KR20060126493A - Coating resin composition - Google Patents

Abstract

Disclosed is a coating resin composition characterized by containing a fluorine surfactant, which is composed of a fluorinated alkyl group- containing vinyl polymer (A) having a fluorinated alkyl group (a1), an aromatic ring (a2) and an acidic group (a3), and a binder resin (B) having an aromatic ring (b1) and an acidic group (b2).

Description

Coating resin composition {COATING RESIN COMPOSITION}

The present invention relates to a coating resin composition excellent in thin film homogeneity of a coating film.

 In the manufacturing process of semiconductor devices, such as LSI, IC, VLSI, and flat panel display devices (FPD), such as a liquid crystal display (LCD), the photolithographic method is generally employ | adopted as a method of forming a fine pattern, such as a circuit, or a coloring pattern in a board | substrate. It is becoming. In this method, a photoresist is formed by coating a resist (photosensitive resin composition) on the surface of a silicon wafer, and irradiating active energy rays such as ultraviolet rays, far ultraviolet rays, excimer laser light, and X-rays to form a latent image. This is then developed to form a negative or positive image. At this time, the resist is usually coated on the silicon wafer so that the thickness is about 1 to 2㎛ by spin coating or the like. Here, when the coating property of a resist agent is bad, the film thickness of the coating film obtained is not uniform, or the radiation coating unevenness generally called a striation generate | occur | produces. Such a non-uniformity of the coating film, for example, in a field where fine pattern precision is required, such as a thin film transistor (TFT) array of an LSI or LCD, causes problems such as deterioration of linearity and reproducibility of the fine pattern. Moreover, when manufacturing the color filter used for a color LCD etc., the color unevenness of a pixel generate | occur | produces, and as a result, the problem that the image obtained by the said display also produces color unevenness arises.

As a method for solving the above problems, a method of adding a fluorine-based surfactant to a resist is conventionally used, and various fluorine-based surfactants have been proposed (see Patent Document 1, for example). However, in recent years, as a board | substrate becomes large, the coating method is also diversified and the effect may not be enough even if it uses the conventional fluorine-type surfactant and the fluorine-type surfactant of patent document 1. In particular, when the thin film is formed by the slit & spin coating method or the slit coating method used in large LCD manufacturing, even if the above-mentioned fluorine-based surfactant is used, the homogeneity of the thin film is not sufficient.

In order to cope with the diversified coating method, the photosensitive colored resin composition excellent in thin film homogeneity is proposed not only for the spin coating method but also the coating film obtained by the slit coating method (for example, refer patent document 2). In Patent Document 2, by containing a fluorine-based organic compound (so-called fluorine-based surfactant) having a content of fluorine atoms in the composition of 3 to 40% by mass, the wettability to the substrate is improved, and the thickness is small even if the amount of liquid is small. A method for obtaining a uniform coating film is described. However, in Patent Document 2, commercially available fluorine-based surfactants are used, and in a precise application as described above, an inhomogeneous portion (coating stain) may still occur. This is the same as that used in Patent Document 2, which is a conventional additive known in the prior art, which is designed to maintain compatibility with a wide range of resins and can be used for precise purposes in this respect. It is considered that the compatibility with the resin having an acidic group or an aromatic ring is insufficient, and as a result, sufficient surfactant activity is not realized. Resin which has an acidic group and an aromatic ring is used for photosensitive resin compositions, such as photoresists for spacers for liquid crystal cells, overcoating agents of color filters, various hard coating agents, etc. besides the photosensitive coloring resin composition as described in the said patent document 2 . In such applications, thin films must be formed by spin coating, slit & spin coating, slit coating, or the like. In this regard, there is an urgent need for a resin composition for coating that can obtain a coating film having excellent homogeneity in a thin film.

Patent Document 1: Japanese Patent Application Laid-Open No. 10-309455 (page 3-14)

Patent Document 2: Japanese Patent Application Laid-Open No. 2003-222997 (No. 13)

The present invention has been made in view of the above facts, and an object of the present invention is to provide a coating resin composition excellent in thin film homogeneity of a coating film.

MEANS TO SOLVE THE PROBLEM The present inventors conducted research in order to solve the said subject, Comprising: It contains the fluorine-type surfactant which consists of a fluorinated alkyl group containing vinyl-type polymer which has a fluorinated alkyl group, an aromatic ring, and an acidic group, and a binder resin which has an aromatic ring and an acidic group. When the resin composition for coating is used, a thin film having a film thickness of submicron to tens of microns, in particular a few microns, is formed by a method such as spin coating, slit & spin coating, slit coating, or the like. The present invention was completed by discovering that coating unevenness did not occur at the time of forming a thin film, and was excellent in thin film homogeneity.

That is, this invention is a fluorine-type surfactant which consists of a fluorinated alkyl-group containing vinyl type polymer (A) which has a fluorinated alkyl group (a1), an aromatic ring (a2), and an acidic group (a3), and an aromatic ring (b1), It provides the resin composition for coating containing the binder resin (B) which has an acidic group (b2).

According to this invention, the coating resin composition excellent in the thin film homogeneity of a coating film can be provided. The composition may be used in areas where fine pattern precision is required, such as LSI and TFT arrays of LCDs, manufacturing of color filters used in color LCDs, overcoating agents for color filters, photoresists for spacers for liquid crystal cells, spin coating methods, slits, etc. & Spin coating, slit coating and the like can be preferably used in the field that needs to form a thin film.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

In the present invention, the fluorinated alkyl group is one in which all hydrogen atoms in the alkyl group are replaced with fluorine atoms (perfluoroalkyl group), and those in which some hydrogen atoms in the alkyl group are replaced with fluorine atoms (for example, HCF ₂ CF ₂ CF ₂ CF ₂ -etc.) may be any linear or branched group. In addition, what contains an oxygen atom in the said fluorinated alkyl group (for example, CF _3- (OCF ₂ CF ₂ ) ₂ -etc.) shall also be included in the definition of the fluorinated alkyl group of this invention.

The fluorinated alkyl group-containing vinyl polymer (A) used in the present invention is at least one having at least one fluorinated alkyl group (a1), at least one aromatic ring (a2), and at least one acidic group (a3). Vinyl-based polymers. This polymer is called a polymerization fluorine type surfactant. As a molecular weight of the said polymer (A), the thin film of the coating film obtained by compatibility with binder resin (B) mentioned later, the excellent compatibility with the other component mix | blended as needed, and also preventing aggregation between fluorinated alkyl groups mutually. In order to improve homogeneity, suppress foamability in the composition, and express antifoaming, the weight average molecular weight is usually 1,000 to 200,000, more preferably 5,000 to 100,000, particularly 8,000 to 80,000. desirable.

In general, fluorinated alkyl groups are both hydrophobic and oleophobic. Therefore, in order to use the compound which has a fluorinated alkyl group as surfactant, it is necessary to maintain compatibility with the various media (solution or resin) to which this surfactant is added. That is, it is necessary to introduce a lipophilic group (lipophilic group and / or hydrophilic group) in the active agent. Usually, the medium in which the fluorine-based surfactant is used is not specified. Therefore, it is often advantageous when designing a lipophilic group to select a lipophilic group that maintains compatibility with a wider range of media. In addition, since the fluorine-based surfactant has a high surface active ability derived from an fluorinated alkyl group, since the amount of addition to the medium is small, the lipophilic group is usually not designed in consideration of compatibility with the resin component contained in the medium. . In addition, even when the surfactant is selected for the type of the target medium, the compatibility with the solution (in this case, the solubility) is confirmed, but the compatibility with the resin in the medium is not usually considered. That is, in the prior art, a surfactant may be selected that is compatible (dissolved) only in the solvent in the medium, and which is hardly compatible with the resin. However, in reality, in the field where excellent thin film homogeneity and the like are required, the coating property of the nonvolatile matter contained in a medium such as resin and the surface property after film formation are important. Therefore, the surfactant compatible with the solvent (dissolved) cannot fully express its function as a surfactant. That is, even if the surfactant is commonly used (dissolved) in the solution, if the solvent or water is volatilized and the concentration of the nonvolatile matter (resin concentration) becomes high in the drying step during or after coating, coating appearance defects may occur. On the other hand, in the thin film formation process of the film thickness submicron-tens of micron level especially the several micron level which needs to apply | coat with low non volatile matter and low viscosity, the influence of surfactant on coating appearance is large (thin film in this invention) Iran, sub-microns to tens of microns). The present invention improves the compatibility between the resin and the fluorine-based surfactant in view of the functional groups constituting the resin when selecting the lipophilic group in the fluorine-based surfactant, thereby improving the homogeneity of the thin film.

The fluorinated alkyl group (a1) in the fluorinated alkyl group-containing vinyl polymer (A) is essential for expressing the surface-active ability to prevent coating staining. In order to enhance the effect of the surfactant activity, the carbon number in the fluorinated alkyl group (a1) is usually an integer of 1 to 20, preferably an integer of 3 to 12, more preferably an integer of 6 to 10, and a linear It is preferable that it is a perfluoro alkyl group. In addition, the higher the fluorine atom content in the polymer, the more excellent the surface active ability, but considering that the surface active agent having a high fluorine atom content decreases in compatibility with the resin or the solvent, the fluorine atom content in the polymer (A) is usually It is 5-50 weight%, it is preferable that it is 7-35 weight%, and it is more preferable that it is 10-30 weight%. In addition, the fluorine atom content rate in the said polymer (A) was computed by carrying out the combustion decomposition of the polymer (A), extracting the decomposed | disassembled product with water or alkaline water, and quantifying a fluorine ion concentration by the ion chromatography method.

In addition, the aromatic ring (a2) and acidic group (a3) in the said polymer (A) are necessary in order to improve compatibility with the binder resin (B) mentioned later. Although it does not specifically limit as said aromatic ring (a2), For example, the benzene ring and naphthalene ring which may have substituents, such as an alkyl group, can be mentioned, Moreover, the structure which two or more aromatic rings, such as a biphenyl skeleton, connected may be sufficient as it. have. Moreover, 2 or more types of other aromatic rings (a2) may be contained in the said polymer (A). Among these, it is preferable that it is a benzene ring in order to make compatible with the said polymer (A) and binder resin (B) mentioned later, and an interface activity capability easily. FT-IR was used for the content rate measuring method of the aromatic ring (a2) in the said polymer (A). First, the copolymerization ratio of benzyl methacrylate and methyl methacrylate is changed, azoisobutyl nitrile (AIBN) is used as an initiator in methyl isobutyl ketone (MIBK), and the copolymer of the weight average molecular weight 30,000 is subjected to radical polymerization. Synthesized. FT-IR measurement was performed using the obtained copolymer, and the analytical curve was previously prepared based on the peak intensity near 1500 cm <^-1> derived from C = C bond in an aromatic ring. It is preferable that it is 10-40 weight%, and, as for the aromatic ring (a2) content rate in the said polymer (A) measured based on this calibration curve, it is more preferable that it is 20-35 weight%.

As said acidic group (a3), a carboxy group, a hydroxyl group, a phosphoric acid group, a sulfonic acid group, etc. are mentioned, for example. These groups may exist in the polymer (A) as a substituent of the fluorinated alkyl group (a1) or the aromatic ring (a2), and the presence position in the polymer (A) is not limited. Moreover, you may have 2 or more types of other acidic groups (a3) in the said polymer (A). Among these, it is preferable that it is compatible with compatibility of the said polymer (A) and binder resin (B) mentioned later, and surfactant capability, and is excellent in the storage stability of the coating resin composition obtained, It is preferable that it is a carboxyl group or a hydroxyl group, When manufacturing the said composition, when it considers that foaming is few, it is preferable that it is a hydroxyl group. The acidic group (a3) content in the polymer (A) is preferably an acid value of 2 to 100 mgKOH / g, more preferably 7 to 70 mgKOH / g, and a hydroxyl group is preferably 20 to 200 mgKOH / g. Preferably it is 30-130 mgKOH / g.

Although the manufacturing method of the said polymer (A) is not specifically limited, The ease of industrial raw material acquisition, the ease of a manufacturing method, the ease of adjustment of a weight average molecular weight, or the introduction of the above-mentioned essential functional groups (alkyl fluoride group, aromatic ring, acidic group) are introduced. It is preferable to copolymerize the monomers (I) containing a fluorinated alkyl group containing vinylic monomer (x1), an aromatic ring containing vinylic monomer (x2), and an acidic group containing vinylic monomer (x3) from a viewpoint of ease.

Although the content rate of the fluorinated alkyl group containing vinylic monomer (x1), the aromatic ring containing vinylic monomer (x2), and the acidic group containing vinylic monomer (x3) in the said monomer (I) is not specifically limited, Above-mentioned preferable fluorine atom content rate It is preferable to select suitably so that it may become an aromatic ring content rate and an acid value. Specifically, the sum total of the fluorinated alkyl group-containing vinyl monomer (x1), the aromatic ring-containing vinyl monomer (x2) and the acidic group-containing vinyl monomer (x3) in the monomers (I) is 60% by weight or more, Moreover, the content rate of the said fluorinated alkyl group containing vinylic monomer (x1) in the said monomers (I) is 3-50 weight% normally, Preferably it is 10-40 weight%, The said aromatic ring containing vinylic monomer (x2) ) Is usually 40 to 90% by weight, preferably 50 to 80% by weight, and the content of the acidic group-containing vinyl monomer (x3) is usually 0.1 to 30% by weight, preferably 0.5 to 7% by weight. %to be. In addition, the monomers (x4) which are one or more other monomer sets mentioned later can also be used together as needed, and when used together, the ratio of the said monomers (I) is used in the range which does not impair the effect of this invention. ) Is preferably 40% by weight or less, more preferably 20% by weight or less.

 The structure of the fluorinated alkyl group-containing vinyl monomer (x1) is not particularly limited, and various kinds can be used. Examples thereof include those represented by the following general formulas (x1-1) and (x1-2). .

(Wherein R _f ¹ , R _f ² , R _f ³ are the same or different fluorinated alkyl groups of ₁ to 20 carbon atoms, R ₁ is a hydrogen atom, a methyl group, a chlorine atom or a fluorine atom, X ¹ , X ² , X ³ are the same or different divalent linking groups, m ¹ , m ² , m ³ are the same or different O or 1)

X ¹ , X ² , and X ³ (bivalent linking group) in the general formulas (x1-1) and (x1-2) are not particularly limited, and examples include the following.

(Wherein n is an integer of 1 to 10 and R ₂ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms),

or,

As said monomer (x1), the compound represented by the following structural formula (x1-1-1) (x1-1-55) and (x1-2-1) is mentioned, for example.

As said monomer (x1), only one type may be used and it can also be used as a mixture of 2 or more types of compounds from which a structure differs. Moreover, it is preferable that carbon number in the fluorinated alkyl group in the said monomer (x1) is an integer of 3-12, It is more preferable that it is an integer of 6-10, Furthermore, it is preferable that it is a linear perfluoro alkyl group.

The aromatic ring-containing vinyl monomer (x2) can be used without particular limitation as long as it is a compound having a structure having an aromatic ring such as a benzene ring or a naphthalene ring which may have a vinyl group and a substituent in the same molecule. For example, styrene, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonylphenoxy Ciethylene glycol (meth) acrylate, etc. are mentioned, Among these, benzyl (meth) acrylate is preferable for the outstanding compatibility with the obtained fluorinated alkyl-group containing vinyl type polymer (A) and binder resin (B) mentioned later. Do. In addition, in this invention, (meth) acrylate represents an acrylate and / or methacrylate unless there is particular notice.

As the monomer (x2), only one kind may be used, or a mixture of two or more kinds of compounds having different structures may be used.

As said acidic group containing vinylic monomer (x3), if it is a compound of the structure which has an acidic group, such as a vinyl group, a carboxyl group, a hydroxyl group, a phosphoric acid group, and a sulfonic acid group, in the same molecule, it can be used without a restriction | limiting in particular. For example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyphthalic acid, 2- ( Carboxyl group-containing vinyl monomers, such as a meta) acryloyloxy hexahydrophthalic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethylacrylamide, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerin mono (meth) acrylate, alkylene glycol mono (meth) Phosphoric acid group containing vinyl type monomers, such as hydroxyl-containing vinyl monomers, such as an acrylate, a mono (acryloyloxyethyl) phosphate, and a mono (methacryloyloxyethyl) phosphate, 2-acrylamide- 2-methyl Propanesulfonic acid, partial sulfonated Include a sulfonic acid group-containing vinyl-based monomers such as alkylene. Among these, it is preferable to use the acidic group containing vinylic monomer in which an acidic group is a carboxyl group or a hydroxyl group from the point which is excellent in the storage stability of the resin composition for coating obtained, and also has a low foaming when the said resin composition is manufactured. In this, it is preferable to use a hydroxyl group-containing vinyl monomer.

As said monomers (I), other monomer (x4) can be used together as needed in the range which does not inhibit the effect of this invention.

As said other monomer (x4), it is good to copolymerize with the said monomer (x1), (x2), and (x3), and various things can be used. For example, a (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms of an alkyl group, that is, methyl, ethyl, propyl, butyl, octyl, 2-ethylhexyl, decyl, dodecyl, stearyl ester and the like of (meth) acrylic acid Can be mentioned.

Moreover, ether oxygen containing alkyl ester of 3-18 carbon atoms of (meth) acrylic acid, for example, methoxy ethyl ester, ethoxy ethyl ester, methoxy propyl ester, methyl carbyl ester, ethyl carbyl ester, butylcarb As a crosslinking containing monomer, such as a bile ester, For example, dicyclopentanyloxyl ethyl (meth) acrylate, isobornyloxyl ethyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) ) Acrylate, dimethyl adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and the like.Alkyl vinyl ether having 1 to 18 alkyl carbon atoms, for example, methyl Glycidyl ester of (meth) acrylic acid, such as vinyl ether, propyl vinyl ether, dodecyl vinyl ether, ie, glycidyl methacrylate, glycidyl acrylate, etc. Can be given four products styrene macromonomer 4500, Shin-Nakamura Chemical Co., Ltd. product, NK ester macromonomer, such as M-230G and the like.

Moreover, silane coupling group containing monomers, such as fatty acid vinyl, such as acrylonitrile, a vinyl chloride, vinylidene chloride, N-vinylpyrrolidone, vinylsulfonic acid, and vinyl acetate, and 3- (meth) acryloxypropyl trimethoxysilane, Silicone chain containing monomers, such as polydimethylsiloxane chain containing (meth) acrylate, etc. are mentioned.

There is no limitation in the method of copolymerizing the said monomers (I), and various methods can be used. For example, the radical polymerization method, the cationic polymerization method, and the anion polymerization method can be used to produce the solution polymerization, the bulk polymerization, the emulsion polymerization, and the like, respectively, but the radical polymerization method is particularly convenient and industrially preferable.

The polymerization initiator that can be used in this case is not particularly limited, but for example, a peroxide such as benzoyl peroxide, diacyl peroxide, azo compounds such as AIBN, phenylazotriphenylmethane, metal chelate compounds such as Mn (acac) _3, and the like. There is this. Although the usage-amount of a polymerization initiator is not specifically limited, Although it selects suitably by the weight average molecular weight etc. of a desired copolymer, it is normally 0.1-5 mol% with respect to monomers (I), It is preferable that it is 0.3-3 mol%. .

Furthermore, if necessary, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, ethylthioglycolic acid, octylthioglycolic acid, and the like, and a coupling group-containing thiol such as γ-mercaptopropyltrimethoxysilane can be used. The compound may be used as an additive such as a chain transfer agent.

In the present invention, random or block copolymers can also be obtained by photopolymerization carried out in the presence of a photosensitizer or photoinitiator or polymerization using radiation or heat as an energy source.

The polymerization can be carried out in the presence or absence of a solvent, but it is preferable that a solvent be present for ease of operation. Examples of the solvent include alcohols such as ethanol, isopropyl alcohol, n-butanol, iso-butanol and tert-butanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, methyl acetate, ethyl acetate and acetic acid. Esters such as butyl, polar solvents such as dimethylformamide and dimethyl sulfoxide, halogen solvents such as 1,1,1-trichloroethane and chloroform, ethers such as tetrahydrofuran and dioxane, benzene and toluene, Aromatic organic solvents such as xylene, and fluorinated inert liquids such as perfluorooctane and perfluorotri-n-butylamine can be used.

In addition, the method of injecting a reaction material such as monomers (I), a polymerization initiator, and a solvent is not limited at all, and the polymerization reaction may be carried out by injecting them in a reaction vessel collectively or by dropping monomers (I) into a solvent. In particular, in order to easily control the heat generation associated with the polymerization and to easily obtain a copolymer having a uniform composition, a dropping solution in which the monomers (I) which may contain a solvent is uniformly mixed is prepared, and this is added to the reaction solvent. It is preferable to perform a polymerization reaction, dropwise.

The copolymer obtained by the said method can also isolate | separate and refine | purify by various methods, such as various column processes, the washing with a solvent, and the reprecipitation operation. In addition, only one type of copolymer can be used for the fluorine-based surfactant used in the present invention, and two or more types can be used simultaneously.

The binder resin (B) used by this invention may be at least 1 resin which has at least 1 aromatic ring (b1) and at least 1 acidic group (b2), The structure is not specifically limited. Moreover, as binder resin (B), resin which has 2 or more types of different structures can also be used together.

As said aromatic ring (b1), the benzene ring and naphthalene ring which may have a substituent are mentioned, for example, Moreover, the structure in which two or more aromatic rings, such as a biphenyl skeleton, were connected. Moreover, 2 or more types of different aromatic rings (b1) may be contained in the said binder resin (B). Among these, it is preferable that it is the benzene ring which can have a substituent from the point that the coating film excellent in compatibility with the said fluorinated alkyl group containing vinylic polymer (A), and excellent in thin film homogeneity is obtained. As said substituent, a C1-C10 alkyl group, a hydroxyl group, an alkoxy group, a carboxy group, a sulfonic acid group, a fluorine atom, etc. are mentioned, for example. Incidentally, the aromatic ring (a2) in the fluorinated alkyl group-containing vinyl polymer (A) and the aromatic ring (b1) in the binder resin (B) may be the same as or different from each other by including the presence or absence of a substituent. It doesn't work.

As said acidic group (b2), a carboxy group, a hydroxyl group, a phosphoric acid group, a sulfonic acid group, etc. are mentioned, for example. These groups can exist in binder resin (B) as a substituent on the said aromatic ring (b1), for example, and the presence position is not limited. Moreover, you may have 2 or more types of different acidic groups (b2) in the said binder resin (B). Among these, an acidic group (b2) is excellent in compatibility with the said fluorinated alkyl group containing vinylic polymer (A), excellent in the thin film homogeneity of the coating film obtained, and excellent in the storage stability of the resin composition for coating obtained. It is preferable that it is a carboxy group or a hydroxyl group, and it is preferable that it is a hydroxyl group in the point that foaming is small when the said composition is manufactured. The acidic group (a3) in the fluorinated alkyl group-containing vinyl polymer (A) and the acidic group (b2) in the binder resin (B) may be the same or different from each other, but are not limited at all, but are more compatible. It is preferable that it is the same acidic group from an excellent point.

The binder resin (B) is the main component of the coating, and the inventors have found that optimizing the combination of the binder resin (B) and the fluorinated alkyl group-containing vinyl polymer (A) in homogeneous thin film coating properties Extremely important. The selection of the binder resin (B) is mainly determined by the use of the resin composition for coating, the required properties (for example, mechanical properties, chemical resistance, optical properties, etching resistance), manufacturing processes, and the like.

For example, in the case of a positive photoresist using i line, phenol novolac resin is used as binder resin (B), and in the case of photoresist using KrF line, hydroxy styrene resin is used, and A photosensitive agent which is various reactive compounds, respectively, is used in combination. On the other hand, in the case of a color resist, for example, as the binder resin (B), an acrylic resin which is non-photosensitive and soluble in an aqueous alkali solution [for example, benzyl (meth) acrylate and (meth) acrylic acid copolymer, benzyl (meth) ) Acrylate (meth) acrylic acid, alkyl polyoxyethylene (meth) acrylate copolymer, and the like], and is used in combination with a polyfunctional acrylate and the like and a photopolymerization initiator as a photosensitive polymerization component which is a reactive compound. In the use of an overcoat agent for color filters, an antireflective coating agent on the surface of the polarizing plate, and the like, a developing step is not accompanied. That is, in such a use, as a binder resin (B), what is called photocurable resin (for example, an acrylic resin, an acrylic oligomer, an acrylic monomer, an epoxy resin, an acrylic modified epoxy resin, an epoxy modified acrylic resin, a urethane modified acrylic resin, polyester) Modified acrylic resins, etc.), which are used in combination with a photopolymerization initiator to produce a coating agent, and are coated on the entire surface of the target substrate, followed by photocuring.

Among these, in order to realize the effect of this invention easily, especially the acrylic copolymer which has an aromatic ring and a carboxy group together, for example, the copolymer of benzyl (meth) acrylate and (meth) acrylic acid, benzyl (meth) acrylate, The multicomponent copolymer of (meth) acrylic acid and another monomer is preferable as binder resin (B). Moreover, it is preferable that the acid value of binder resin (B) is 30-400 mgKOH / g, It is preferable that the weight average molecular weight is the range of 1,000-300,000, It is more preferable that it is 5,000-200,000.

The resin composition for coating of this invention has no restriction | limiting except the resin composition containing the above-mentioned fluorinated alkyl-group containing vinyl type polymer (A) and binder resin (B). Depending on the use, other components, for example, a photosensitive colored resin composition, may further contain a colorant (pigment, dye, etc.), a dispersant, and the like. Since the fluorinated alkyl group-containing vinyl polymer (A) used in the present invention has an aromatic ring, compatibility with an organic colorant (pigment) generally used is also good. In addition, if necessary, other components, for example, reactive compounds, solvents, other surfactants, storage stabilizers, plasticizers, fluorescent agents, colorants, thickeners, thixotropic agents, resin dissolution inhibitors, and silane coupling agents, which are necessary when used as photoresists It is also possible to add various additives, such as adhesive strengthening agents, such as a ring agent, to the resin composition of this invention.

For example, as an example of the component which can be used when used as a negative photoresist, the combination of the vinyl monomers and photoinitiator which can be superposed | polymerized by light irradiation is mentioned. Specific examples of such vinyl monomers include trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like. As an example of the component which can be used when used as a positive photoresist, the quinonediazide type compound etc. which can be used suitably in combination with the novolak-type binder resin are mentioned.

As the solvent, various substances can be used without any limitation, and for example, acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, butyrolactone, etc. Alcohols such as ketones, methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-butyl alcohol, pentanol, heptanol, octanol, nonanol and decanol Ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Alcohol ethers such as glycol monopropyl ether, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, acet Esters such as propyl, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate and butyl butyrate, methyl 2-oxypropionate, ethyl 2-oxypropionate, ethyl 2-oxypropionate, 2- Monocarboxylic acid esters such as butyl oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, cellulose acetate, methylcellulose solution, ethylcellulose solution Cellulose esters such as acetates, propyl cellulose acetates, butyl cellulose acetates, propylene glycols, propylene glycol monomethyl ethers, propylene glycol monomethyl ether acetates, propylene glycol monoethyl ether acetates, and propylene glycol monobutyl ether acetates Glee Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, trichloroethylene, fluoro solvent, HCFC , Halogenated hydrocarbons such as HFC, fully fluorinated solvents such as perfluorooctane, aromatic organic solvents such as toluene and xylene, dimethylacetiamide, dimethylformamide, N-methylacetamide, N-methylpyrrolidone Polar solvents, such as these, etc. are mentioned, You may use individually, or may mix and use 2 or more types of different solvents.

Among these, it is preferable to use the thing whose boiling point in normal pressure is 80-200 degreeC in order to make the balance of the coating property and drying property of the resin composition for coating obtained obtained excellent.

The compounding ratio of the said solvent can be suitably adjusted according to the film thickness and application conditions which are necessary when apply | coating the resin composition for coating. However, it is 10-10,000 weight part normally with respect to 100 weight part of total resin components (binder resin (B) and the above-mentioned various reactive compounds used together as needed) in the resin composition for coating, Preferably it is 50-2,000 weight part It is wealth.

As the colorant, pigments and dyes such as red, green, blue and black can be used without particular limitation. In terms of heat resistance and light resistance, pigments are preferable, and in general, the average particle diameter of the pigment is 0.005 to 3 µm, and in particular, the coating property of the coating resin composition is preferably in the range of 0.1 to 1 µm in order to obtain a transparent coating film.

The dispersant is not particularly limited as long as it is an effective dispersant at the time of dispersing the colorant. For example, there are intermediates of pigments, intermediates of dyes, polyamide compounds, polyurethane compounds, acrylic compounds, polyester compounds and the like.

Content of the said fluorinated alkyl group containing vinyl type polymer (A) in the resin composition for coating of this invention is suitably selected according to the film thickness, application conditions, etc. which are needed when apply | coating the said resin composition to a board | substrate. Usually, the fluorinated alkyl group-containing vinyl polymer (A) is 0.0005 to 10 parts by weight, preferably 0.005 to 5 parts by weight, and more preferably 0.05 to 1 part by weight based on 100 parts by weight of the resin composition.

In addition, when using the fluorinated alkyl group containing vinyl type polymer (A) with low fluorine atom content rate, by increasing content of the fluorinated alkyl group containing vinyl type polymer (A) in the coating resin composition of this invention, The effect can fully be exhibited.

In manufacture of the coating resin composition of this invention, it is not restrict | limited also in the method of mixing the said fluorinated alkyl-group containing vinyl type polymer (A). For example, the method of adding and mixing a vinyl polymer (A) to what mixed each said component uniformly previously, and the coloring agent normally performed when manufacturing the photosensitive colored resin composition are binder resin (B) and a dispersing agent. And dispersing or dispersing the vinyl polymer (A) in a specific single component or a plurality of components in the resin composition for coating in advance in the method of adding during the production of the so-called color paste, which is dispersed by a solvent or the like. And the like can be mentioned.

As the coating method of the resin composition for coating of this invention, various methods can be applied and it does not restrict | limit in particular. For example, spin coating method, roll coating method, dip coating method, spray coating method, Freud coating method, curtain coating method, slit coating method, slit & spin coating method, etc. can be mentioned. It can use suitably for thin film coating methods, such as a spin coating method and a slit coating method. Moreover, it does not specifically limit also about the method of forming a coating film, It selects according to the use etc. of resin composition for coating. As a method for obtaining the target film | membrane, it is preferable to use natural binder (lacquer), thermosetting reaction, photocuring reaction, etc. suitably by binder resin (B), the other reactive compound used as needed, etc. suitably. .

Moreover, the use of the coating resin composition of this invention is not specifically limited, either. In particular, photolithography in the production of color filters for liquid crystal display production such as personal computers, PDAs (portable information terminals), televisions, mobile phones, video, liquid crystal substrates, and PS plates, or in various semiconductor production such as LSIs and ICs. It can be preferably used in various fields using a method. Especially when used as the photosensitive colored resin composition for color filters for liquid crystal display manufacture, the overcoat agent for color filters, the spacer material for liquid crystal cells, the anti-reflective film material for optical films, various hard coating materials, etc. which require a fine coloring pattern, The effect can be easily realized, and it can be said to be the most preferable use.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples. In addition, "part" and "%" of an Example are a basis of weight unless there is particular notice.

Synthesis Example  One

200 parts of methyl isobutyl ketones (MIBK) were injected into the glass flask provided with the stirring apparatus, the condenser, the thermometer, and the dropping rod, and the nitrogen in the reaction container was fully nitrogen-substituted under stirring. Subsequently, the monomer (I-1) which raised temperature to 90 degreeC, mixed 20 parts of fluorinated alkyl-group containing vinylic monomers (x1-1-1), 78 parts of benzyl methacrylate, and 2 parts of methacrylic acid at the same temperature. And a mixture of 100 parts of MIBK and 4.0 parts of azobisisobutyronitrile (AIBN) were added dropwise over 2 hours by a dropping rod. After completion of the dropwise addition, the polymerization reaction was carried out by holding at the same temperature for 10 hours, then the solvent was removed at 80 ° C under reduced pressure, and the remaining solid was dried to obtain a copolymer (A-1). As a result of measuring the weight average molecular weight of the obtained copolymer by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a mobile phase, it was 10,900 in polystyrene conversion value.

Synthesis Example  2

In Synthesis Example 1, monomers (I-2) consisting of 20 parts of a fluorinated alkyl group-containing vinyl monomer (x1-1-7), 78 parts of benzyl methacrylate, and 2 parts of methacrylic acid A copolymer (A-2) was synthesized in the same manner as in Synthesis example 1 except for setting it as the above. The weight average molecular weight of the obtained copolymer (A-2) was 10,200.

Synthesis Example  3

In the synthesis example 1, the monomers (I-1) consist of 20 parts of fluorinated alkyl-group-containing vinyl monomers (x1-1-1), 55 parts of benzyl methacrylate, and 25 parts of 2-hydroxyethyl methacrylates. A copolymer (A-3) was synthesized in the same manner as in Synthesis Example 1 except that (I-3) was used. The weight average molecular weight of the obtained copolymer (A-3) was 11,000.

Synthesis Example  4

In Synthesis Example 1, monomers (I-4) comprising monomers (I-1) comprising 35 parts of fluorinated alkyl group-containing vinyl monomer (x1-1-1), 63 parts of benzyl methacrylate and 2 parts of methacrylic acid A copolymer (A-4) was synthesized in the same manner as in Synthesis Example 1 except for setting it as the above. The weight average molecular weight of the obtained copolymer (A-4) was 11,600.

Synthesis Example  5

In Synthesis Example 1, monomers (I-5) consisting of 10 parts of a fluorinated alkyl group-containing vinyl monomer (x1-1-1), 80 parts of benzyl methacrylate, and 10 parts of methacrylic acid A copolymer (A-5) was synthesized in the same manner as in Synthesis example 1 except for setting it as the above. The weight average molecular weight of the obtained copolymer (A-5) was 10,700.

Synthesis Example  6

In Synthesis Example 1, monomers (I-6) consisting of 20 parts of fluorinated alkyl group-containing vinyl monomers (x1-1-1), 70 parts of benzyl methacrylate, and 10 parts of methacrylic acid (I-6) A copolymer (A-6) was synthesized in the same manner as in Synthesis example 1 except for setting it as the above. The weight average molecular weight of the obtained copolymer (A-6) was 10,000.

Synthesis Example  7

In Synthesis Example 1, monomers (I-1) were composed of 20 parts of fluorinated alkyl group-containing vinyl monomers (x1-1-1), 48 parts of benzyl methacrylate, 2 parts of methacrylic acid, and 30 parts of methyl methacrylate. A copolymer (A-7) was synthesized in the same manner as in Synthesis Example 1 except that Monomer (I-7) was used. The weight average molecular weight of the obtained copolymer (A-7) was 12,000.

Synthesis Example  8

In Synthesis Example 1, 20 parts of the fluorinated alkyl group-containing vinyl monomer (x1-1-1), 65 parts of benzyl methacrylate, 2 parts of methacrylic acid, and 2-hydroxyethyl meta A copolymer (A-8) was synthesized in the same manner as in Synthesis Example 1 except that Monomer (1-8) consisting of 13 parts of acrylate was used. The weight average molecular weight of the obtained copolymer (A-8) was 12,300.

Synthesis Example  9

100 parts of methyl isobutyl ketones were injected into the glass flask provided with the stirring apparatus, the condenser, the thermometer, and the dropping rod, and the nitrogen in the reaction container was fully nitrogen-substituted under stirring. Subsequently, the monomer (I-9) which heated up at 80 degreeC and mixed 20 parts of fluorinated alkyl-group containing vinylic monomers (x1-1-1), 78 parts of benzyl methacrylate, and 2 parts of methacrylic acid at the same temperature was carried out. And a mixture of 50 parts of MIBK and 1.0 part of AIBN were added dropwise over 2 hours by a dropping rod. After completion of the dropwise addition, the polymerization reaction was carried out by maintaining the mixture at the same temperature for 10 hours, and then the solvent was removed at 80 ° C under reduced pressure, and then the remaining solid was dried to obtain a copolymer (A-9). The weight average molecular weight of the obtained copolymer (A-9) was 46,500.

Synthesis Example  10

In Synthesis Example 9, monomers (I-9) comprising 20 parts of a fluorinated alkyl group-containing vinyl monomer (x1-1-1), 55 parts of benzyl methacrylate, and 25 parts of 2-hydroxyethyl methacrylate A copolymer (A-10) was synthesized in the same manner as in Synthesis Example 9 except that (I-10) was used. The weight average molecular weight of the obtained copolymer (A-10) was 48,000.

Synthesis Example 11 ( Synthesis of fluorinated alkyl group-containing vinyl monomer described in Patent Document 1)

In Synthesis Example 1, a copolymer of ethylene oxide and propylene oxide having 20 parts of fluorinated alkyl group-containing vinyl monomer (x1-1-1), 30 parts of isostearyl acrylate and a molecular weight of about 400 A copolymer (A-11) was synthesized in the same manner as in Synthesis Example 1 except that Monomer (I-11) consisting of 42 parts of single-ended acrylate and 8 parts of methyl methacrylate was used. The weight average molecular weight of the obtained copolymer (A-11) was 11,00.

Synthesis Example 12 ( Synthesis of fluorinated alkyl group-containing vinyl monomer described in Patent Document 1)

In Synthesis Example 1, 20 parts of fluorinated alkyl group-containing ethylenically unsaturated monomers (x1-1-1), 30 parts of isostearyl acrylate, and a polyethylene terminal having a methyl group of a single terminal having a molecular weight of about 500 in monomer (I-1) A copolymer (A-12) was synthesized in the same manner as in Synthesis Example 1 except that Monomer (I-12) consisting of 42 parts of single-ended acrylates and 8 parts of methyl methacrylate was used. The weight average molecular weight of the obtained copolymer (A-12) was 12,200.

Synthesis Example  13

In the synthesis example 9, the monomers (I-9) consist of 30 parts of fluorinated alkyl-group containing vinylic monomers (x1-1-1), 30 parts of methacrylic acid, and 40 parts of methyl methacrylates (I-13). A copolymer (A-13) was synthesized in the same manner as in Synthesis Example 1, except that () was used. The weight average molecular weight of the obtained copolymer (A-13) was 46,000.

Table 1 shows the fluorine atom content, aromatic ring content and acid value / hydroxyl value of the fluorinated alkyl group-containing vinyl polymer synthesized as described above.

TABLE 1

Properties of Fluorinated Surfactants

Fluorinated alkyl group-containing vinyl polymer Fluorine atom content rate (%) Aromatic ring content rate (%) Acid value / hydroxyl value (mg / KOH) A-1 12.5 34 13/0 A-2 11.2 34 13/0 A-3 12.5 24 0/108 A-4 21.8 27 13/0 A-5 6.2 35 65/0 A-6 12.5 31 65/0 A-7 12.5 21 13/0 A-8 18.7 28 13/56 A-9 12.5 34 13/0 A-10 12.5 24 0/108 A-11 12.5 0 0/59 A-12 12.5 0 0/0 A-13 18.7 0 196/0

Example  1 to 10 and Comparative example  1 to 3

A high-speed disperser in which 200 parts of zirconia beads having a diameter of 0.5 mm was injected, was used as a colorant. Pigment Red 254 8.0 parts, as a polyester dispersant, Adispa PB814 (trade name, Ajinomoto Co., Ltd.) 2.5 parts, methacrylic acid / benzyl methacrylate = 13/87 (weight ratio) as binder resin (B) 25.0 parts of a propylene glycol monomethyl ether acetate solution (39.7 weight% of non volatile matters) of a copolymer (acid value 84 mgKOH / g, weight average molecular weight 22,000), 64.5 parts of propylene glycol monomethyl ether acetate as a solvent are injected, and it is 8 hours at 2000 rpm. Dispersed during, a red pigment dispersion was obtained. Subsequently, to 100 parts of the prepared red pigment dispersion, 7.0 parts of dipentaerythritol hexaacrylate as a photopolymerizable monomer, 0.3 part of Monocure # 369 (trade name, manufactured by Chivas Specialty Chemicals Co., Ltd.) as a photopolymerization initiator, and Synthesis Example 1 After adding 0.11 parts of fluorosurfactant consisting of the copolymers (A-1) to (A-13) obtained in ˜14, the mixture was filtered through a filter having a diameter of 0.1 μm to prepare a resin composition for coating ( Examples 1-10 and Comparative Examples 1-3. The following test was done about the applicability | paintability of the obtained resin composition. The evaluation results are shown in Table 2.

Comparative Example 4 (Fluoro-based Surfactant Used in Patent Document 2)

Except for using MegaPuck R-30 (manufactured by Dainippon Ink and Chemicals, Inc., a perfluoroalkyl group-containing fluorinated acrylic oligomer) as the fluorine-based surfactant, the coating properties were the same as those of Examples 1 to 10 and Comparative Examples 1 to 3. Evaluation was performed.

Comparative Example 5 (Fluoro-based Surfactant Used in Patent Document 2)

As a fluorine-based surfactant, MegaPuck F-143 (manufactured by Dainippon Ink and Chemicals, Inc., C ₈ F ₁₇ SO ₂ N (R) CH ₂ CH ₂ O (CH ₂ CH ₂ O) _n H (R is an alkyl group, n An average of 15)] was used, and applicability evaluation was performed similarly to the said Examples 1-10 and Comparative Examples 1-3.

Comparative example  6

Coating properties were evaluated in the same manner as in Examples 1 to 10 and Comparative Examples 1 to 3 except that a non-polymerized C ₆ F ₁₃ CH ₂ CH ₂ SCH ₂ CH ₂ COONH ₄ was used as the fluorine-based surfactant.

Applicability  Test Methods

1 ml of the coating resin composition prepared by the above method was added to a central portion on a glass plate having a width of 12 cm and spin-coated at a rotation speed of 600 rpm and a rotation time of 30 seconds. Subsequently, the surface state of the coating film heated by drying at 90 degreeC for 3 minutes, and hardened | cured by 120 W / cm high pressure mercury lamp was visually observed.

Evaluation standard

1: coating smear does not occur

2: slight smear of coating occurs practically without problems

3: coating smear partially occurs

4: application smear occurs remarkably

On the other hand, the four numbers indicate that the smaller the number, the better the result.

In addition, the present coating method is spin coating, but the rotation speed is relatively low, so that the scattering of the solvent during spin coating is about 15 to 30% or less (typically, when it is rotated at high speed (2000 to 3000 revolutions), 85 to 95% of the solvent Scattered during spin coating]. Therefore, in addition to the coating stain (coating stain which is a problem with spin coating) caused by the shearing force due to rotation, the presence or absence of dry staining of the solvent in the drying process, which is particularly problematic at the time of slit coating, can also be observed.

TABLE 2

Coating film evaluation result of resin plastics for coating

Fluorinated Surfactant Application appearance Example 1 A-1 One Example 2 A-2 2 Example 3 A-3 One Example 4 A-4 One Example 5 A-5 2 Example 6 A-6 One Example 7 A-7 2 Example 8 A-8 One Example 9 A-9 One Example 10 A-10 One Comparative Example 1 A-11 3 Comparative Example 2 A-12 3 Comparative Example 3 A-13 4 Comparative Example 4 Megapuck R-30 3 Comparative Example 5 Megapuck F-143 4 Comparative Example 6 C ₆ F ₁₃ CH ₂ CH ₂ SCH ₂ CH ₂ COONH ₄ 4

Example  11-20, Comparative example  7-12

Propylene glycol monomethyl ether acetate solution (non-volatile content 39.7 weight%) of methacrylic acid / benzyl methacrylate = 13/87 (weight ratio) copolymer (acid value 84 mgKOH / g, weight average molecular weight 22,000) as binder resin (B) 25.0 In addition, 64.5 parts of propylene glycol monomethyl ether acetate as a solvent were injected into a container, and the fluorine-type surfactant consisting of copolymers (A-1)-(A-13) obtained by the synthesis examples 1-13, MegaFuck R-30, the F-143, and _{C 6 F 13 CH 2 CH 2} SCH 2 CH 2 COONH 4 , respectively were mixed with 0.11 part was added. Subsequently, the resin composition for coating (Examples 11-20 and Comparative Examples 7-12) was manufactured by filtration with a filter of 1.0 micrometer in diameter.

Applicability  Test Methods

1 ml of the coating resin composition prepared by the above method was added to a central portion on a glass plate having a width of 12 cm, and spin-coated at a rotation speed of 600 rpm and a rotation time of 30 seconds. Next, the surface state of the coating film heated and dried at 90 degreeC for 3 minutes was visually observed. The results are shown in Table 3.

Evaluation standard

1: coating smear does not occur

2: slight smear of coating occurs practically without problems

3: coating smear partially occurs

4: application smear occurs remarkably

Vesicular  Test Methods

50 g of the coating resin composition prepared by the above method was placed in a glass bottle of 100 cc and sealed. After manually reciprocating 10 times of shaking, the time until the foamed foam disappeared and the liquid level was exposed was measured. The results are shown in Table 3.

TABLE 3

Coating film evaluation result of resin composition for coating

Fluorinated Surfactant Application appearance Liquid exposure time (sec.) Example 11 A-1 One 95 Example 12 A-2 2 70 Example 13 A-3 One 130 Example 14 A-4 One 140 Example 15 A-5 2 90 Example 16 A-6 One 180 Example 17 A-7 2 110 Example 18 A-8 One 110 Example 19 A-9 One 250 Example 20 A-10 One 280 Comparative Example 7 A-11 3 190 Comparative Example 8 A-12 3 300 Comparative Example 9 A-13 4 420 or more Comparative Example 10 Megapuck R-30 3 120 Comparative Example 11 Megapuck R-143 4 330 Comparative Example 12 C ₆ F ₁₃ CH ₂ CH ₂ SCH ₂ CH ₂ COONH ₄ 4 420 or more

The present invention provides a coating resin composition excellent in thin film homogeneity of the coating film. The composition of this invention can be used suitably for the field | area which requires fine pattern precision, the field | area which needs to form a thin film, etc.

Claims (8)

Fluorine-type surfactant which consists of a fluorinated alkyl-group containing vinyl type polymer (A) which has a fluorinated alkyl group (a1), an aromatic ring (a2), and an acidic group (a3); And Binder resin (B) which has an aromatic ring (b1) and an acidic group (b2) Resin composition for coating comprising a. The method of claim 1, The fluorine atom content of the fluorinated alkyl group-containing vinyl polymer (A) is 7 to 35% by weight, the aromatic ring content is 10 to 40% by weight based on the FT-IR method, and the acid value is 2 to 100 mgKOH. / g, and / or hydroxyl value is 20-200 mgKOH / g, and the weight average molecular weight is 5,000-100,000, The resin composition for coating characterized by the above-mentioned. The method of claim 1, Monomers (I) in which the fluorinated alkyl group-containing vinyl polymer (A) comprises a fluorinated alkyl group-containing vinyl monomer (x1), an aromatic ring-containing vinyl monomer (x2) and an acidic group-containing vinyl monomer (x3) (I) It is a copolymer obtained by superposing | polymerizing), The resin composition for coating characterized by the above-mentioned. The method of claim 3, The sum total of the said fluorinated alkyl group containing vinylic monomers (x1), the said aromatic ring containing vinylic monomer (x2), and the said acidic group containing vinylic monomer (x3) in the said monomers (I) is 60 weight% or more, The content rate of the said fluorinated alkyl-group containing vinylic monomer (x1) in the said monomers (I) is 3-50 weight%, The content rate of the said aromatic ring containing vinylic monomer (x2) is 40-90 weight%, The said acidity The content rate of group containing vinylic monomer (x3) is 0.1-30 weight%, The coating resin composition characterized by the above-mentioned. The method of claim 4, wherein The said aromatic ring containing vinylic monomer (x2) is benzyl (meth) acrylate, The resin composition for coating characterized by the above-mentioned. The method of claim 4, wherein The resin composition for coating, wherein the acidic group in the acidic group-containing vinyl monomer (x3) is a carboxyl group or a hydroxyl group. The method of claim 1, The binder resin (B) is a resin composition for coating, characterized in that the acrylic polymer having an aromatic ring and a carboxyl group. The method of claim 1, The compounding ratio of the said fluorinated alkyl group containing vinyl type polymer (A) in the coating resin composition is 0.0005-10 weight%, The coating resin composition characterized by the above-mentioned.