , C ₅ F ₁₁ H, C ₆ F ₁₃ H, CF ₃ CF ₂ CH ₂ CH ₂ F, CHF ₂ CF ₂ CF ₂ CHF ₂ , 1,2-dihydroperfluoro Rocyclopentane and 1,1,2-trihydroperfluorocyclopentane. Examples of useful HFCs include E.I. VERTREL® available from EI duPont de Nemours & Co. and ZEORORA-H® available from Nippon Zeon Co. Ltd., Tokyo, Japan Included are HFCs.

In general, the more preferred fluorinated solvent is HFE. Because HFE exhibits the best combination of optimal safety (non-flammability and low toxicity) and environmental characteristics (non-zone depletion and low global warming capacity). HFE is a compound comprising carbon, fluorine, hydrogen, one or more ether oxygen atoms, and optionally one or more other hetero atoms, such as sulfur or trivalent nitrogen, inserted in the carbon backbone. HFE may be straight chain, branched chain, cyclic, or a combination thereof, for example alkyl alicyclic. Preferably the HFE does not include unsaturated moieties.

Such highly fluorinated ethers can be represented by the following formula (IV).

(R ⁴ -O) _a -R ⁵

Wherein a is a number from 1 to 3, and R ⁴ and R ⁵ are the same or different and are selected from the group consisting of alkyl, aryl and alkylaryl groups. At least one of R ⁴ and R ⁵ comprises at least one fluorine atom, at least one of R ⁴ and R ⁵ comprises at least one hydrogen atom, and either or both of R ⁴ and R ⁵ are optionally at least one of the chains; It may comprise hetero atoms, for example oxygen, sulfur or nitrogen, preferably the total number of fluorine atoms in HFE is at least the total number of hydrogen atoms. R ⁴ and R ⁵ may be straight, branched or cyclic and may comprise one or more unsaturated carbon-carbon bonds, but preferably R ⁴ and R ⁵ are both saturated.

Examples of suitable HFEs include (1) isolated HFE (ether-bonded alkyl or alkylene, which is a segment in HFE, are not perfluorinated (eg, perfluorocarbon chains) or fluorinated (eg, hydrocarbon chains) , And not partially fluorinated), and (2) at least one of the non-separable HFE (ether bonded segments is neither perfluorinated nor contains fluorine and is partially fluorinated (ie a mixture of fluorine and hydrogen atoms) It includes)). Separate HFE is the most preferred fluorinated solvent because it exhibits the shortest atmospheric life and the lowest warming coefficient.

Isolated HFE is a mono-, di- or tri-alkoxy substituted perfluoroalkane, perfluorocycloalkane, perfluorocycloalkyl containing perfluoroalkane or perfluorocycloalkylene containing perfluoroalkane compound It includes HFE containing more than one species. Such HFEs are described, for example, in the specification of PCT Publication WO96 / 22356 and can be represented by the formula:

R _f '-(OR _h ) _x

Wherein x is 1 to about 3, and R _f ′ is a perfluorinated hydrocarbon group having x, which may be linear, branched or cyclic, etc., preferably has 2 to 9 carbon atoms, more preferably 3 Including from 6 to 6 carbon atoms, each R _h is independently a straight or branched chain alkyl group having 1 to 3 carbon atoms, and either or both of R _f 'and R _h may optionally include one or more hetero atoms in the chain; And the total number of carbon atoms in the group R _f 'and carbon atoms in the group R _h is preferably 4 to 10.

Preferably x is 1. Most preferred R _f 'groups are C ₃ F ₇ isomers (ie n-, iso-), C ₄ F ₉ isomers (ie n-, iso-, sec-, tert-), C ₅ F ₁₁ isomers, C ₆ F ₁₃ -isomers and perfluorocyclohexyl, with the most preferred R _h groups comprising methyl and ethyl.

Preferred isolated HFEs are nC ₃ F ₇ OCH ₃ , (CF ₃ ) ₂ CFOCH ₃ , nC ₄ F ₉ OCH ₃ , (CF ₃ ) ₂ CFCF ₂ OCH ₃ , nC ₃ F ₇ OC ₂ H ₅ , nC ₄ F ₉ OC ₂ H ₅ , (CF ₃ ) ₂ CFCF ₂ OC ₂ H ₅ , (CF ₃ ) ₃ COCH ₃ , (CF ₃ ) ₃ COC ₂ H ₅ , CF ₃ CF (OCH ₃ ) CF (CF ₃ ) ₂ , CF ₃ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ , CF ₃ CF ₂ CF ₂ CF (OC ₂ H ₅ ) CF (CF ₃ ) ₂ , CF ₃ CF (CF ₃ ) CF ₂ OCH ₃ , CF ₃ CF ( CF ₃ ) CF ₂ OC ₂ H ₅ , C ₈ F ₁₇ OCH ₃ , CH ₃ O (CF ₂ ) ₄ OCH ₃ , C ₅ F ₁₁ OC ₂ H ₅ , C ₃ F ₇ OCH ₃ , CF ₃ OC ₂ F ₄ OC ₂ H ₅ , C ₃ F ₇ OCF (CF ₃ ) CF ₂ OCH ₃ , (CF ₃ ) ₂ CFOCH ₃ , C ₄ F ₉ OC ₂ F ₄ OC ₂ F ₄ OC ₂ H ₅ , C ₄ F ₉ O ( CF ₂ ) ₃ OCH ₃ and 1-dimethoxy perfluorocyclohexane and mixtures thereof. Isolated HFE is available from the Minnesota Mining and Manufacturing Company as 3M® NOVEC® HFE-7100, HFE-7200 and HFE-7500 engineering fluids.

Azeotropic mixtures and azeotropic mixtures compositions which are blends of separate HFEs with non-halogenated organic compounds are also useful as fluorinated solvents. Particularly useful are organic solvents and C ₄ F ₉ OCH ₃ (described in PCT Publication WO96 / 36689), C ₄ F ₉ OC ₂ H ₅ (described in PCT Publication WO96 / 36688) and C ₃ F ₇ OCH ₃ (PCT Publication WO98 / 37163) and azeotropic mixtures and azeotropic mixtures compositions.

Examples of useful non-isolated HFEs include those described in the specification of US Pat. No. 5,658,962 to Moore et al., And Archonni et al., “Hydrofluoropolyethers”, Journal of Fluorine Chemistry 95 (1999), α-, β- and ω-substituted hydrofluoroalkyl ethers as described in pp. 41 to 50). Such non-isolated HFE can be described by the following general structural formula.

X '-[R _f "-O] _y R" H

Wherein X 'is a perfluoroalkyl group having 1 to 3 carbon atoms which may be hydro-substituted at F, H, or optionally in the ω-position, and each R _f "is -CF _2- , -C ₂ F Independently selected from the group consisting of ₄ -and -C ₃ F ₆ -and when X 'is perfluorinated at least one of the R _f "groups adjacent to X' together may form a perfluorocycloalkyl group , R "is a divalent organic group having 1 to 3 carbon atoms, may be perfluorinated, not fluorinated or partially fluorinated, y is an integer from 1 to 7, and R" when X 'is F It contains at least one F atom, preferably 3 to 8 carbon atoms in total.

Representative non-isolated HFEs useful in the present invention include, but are not limited to, the following compounds.

Preferred non-flammable, non-isolated HFEs include C ₄ F ₉ OC ₂ F ₄ H, C ₆ F ₁₃ OCF ₂ H, HC ₃ F ₆ OC ₃ F ₆ H, C ₃ F ₇ OCH ₂ F, HCF ₂ OCF ₂ OCF ₂ H, HCF ₂ OC ₂ F ₄ OCF ₂ H, HCF ₂ OCF ₂ OCF ₂ OCF ₂ H, HCF ₂ OCF ₂ CF ₂ OCF ₂ H, HC ₃ F ₆ OCH ₃ , HCF ₂ OCF ₂ OC ₂ F ₄ OCF ₂ H , And mixtures thereof. Many non-isolated HFEs useful in the present invention are available from Ausimont Corp., Milano, Italy as GALDEN H®.

The coating method of the coating composition of the present invention may be any conventional method of spin coating, dipping, potting, die coating or spray coating. The coating method is appropriately selected depending on the shape of the substrate to be coated and the thickness of the coating film required. If the coating composition comprises a solvent, the solvent may be removed by heating after applying the composition to the substrate. It is considered that the monomer portion derived from the silane unsaturated monomer in the copolymer is hydrolyzed to cause a chemical reaction with a functional group such as an OH group on the substrate to form a coating film having high adhesion on the substrate. This hydrolysis is easily caused by ambient humidity at room temperature (about 20 ° C.). Therefore, a coating film having high adhesion can be formed at a sufficiently high rate even without applying a special treatment after applying the coating liquid. Of course, the coating composition may be applied by raising the temperature and ambient humidity of the substrate during application. It is also possible to carry out a quick drying treatment such as baking.

The coating composition of the present invention can form a coating film with good adhesion to any substrate of organic, inorganic and metal. For example, the coating composition of the present invention may be an oil diffusion preventing coating (e.g., preventing diffusion of motor shaft lubricating oil, preventing diffusion of gear shaft lubricating oil such as watch parts, preventing leakage of bearing lubricating grease or sliding parts). Coatings to prevent the diffusion of grease), moisture proof coatings (eg moisture proofing of watch parts and precision mechanical parts, moisture proofing of electronic boards, moisture proofing of condensers or sensors), insulation coatings (eg condenser) Or insulation of the sensor), an antireflection coating (for example, a pellicle film or a protective film of the pellicle film), an antifouling coating (for example, prevention of adhesion of fingerprints, oil contamination or dust to an optical part or an electronic part, or the like, or such Coatings to improve the ability to remove deposits, prevent flux creep, or prevent the adhesion of organic matter to the HDD head) and weatherproof protective coatings (e.g., electronic As a coating to protect the substrate from moisture, water droplets or oil.

FIELD OF THE INVENTION The present invention relates to surface coating compositions, and more particularly to moisture proof and oil resistant coating compositions for surface application of electronic device components.

The invention is further illustrated in the following examples.

Preparation of Coating Composition

Fluoroalkyl (meth) acrylate (fluoroaliphatic group-containing unsaturated ester monomer) and vinylalkoxysilane (unsaturated silane monomer) were charged to the reactor. To this was added nC ₄ F ₉ OC ₂ H ₅ as solvent and azobisisobutyronitrile (ABIN) as initiator. The mixture was shaken for approximately 5 minutes with a shaker to completely dissolve the monomers and initiator in the solvent and bubble dry nitrogen for about 3 minutes using free Pastur. The reactor was then sealed and set in a rotary constant temperature water bath to polymerize at 65 ° C. for 16 hours. Then, the reactor was taken out of the constant temperature water bath and cooled to room temperature. The reaction solution was transferred to a measuring flask and the solvent was removed by an evaporator. Thereby, a transparent fluororesin copolymer was obtained, and the weight thereof was measured. Again nC ₄ F ₉ OC ₂ H ₅ was added so that the concentration of the fluorine resin was 2% by weight, and ultrasonic waves were irradiated to dissolve the fluorine resin in the solvent. This solution was used as coating liquid. In another embodiment, a coating solution including a terpolymer prepared from a monomer further comprising acrylic acid as a comonomer was prepared.

As a comparative example, a coating liquid comprising a homopolymer made only of fluoroalkyl (meth) acrylate containing no unsaturated silane monomer and fluoroalkyl (meth) acrylate and acrylic acid containing no unsaturated silane monomer (CH ₂ CH— A coating solution containing a copolymer prepared using C (= 0) OH) was also prepared.

Evaluation order

a) water and oil repellent properties

Water repellent and oil repellent properties were measured based on the measurement of the static contact angle to the test liquid. First, a glass plate of 76 × 16 mm that had been cleaned in advance was immersed in the coating solution (room temperature) prepared above, and then quickly pulled up, and dried to obtain a test piece. (I) pure water, (ii) silicone oil (KF-96-20cp manufactured by Shin-Etsu Chemical Co., Ltd.) or (iii) n-hexadecane (manufactured by Wako Pure Chemical Industries, Ltd.) on top of this test piece. Was added dropwise to measure the contact angle at 25 ℃.

b) water resistance test

Water resistance was evaluated by dropwise dropping. The glass plate was partially immersed in the coating solution in the same manner as described in a) to obtain a partially coated test piece. The test piece was inclined at about 45 °, and five drops of water droplets were successively dropped with a dropper so as to flow toward the boundary at an upper portion of about 5 mm from the boundary between the portion where the coating film was attached and the portion that was not attached. Then, the degree of peeling of the coating film was visually observed. As the water droplets enter the bottom of the membrane, you can observe the membrane swelling and peeling as usual. In Table 1, the test piece in case a film was peeled off was described as x, and the test piece in case the film was not peeled off was described as ■.

c) film forming ability, film hardness and adhesion test

The film forming ability, the film hardness, and the adhesiveness were tested by pencil drawing measurement in accordance with JIS K5400 84.1 using a pencil drawing tester manufactured by Rigaku Kogyo Co., Ltd. The load was 500 g.

Example 1

F (CF ₂ ) ₆ CH ₂ OC (= 0) C (CH ₃ ) = CH ₂ (component 1) as the fluoroaliphatic group-containing unsaturated ester monomer (monomer A), and (C) as the unsaturated silane monomer (monomer B) ₂ H ₅ O) ₃ SiCH = CH ₂ (component 10) to prepare a coating liquid as described in the General Procedure in Production of Coating Composition, and coated on a glass plate as described above A coating film was formed (coating 1). The physical properties of the obtained coating film were evaluated. In addition, a coating liquid containing a terpolymer was prepared from the monomer containing acrylic acid (component 12) as a comonomer (monomer C) in addition to the above monomers, and evaluated in the same manner. (Coating 2). As a comparative example, the coating liquid obtained by superposition | polymerization of the monomer which does not contain an unsaturated silane monomer (monomer B), ie, the monomer which consists of monomer A, or the monomer which consists of monomers A and C (coating 3 and coating 4, respectively) was used. Coating compositions and results are shown in Table 1 below.

Coating and its evaluation Coating number One 2 3 (comparative) 4 (comparative) Monomer A (parts by weight) Ingredient 13.0 Ingredient 13.0 Ingredient 13.0 Ingredient 13.0 Monomer B (parts by weight) Ingredient 100.09 Ingredient 100.09 - - Monomer C (parts by weight) - Ingredient 120.09 - Ingredient 120.09 Initiator (parts by weight) 0.09 0.09 0.09 0.09 Solvent (parts by weight) 22 22 22 22 Contact angle for water 118 ° 111 ° 117 ° 114 ° Contact angle for silicone oil - - - - contact angle for n-hexadecane - - - - Pencil hardness 2B 5B <6B <6B Water resistance ■ ■ × ×

Example 2

C ₇ F ₁₅ SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ OC (= 0) C (CH ₃ ) = CH ₂ (component 2) as a fluoroaliphatic group-containing unsaturated ester monomer (monomer A) Using (C ₂ H ₅ O) ₃ SiCH = CH ₂ (component 10) as the silane monomer (monomer B), a coating solution is prepared as described in the general procedure for the preparation of the coating composition described above, and on a glass plate as above Coating to form a coating film (coating 5). The physical properties of the obtained coating film were evaluated. As a comparative example, the coating liquid obtained by superposition | polymerization of the monomer which does not contain an unsaturated silane monomer (monomer B), ie, the monomer which consists of monomer A, was used (coating 6). Coating compositions and results are shown in Table 2 below.

Example 3

CC ₆ F ₁₁ CH ₂ OC (= 0) C (CH ₃ ) = CH ₂ (component 3) as the fluoroaliphatic group-containing unsaturated ester monomer (monomer A) and (C ₂ H as the unsaturated silane monomer (monomer B) ₅ O) ₃ SiCH = using CH ₂ (component 10) to prepare a coating solution as described in the general procedure of the coating composition prepared and allowed to form a coating film by coating on a glass plate as described above (coating 7). The physical properties of the obtained coating film were evaluated. As a comparative example, the coating liquid obtained by superposition | polymerization of the monomer which does not contain an unsaturated silane monomer (monomer B), ie, the monomer which consists of monomer A (coating 8), or does not contain an unsaturated silane monomer (monomer B), and is monomer A As a comonomer (monomer C), a coating liquid obtained by polymerization of a monomer composed of acrylic acid (component 12) was used (coating 9). Coating compositions and results are shown in Table 2 below.

Coating and his evaluation (continued) Example number 2 3 Coating number 5 6 (Compare) 7 8 (comparative) 9 (Compare) Monomer A (parts by weight) Ingredient 23.0 Ingredient 23.0 Ingredient 33.0 Ingredient 33.0 Ingredient 33.0 Monomer B (parts by weight) Ingredient 100.09 - Ingredient 100.09 - - Monomer C (parts by weight) - - - Ingredient 120.09 - Initiator (parts by weight) 0.09 0.09 0.09 0.09 0.09 Solvent (part by weight) 22 22 22 22 Contact angle for water 110 ° 109 ° 106 ° 104 ° 105 ° Contact angle for silicone oil - - - - - contact angle for n-hexadecane - - - - - Pencil hardness 2B <6B 6B <6B <6B Water resistance ■ × ■ × ×

Example 4

C ₆ F ₁₃ C ₂ H ₄ OC (= 0) CH = CH ₂ (component 4) as the fluoroaliphatic group-containing unsaturated ester monomer (monomer A) and (C ₂ H ₅ O as the unsaturated silane monomer (monomer B) A coating solution was prepared as described in the general procedure of preparing the coating composition described above using ₃ SiCH = CH ₂ (component 10) and coated on a glass plate as above to form a coating film (coating 10). The physical properties of the obtained coating film were evaluated. As a comparative example, the coating liquid obtained by superposition | polymerization of the monomer which does not contain an unsaturated silane monomer (monomer B), ie, the monomer which consists of monomer A, was used (coating 11). Coating compositions and results are shown in Table 3 below.

Example 5

As a fluoroaliphatic group-containing unsaturated ester monomer (monomer A), (CF ₃ ) ₂ CF (CF ₂ ) ₂ C ₂ H ₄ OC (= O) CH = CH ₂ (component 5), and an unsaturated silane monomer (monomer B) As (CH ₃ O) ₃ SiCH = CH ₂ (component 9), (C ₂ H ₅ O) ₃ SiCH = CH ₂ (component 10) or (CH ₃ O) ₃ SiCH ₂ CH = CH ₂ (component 11) The coating liquid was prepared as described in the general procedure of preparing the coating composition described above, and coated on a glass plate as above to form a coating film (coatings 12, 13 and 14, respectively). The physical properties of the obtained coating film were evaluated. As a comparative example, the coating liquid obtained by superposition | polymerization of the monomer which does not contain an unsaturated silane monomer (monomer B), ie, the monomer which consists of monomer A, was used (coating 15). Coating compositions and results are shown in Table 3 below.

Coating and his evaluation (continued) Example number 4 5 Coating number 10 11 (comparative) 12 13 14 15 (comparative) Monomer A (parts by weight) Ingredient 43.0 Ingredient 43.0 Ingredient 53.0 Ingredient 53.0 Ingredient 53.0 Ingredient 53.0 Monomer B (parts by weight) Ingredient 100.30 - Ingredient 100.3 Ingredient 90.3 Ingredient 110.3 - Monomer C (parts by weight) - - - - - - Initiator (parts by weight) 0.09 0.09 0.09 0.09 0.09 0.09 Solvent (part by weight) 22 22 22 22 22 22 Contact angle for water 119 ° 116 ° 116 ° 119 ° 119 ° 122 ° Contact angle for silicone oil - - - - - - contact angle for n-hexadecane - - - - - - Pencil hardness - - 2H 9H 9H 6B Water resistance ■ × ■ ■ ■ ■

Example 6

H (CF ₂ ) ₄ CH ₂ OC (= 0) CH = CH ₂ (component 6) as the fluoroaliphatic group-containing unsaturated ester monomer (monomer A), and (C ₂ H ₅ O as the unsaturated silane monomer (monomer B) A coating solution was prepared as described in the general procedure of preparing the coating composition described above using ₃ SiCH = CH ₂ (component 10) and coated on a glass plate as above to form a coating film (coating 16). As a comparative example, the coating liquid obtained by superposition | polymerization of the monomer which does not contain an unsaturated silane monomer (monomer B), ie, the monomer which consists of monomer A, was used (coating 17). Coating compositions and results are shown in Table 4 below.

Example 7

F (CF ₂ ) ₄ C ₂ H ₄ OC (= 0) CH = CH ₂ (component 7) as the fluoroaliphatic group-containing unsaturated ester monomer (monomer A) and (C ₂ H as the unsaturated silane monomer (monomer B) ₅ O) ₃ SiCH = CH ₂ to prepare a coating liquid, and as described in the general procedure of the above-described coating compositions prepared using the (component 10) to form a coating film by coating on a glass plate as described above (coating 18). The physical properties of the obtained coating film were evaluated. As a comparative example, the coating liquid obtained by superposition | polymerization of the monomer which does not contain an unsaturated silane monomer (monomer B), ie, the monomer which consists of monomer A, was used (coating 19). Coating compositions and results are shown in Table 4 below.

Coating and his evaluation (continued) Example number 6 7 Coating number 16 17 (Compare) 18 19 (Compare) Monomer A (parts by weight) Ingredient 63.0 Ingredient 63.0 Ingredient 73.0 Ingredient 73.0 Monomer B (parts by weight) Ingredient 100.3 - Ingredient 100.15 - Monomer C (parts by weight) - - - - Initiator (parts by weight) 0.09 0.09 0.09 0.09 Solvent (part by weight) 22 22 22 22 Contact angle for water 96 ° 94 ° 116 ° 100 ° Contact angle for silicone oil - - - - contact angle for n-hexadecane - - - - Pencil hardness 3B <6B 3B 6B Water resistance - - ■ ■

Example 8

F (CF ₂ ) ₃ CH ₂ OC (= 0) CH = CH ₂ (component 8) as the fluoroaliphatic group-containing unsaturated ester monomer (monomer A) and (C ₂ H ₅ O as the unsaturated silane monomer (monomer B) A coating solution was prepared as described in the general procedure of preparing the coating composition described above using ₃ SiCH = CH ₂ (component 10) and coated on a glass plate as above to form a coating film (coating 20). As a comparative example, the coating liquid obtained by superposition | polymerization of the monomer which does not contain an unsaturated silane monomer (monomer B), ie, the monomer which consists of monomer A, was used (coating 21). Coating compositions and results are shown in Table 5 below.

Coating and his evaluation (continued) Example number 8 Coating number 20 21 (comparative) Monomer A (parts by weight) Ingredient 83.0 Ingredient 83.0 Monomer B (parts by weight) Ingredient 100.15 - Monomer C (parts by weight) - - Initiator (parts by weight) 0.09 0.09 Solvent (part by weight) 22 22 Contact angle for water 116 ° 119 ° Contact angle for silicone oil - - contact angle for n-hexadecane - - Pencil hardness 4H 5H Water resistance ■ ×

Example 9

As a fluoroaliphatic group-containing unsaturated ester monomer (monomer A), (CF ₃ ) ₂ CF (CF ₂ ) ₂ C ₂ H ₄ OC (= O) CH = CH ₂ (component 5), and an unsaturated silane monomer (monomer B) The coating liquid was prepared as described in the general procedure of preparing the coating composition described above using four different amounts of (CH ₃ O) ₃ SiCH = CH ₂ (component 9) as To form a coating film (coatings 22, 23, 24 and 25, respectively). As a comparative example, the coating liquid obtained by superposition | polymerization of the monomer which does not contain an unsaturated silane monomer (monomer B), ie, the monomer which consists of monomer A, was used (coating 26). Coating compositions and results are shown in Table 6 below.

Coating and his evaluation (continued) Example number 9 Coating number 22 23 24 25 26 (Compare) Monomer A (parts by weight) Ingredient 53.0 Ingredient 53.0 Ingredient 53.0 Ingredient 53.0 Ingredient 53.0 Monomer B (parts by weight) Ingredient 90.3 Ingredient 90.2 Ingredient 90.1 Ingredient 90.05 - Monomer C (parts by weight) - - - - - Initiator (parts by weight) 0.09 0.09 0.09 0.09 0.09 Solvent (part by weight) 22 22 22 22 22 Contact angle for water 119 ° 121 ° 123 ° 123 ° 122 ° Contact angle for silicone oil 60 ° 66 ° 68 ° 72 ° 57 ° contact angle for n-hexadecane 79 ° 78 ° 81 ° 83 ° - Pencil hardness 9H 9H 8H H 6B Water resistance ■ ■ ■ ■ ■

Example 10

F (CF ₂ ) ₃ CH ₂ OC (= 0) CH = CH ₂ (component 8) as the fluoroaliphatic group-containing unsaturated ester monomer (monomer A), and 4 different amounts of the unsaturated silane monomer (monomer B) The coating liquid was prepared as described in the general procedure of preparing the coating composition described above using (CH ₃ O) ₃ SiCH ₂ CH = CH ₂ (component 11) and coating on a glass plate as above to form a coating film ( Coatings 27, 28, 29 and 30, respectively. As a comparative example, the coating liquid obtained by superposition | polymerization of the monomer which does not contain an unsaturated silane monomer (monomer B), ie, the monomer which consists of monomer A, was used (coating 31). Coating compositions and results are shown in Table 7 below.

Coating and his evaluation (continued) Example number 10 Coating number 27 28 29 30 31 (Compare) Monomer A (parts by weight) Ingredient 83.0 Ingredient 83.0 Ingredient 83.0 Ingredient 83.0 Ingredient 83.0 Monomer B (parts by weight) Ingredient 110.3 Ingredient 110.2 Ingredient 110.1 Ingredient 110.05 - Monomer C (parts by weight) - - - - - Initiator (parts by weight) 0.09 0.09 0.09 0.09 0.09 Solvent (part by weight) 22 22 22 22 22 Contact angle for water 116 ° 118 ° 122 ° 121 ° 120 ° Contact angle for silicone oil 65 ° 68 ° 70 ° 74 ° 69 ° contact angle for n-hexadecane 71 ° 75 ° 80 ° 83 ° 76 ° Pencil hardness 4H H 3B 4B 5B Water resistance ■ ■ ■ ■ ■

In the above tables, monomer A is a fluoroalkyl containing unsaturated ester monomer, monomer B is a silane unsaturated monomer and monomer C is a comonomer (acrylic acid). The initiator is azobisisobutyronitrile and the solvent is nC ₄ F ₉ OC ₂ H ₅ .

Monomer A

Component 1: F (CF ₂ ) ₆ CH ₂ OC (= O) C (CH ₃ ) = CH ₂

Component 2: C ₇ F ₁₅ SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ OC (= 0) C (CH ₃ ) = CH ₂

Component 3: cC ₆ F ₁₁ CH ₂ OC (═O) C (CH ₃ ) = CH ₂

Component 4: C ₆ F ₁₃ C ₂ H ₄ OC (= O) CH = CH ₂

Component 5: (CF ₃ ) ₂ CF (CF ₂ ) ₂ C ₂ H ₄ OC (= O) CH = CH ₂

Component 6: H (CF ₂ ) ₄ CH ₂ OC (= O) CH = CH ₂

Component 7: F (CF ₂ ) ₄ C ₂ H ₄ OC (= 0) CH = CH ₂

Component 8: F (CF ₂ ) ₃ CH ₂ OC (= O) CH = CH ₂

Monomer B

Component 9: (CH ₃ O) ₃ SiCH = CH ₂

Component 10: (C ₂ H ₅ O) ₃ SiCH = CH ₂

Component 11: (CH ₃ O) ₃ SiCH ₂ CH = CH ₂

Monomer C

Component 12: acrylic acid

From the above results, the coating film formed by the coating composition of the present invention using a copolymer containing an unsaturated silane monomer is equal to or larger than the coating film formed by a conventional coating composition using a copolymer containing no unsaturated silane monomer. Contact angle (contact angle with respect to water, silicone oil or n-hexadecane). At the same time, it can be seen that it has high pencil hardness and water resistance (see, for example, Examples 1 to 10, in particular Examples 1, 9 and 10). As such, the coating composition of the present invention was found to have improved adhesion to the substrate while maintaining water repellency / oil repellency equivalent or greater than conventional coating compositions. In addition, as can be seen from the result of the coating 2 of Example 1, in addition to the fluoroaliphatic group-containing unsaturated ester monomer (monomer A) and the unsaturated silane monomer (monomer B), a copolymer including other comonomers such as acrylic acid is used. Also in the case, the pencil hardness and the water resistance were improved to improve the adhesion to the substrate. Even when the addition amount of the unsaturated silane monomer was a slight amount of only about 1% by weight, the pencil hardness (adhesion to substrate) of the coating film obtained was significantly improved (see Example 9, coatings 25 and 26, etc.).

Claims (5)

A coating composition comprising a copolymer obtained by copolymerizing a monomer comprising a fluoroaliphatic group-containing unsaturated ester monomer and an unsaturated silane monomer. The coating composition of claim 1 wherein said unsaturated silane monomer is selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane and vinyl tert-butoxysilane. The coating composition according to claim 1 or 2, wherein the unsaturated silane monomer is included in an amount of 1 to 50% by weight based on the total weight of the fluoroaliphatic group-containing unsaturated ester monomer and the unsaturated silane monomer. The coating composition of claim 1, further comprising hydrofluorocarbon ether or hydrofluorocarbon. An article comprising a substrate comprising at least a portion of a surface coated with a composition comprising a copolymerization product of a fluoroaliphatic group containing unsaturated ester monomer and an unsaturated silane monomer.