JP4896618B2 - Thermosetting resin composition and protective film covering material obtained therefrom - Google Patents

Description

  INDUSTRIAL APPLICABILITY The present invention provides a photomask protective film that has excellent antifouling properties, has high light transmittance, does not cause interference fringes even in a thin film, and can effectively prevent electrostatic breakdown even when used in a photomask having a metal pattern. The present invention relates to a thermosetting resin composition used for coating and a protective film covering material obtained from the resin composition. This composition can also form a hard coat layer capable of improving the antifouling property, antifouling durability, scratch resistance, abrasion resistance, etc. of the optical recording medium, optical display device or optical member. .

  In so-called photolithographic technology for forming a fine pattern by using means such as exposure and development, an exposure original plate on which a predetermined pattern called a photomask is drawn is used. Photomasks can be broadly classified as follows: an emulsion mask formed by coating an emulsion (emulsion) layer containing gelatin and silver halide on a glass substrate, and a metal such as chromium or chromium oxide deposited on the glass substrate. It is classified as a chrome mask that forms a circuit pattern or the like.

  Both types of photomasks have some drawbacks. For example, emulsion masks are soft and easily scratched because gelatin is the main component. Further, if dirt such as fingerprints adheres to the film surface, it becomes difficult to remove. The chrome mask is not only expensive, but if the metal pattern is separated, a potential difference occurs between the separated metal patterns, and static electricity is generated to cause discharge between the patterns, which destroys the pattern. It becomes impossible to use.

  In order to eliminate these drawbacks, it is necessary to form a protective film on the circuit pattern. However, the protective film is required not only to protect the circuit pattern but also to prevent electrostatic breakdown in the chrome mask. In addition, the protective film should not greatly reduce the ultraviolet transmittance of light, and an antifouling function for preventing the adhesion of resin and the like to come into contact with the uncured photoresist is also important. Further, the thin protective film generates interference fringes during exposure, disturbs the exposure pattern, and deteriorates the appearance. If the protective film is made thick so as not to generate interference fringes, problems such as light transmittance and workability also occur.

  Patent Document 1 (Japanese Patent Application Laid-Open No. 2003-327896) discloses a coating resin composition in which an aqueous solution of an acrylic resin containing a group I element such as lithium contains a group IV fine metal such as titanium. The composition is basically a resin composition for a protective film of a chromium mask having the above-described metal circuit pattern, and prevents electrostatic breakdown occurring between the metal patterns by blending fine metal. However, since this protective film contains fine metals, a decrease in light transmittance is inevitable, and there are drawbacks such as poor stability due to aggregation of fine metals.

Patent Document 2 (JP-A-11-305420), two-pack crosslinking type antifouling surface coating agent (trade name "DEFENSA TR-310" manufactured by Dainippon Ink and Chemicals, Inc.) and a curing agent (trade name " A protective film agent for a photomask precursor using “Burnock DN-950” (manufactured by Dainippon Ink & Chemicals, Inc.) is described. Although the protective film agent described here is mainly used for a protective film of an emulsion mask, it is a two-component cross-linking antifouling surface coating agent (trade name “Defenser TR-310” manufactured by Dainippon Ink & Chemicals, Inc.). It is not clear what is the main ingredient, and the technical content is not clear. Moreover, since it is a two-component type, a reduction in work efficiency is also expected.
JP 2003-327896 A JP-A-11-305420

  The inventors of the present invention provide a thermosetting resin composition used for a protective film of a photomask that can be cured at a low temperature and provides a composition having excellent work stability because it can be cured even in a one-component type. Provided are those having excellent soiling properties, high light transmittance, no interference fringes even in a thin film, and capable of effectively preventing electrostatic breakdown even when used in a chromium mask for forming a metal pattern.

  That is, the present invention provides a thermosetting resin composition containing a silicone acrylic resin having an alkoxysilyl group and a hydroxyl group, a compound having a fluorene skeleton, an alkoxysilane compound and a metal chelating agent.

  The compound having a fluorene skeleton is preferably a compound having a hydroxyl group or an epoxy group as a functional group.

（式中のＲ_１は水素、メチル基またはエチル基を表し、Ｒ_２はＯＨ、−Ｏ−Ｒ_３−ＯＨまたは

を表し、上記Ｒ_２中のＲ_３は炭素数１〜４のアルキレン基を示す。）
で表される化合物である。 More preferably, the compound having a fluorene skeleton has the formula:

(In the formula, R ₁ represents hydrogen, a methyl group or an ethyl group, and R ₂ represents OH, —O—R ₃ —OH or

R _{3 in} R ₂ represents an alkylene group having 1 to 4 carbon atoms. )
It is a compound represented by these.

  In the present invention, the solid content of the silicone acrylic resin has 5 to 55% by weight of the alkoxysilyl group and 3 to 30% by weight of the hydroxyl group.

  The thermosetting resin composition of the present invention may further contain a monovalent or divalent alcohol solvent.

  The present invention also provides a protective film coating material obtained by coating an original plate with the thermosetting resin composition.

  The film thickness of the layer coated with the thermoplastic resin composition is preferably 1 to 5 μm.

  The thermosetting resin composition of the present invention may be a one-pack type or a two-pack type, and since a silicone acrylic resin is used as a main agent, it has high solvent resistance and high light transmittance. Excellent as a protective film. In the case of a material using a silicone resin, the refractive index of light tends to decrease. However, by introducing a fluorene compound, the refractive index is improved, and no interference fringes occur even in a thin film. Furthermore, static electricity is generated when the photomask is repeatedly attached and peeled over and over, and in the case of a chromium mask having a metal pattern, a discharge phenomenon occurs and the circuit pattern is destroyed. When used, it has high resistance to electrostatic breakdown, and durability is improved even with a chrome mask.

  The thermosetting resin composition of the present invention will be described for each component.

(Silicone acrylic resin)
The first component of the thermosetting resin composition of the present invention is a silicone acrylic resin having an alkoxysilyl group and a hydroxyl group. The alkoxysilyl group can be introduced by a monomer having an alkoxysilyl group, and the hydroxyl group can be introduced by a monomer having a hydroxyl group. The silicone skeleton can be introduced by a monomer having a polysiloxane group.

  More specifically, the silicone acrylic resin having an alkoxysilyl group and a hydroxyl group of the present invention includes a monomer (a) having a polysiloxane group, a monomer (b) having an alkoxysilyl group, and a monomer having a hydroxyl group. It is a resin formed by radical polymerization of the monomer (d) having a functional group that does not react with the monomer (c) and the monomer other than radical polymerization.

〔式中のＲ^４は水素原子または炭素原子数１〜１０の炭化水素基であり、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、フェニル基、シクロヘキシル基、デシル基が挙げられ、好ましくは水素原子、メチル基である。また式中のＲ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９は互いに同一でも異なっていてもよい水素原子または炭素原子数１〜１０の炭化水素基であり、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、フェニル基、シクロヘキシル基、デシル基が挙げられ、好ましくはＲ^５、Ｒ^６、Ｒ^７、Ｒ^８についてはメチル基、フェニル基、Ｒ_６についてはメチル基、ブチル基、フェニル基である。また式中のｎは２以上の整数であり、好ましくは１０以上の整数、より好ましくは３０以上の整数である。〕で、及び／または、一般式（２）

〔式中のＲ^１０は水素原子または炭素原子数１〜１０の炭化水素基であり、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、フェニル基、シクロヘキシル基が挙げられ、好ましくは水素原子、メチル基である。また式中のＲ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５は互いに同一でも異なっていてもよい水素原子または炭素原子数１〜１０の炭化水素基であり、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、フェニル基、シクロヘキシル基が挙げられ、好ましくはＲ^１１、Ｒ^１２、Ｒ¹³、Ｒ¹⁴についてはメチル基、フェニル基、Ｒ¹⁵についてはメチル基、ブチル基、フェニル基である。また式中のｐは０〜１０の整数であり、好ましくは３である。また、式中のｑは２以上の整数であり、好ましくは１０以上の整数、より好ましくは３０以上の整数である。〕で示される。 More specifically, the monomer (a) having a polysiloxane group is represented by the general formula (1)

[Wherein R ⁴ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a phenyl group, a cyclohexyl group, a decyl group. And preferably a hydrogen atom or a methyl group. R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ in the formula are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms which may be the same or different from each other, such as a methyl group, an ethyl group, A propyl group, a butyl group, a pentyl group, a hexyl group, a phenyl group, a cyclohexyl group, and a decyl group may be mentioned. Preferably, for R ⁵ , R ⁶ , R ⁷ , and R ⁸ , a methyl group, and for a phenyl group and R ₆ , methyl Group, butyl group and phenyl group. N in the formula is an integer of 2 or more, preferably an integer of 10 or more, more preferably an integer of 30 or more. And / or general formula (2)

[In the formula, R ¹⁰ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a phenyl group, and a cyclohexyl group. Preferably a hydrogen atom or a methyl group. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ in the formula are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, which may be the same as or different from each other, such as a methyl group, an ethyl group, A propyl group, a butyl group, a pentyl group, a hexyl group, a phenyl group, and a cyclohexyl group are mentioned. Preferably, for R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ , a methyl group, for a phenyl group, and R ¹⁵ , a methyl group and a butyl group Group, a phenyl group. Moreover, p in a formula is an integer of 0-10, Preferably it is 3. Moreover, q in a formula is an integer greater than or equal to 2, Preferably it is an integer greater than or equal to 10, More preferably, it is an integer greater than or equal to 30. ] Is shown.

Although the monomer (a) having such a polysiloxane group can be prepared by a known method, a commercially available product can also be used. As an example of a commercially available product, Silaplane ^{(registered trademark)} FM- 0711 (number average molecular weight 1,000; manufactured by Chisso Corporation), Silaplane ^{(registered trademark)} FM-0721 (number average molecular weight 5,000; manufactured by Chisso Corporation), Silaplane ^{(registered trademark)} FM-0725 (number average molecular weight 10) 000; manufactured by Chisso Corporation), X-22-174DX (number average molecular weight 4,600; manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

  The monomer (a) having a polysiloxane group may be used alone or in combination of two or more.

  The monomer (a) having a polysiloxane group is used in an amount of 5 to 40% by weight, preferably 10 to 30% by weight, based on the total amount of monomers. When it is less than 5% by weight, the antifouling property of the coating composition is deteriorated, and when it exceeds 40% by weight, the crosslinking density per unit area of the coating composition is lowered, and the film hardness becomes insufficient.

  The monomer (b) having an alkoxysilyl group used in the present invention is not particularly limited as long as it has a dialkoxyalkyl group or a trialkoxysilyl group and a radically polymerizable double bond. Roxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, glycidyl (meth) acrylate and 3 , 4-epoxycyclohexylmethyl (meth) acrylate and γ-aminopropyltrimethoxysilane or γ-aminopropyltriethoxysilane molar ratio 1/1 reaction product, glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl Mole ratio 1/1 of (meth) acrylate and γ-mercaptopropyltrimethoxysilane or γ-mercaptopropyltriethoxysilane, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and γ-isocyanate Examples include a reactant having a molar ratio of natopropyltrimethoxysilane of 1/1. Among them, from the viewpoint of copolymerization, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane are preferable, and γ- Particularly preferred are methacryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane.

  These monomers (b) having an alkoxysilyl group may be used alone or in combination of two or more.

  The monomer (b) having these alkoxysilyl groups is used in the range of 5 to 55% by weight, preferably 10 to 50% by weight, based on the total amount of monomers. If it is less than 5% by weight, the crosslink density of the coating composition cannot be increased, so that the film hardness and solvent resistance of the coating composition are lowered. On the other hand, if it exceeds 55% by weight, the crosslink density is too high and the film becomes brittle or the workability may be lowered.

The monomer (c) having a hydroxyl group used in the present invention is not particularly limited as long as it has a hydroxyl group and a radical polymerizable double bond, and examples thereof include p-hydroxystyrene, p-hydroxymethylstyrene, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, di-2-hydroxy In addition to ethyl fumarate, polyethylene glycol or polypropylene glycol mono (meth) acrylate, or their ε-caprolactone adduct, Plaxel ^{(registered trademark)} FM or FA series (manufactured by Daicel Chemical Industries, Ltd .; caprolactone adduct monomer) Α, β-ethylenically unsaturated carboxylic acids such as α, β-ethylenically unsaturated carboxylic acids, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid adducts of acid and ε- caprolactone, or of alpha, beta-ethylenically unsaturated carboxylic acid and butyl glycidyl ether, phenyl glycidyl ether, Cardura ^(R) E of such epoxy compound (shell chemical Co., Ltd.) Examples include adducts. Among them, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) mainly from the viewpoint of hardening by adjusting the Tg of the polymer. Acrylate and 4-hydroxybutyl (meth) acrylate are preferably used.

  These monomers (c) having a hydroxyl group may be used alone or in combination of two or more.

The monomer (c) having a hydroxyl group is used in an amount of 3 to 30% by weight, preferably 5 to 15% by weight, based on the total amount of monomers. Crosslink density and less than 3 by weight% of monomer (c) having a hydroxyl group is not increased, film hardness and solvent resistance of the coating composition is lowered. On the other hand, if it exceeds 30% by weight, the crosslink density is too high and the coating film becomes brittle or the workability is lowered.

The monomer (d) having a functional group that does not react other than radical polymerization with the monomers (a) to (c) in the present invention is the monomer (a) to (a) at the reaction temperature and reaction conditions when radical polymerization is performed. Those that do not react with (c) other than radical polymerization are selected, for example, styrenes such as styrene, p-methylstyrene, p-chloromethylstyrene, vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate Stearyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylates having a hydrocarbon group such as benzyl (meth) acrylate, these hydrogen atoms are fluorine, chlorine , Vinyl esters such as (meth) acrylates substituted with bromine atoms, vinyl acetate, vinyl benzoate, Veova ^{(registered trademark)} (manufactured by Shell Chemical Co .; vinyl ester of branched monocarboxylic acid), acrylonitrile, methacrylo Acrylonitriles such as nitriles, vinyl ethers such as ethyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, cyclohexyl vinyl ether, vinyl ethers in which these hydrogen atoms are substituted with fluorine, chlorine, bromine atoms, etc., (meth) a Acrylamides such as chloramide, dimethyl (meth) acrylamide, diacetone acrylamide, acrylamides in which these hydrogen atoms are substituted with fluorine, chlorine, bromine atoms, etc., glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) Epoxy group-containing vinyl compounds such as acrylate and 3,4-epoxyvinylcyclohexane, olefins such as ethylene and propylene, vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, tetrafluoroethylene, chlorotrifluoroethylene, etc. Halogenated olefins, other maleimides, vinyl sulfones and the like can be mentioned, and a plurality of these are used in appropriate combination, and (meth) acrylates are preferably used mainly from the viewpoint of copolymerization.

  On the other hand, examples of the monomer (d) that are not preferable include vinylpyridine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and N, N-dimethyl (meth) acrylamide. , 4- (N, N-dimethylamino) styrene, N- {2- (meth) acryloyloxyethyl} piperidine and other basic nitrogen-containing vinyl compounds, (meth) acrylic acid, angelic acid, crotonic acid, maleic acid Acidic vinyl compounds such as 4-vinylbenzoic acid, p-vinylbenzenesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, and mono {2- (meth) acryloyloxyethyl} acid phosphate. Since the above basic nitrogen-containing vinyl compounds and acidic vinyl compounds serve as a catalyst for dissociating and condensing the alkoxysilyl group of the monomer (b) having an alkoxysilyl group, when the polymerization or the resin is stored for a long time May thicken or gel.

  The monomer (d) is preferably used in combination so that the final silicone acrylic resin has a Tg of 40 ° C. or higher. When the Tg of the final silicone acrylic resin is less than 40 ° C., the film hardness of the coating composition may decrease. The monomer (d) is used in the range of 0 to 85% by weight based on the total amount of monomers. If it exceeds 85% by weight, the amount of other monomers (a) to (c) introduced will be reduced.

Examples of the solvent used in the polymerization include aromatic hydrocarbons such as toluene, xylene, Solvesso ^{(registered trademark)} 100 (manufactured by Esso Petroleum Co., Ltd.), fats such as n-hexane, cyclohexane, octane, mineral spirit, and kerosene. , Alicyclic hydrocarbons, esters such as ethyl acetate, n-butyl acetate, i-butyl acetate, butyl cellosolve acetate, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, etc. Examples include alcohols, glycols such as ethylene glycol, propylene glycol, ethyl cellosolve, and butyl cellosolve, or glycol ethers. These may be used alone or in combination of two or more.

  The polymerization can be carried out by a conventional method using various known and conventional radical polymerization initiators such as azo compounds or peroxides.

  The polymerization time is not particularly limited, but usually a range of 1 to 48 hours is selected industrially. Moreover, superposition | polymerization temperature is 30-150 degreeC normally, Preferably it is 60-120 degreeC.

  In the polymerization, if a side reaction does not occur as required, a known and commonly used chain transfer agent such as butyl mercaptan, dodecyl mercaptan, α-methylstyrene dimer or the like can be added.

  The silicone acrylic resin in the present invention has a weight average molecular weight in the range of 5,000 to 1,000,000, preferably 10,000 to 500,000 by GPC (gel permeation chromatography) in terms of polystyrene. . If it is less than 5,000, the film formability, the film hardness of the coating, and the solvent resistance are lowered, and if it exceeds 1,000,000, there is a risk of gelation during polymerization, which is not preferred. The silicone acrylic resin preferably has an OH value of 50 to 200, preferably 80 to 120. When the OH value is less than 50, the crosslinking density does not increase, and the film hardness and solvent resistance of the coating composition are lowered. When it is larger than 200, the crosslinking density is excessively increased, the coating becomes brittle or the workability is lowered.

（式中のＲ_１は水素、メチル基またはエチル基を表し、Ｒ_２はＯＨ、−Ｏ−Ｒ_３−ＯＨまたは

を表し、上記Ｒ_２中のＲ_３は炭素数１〜４のアルキレン基を示す。）。 (Compound having a fluorene skeleton)
The compound having a fluorene skeleton has a function of preventing a decrease in refractive index due to the use of a resin having a silicone skeleton and improving the refractive index. The epoxy group of this compound reacts with the hydroxyl group of the aforementioned silicone acrylic resin, or the hydroxyl group of this compound reacts with the alkoxy group of the aforementioned silicone acrylic resin or alkoxysilane compound, resulting in a fluorene group in the resin skeleton. It is thought to be pendant. Accordingly, the compound having a fluorene skeleton is basically a compound having at least a hydroxyl group or an epoxy group, and is preferably represented by the following chemical formula:

(In the formula, R ₁ represents hydrogen, a methyl group or an ethyl group, and R ₂ represents OH, —O—R ₃ —OH or

R _{3 in} R ₂ represents an alkylene group having 1 to 4 carbon atoms. ).

  Specific examples of the compound having a fluorene skeleton include bisphenol fluorene glycidyl ether, bisphenoxyethanol fluorenediglycidyl ether, bisphenol fluorene, biscresol fluorene, bisphenoxyethanol fluorene, and mixtures thereof. Both compounds having a fluorene skeleton are commercially available from Osaka Gas Chemical Co., Ltd.

  The compound having a fluorene skeleton is blended in the resin composition at 5 to 30% by weight, preferably 10 to 20% by weight. If it is less than 5% by weight, the refractive index is lowered, and interference fringes are likely to occur. When it exceeds 30% by weight, the film hardness and antifouling property of the coating composition deteriorate.

(Alkoxysilane compound)
The alkoxysilane compound used in the present invention acts as a curing agent that reacts with and cures the alkoxysilyl group present in the silicone acrylic resin. The alkoxysilane compound specifically means alkylalkoxysilane and its condensate.

  Specific examples of the alkylalkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, and butyltriethoxysilane. , Pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, nonyltrimethoxysilane, nonyltriethoxysilane Decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane, undecyltriethoxysilane, dodecyltrimethoxy Silane, dodecyltriethoxysilane, tridecyltrimethoxysilane, tridecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, pentadecyltrimethoxysilane, pentadecyltriethoxysilane, hexadecyltrimethoxysilane, hexa Decyltriethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, eicosyltrimethoxysilane, eicosyltriethoxysilane Such as alkyltrialkoxysilane, dimethyldimethoxysilane, octylmethyldimethoxysilane, octadecylmethyldimethoxysilane, etc. It can be cited an alkyl dialkoxy silane.

  The alkoxysilane compound is blended in the resin composition in an amount of 20 to 70% by weight, preferably 30 to 50% by weight. If it is less than 20% by weight, the hardness is not sufficient, and if it is more than 50% by weight, the coating film of the coating composition becomes brittle, and adhesion to the substrate, antifouling property and stability are deteriorated.

(Metal chelating agent)
In the thermosetting resin composition of the present invention, a chelating agent is added. By adding a chelating agent, it functions as a curing catalyst for the alkoxysilane compound and improves the coating film performance. As the chelating agent, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate and the like are preferably used.

  When a chelating agent is added, 5 to 15% by weight, more preferably 7 to 11% by weight, is added to the total resin composition of the present invention. When the addition amount of the chelating agent is less than 5% by weight, the film hardness is not sufficient. On the other hand, when the addition amount exceeds 15% by weight, the stability with time of the liquid deteriorates.

(Other ingredients)
The thermosetting resin composition of the present invention contains the above four components as essential components, but may contain various other components such as a reaction terminator and a solvent. Or, characteristics such as durability should not be reduced.

  The reaction terminator is added to increase storage stability, and specifically includes acetylacetone, ethyl acetoacetate, triethyl orthoacetate and the like. The amount of the reaction terminator to be added to the composition is 10 to 55% by weight, preferably 20 to 50% by weight, based on the solid content of the resin composition. If it exceeds 55% by weight, there are disadvantages such as liquid stability and film hardness reduction. If it is less than 10% by weight, the liquid stability cannot be increased.

  In the thermosetting resin composition of the present invention, a solvent can be used as necessary for the coating method and uniformity. The solvent can dissolve or uniformly disperse the above components, and specifically includes alcohols, ethers or acetates. Examples of alcohols include alkyl alcohols having 1 to 8 carbon atoms, specifically methanol, ethanol, propanol, butanol and the like. Examples of ethers include propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol propyl ether, and acetates include propylene glycol monomethyl ether acetate, butyl acetate, ethyl acetate, and the like. Is mentioned. The solvent may be a mixture of the above. Solvents include propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, isoprene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,6-hexanediol, 2-butyl-2 -Ethyl-1,3-propanediol.

  The amount of the solvent varies greatly depending on the coating form and the type of components used and is difficult to specify, but is, for example, 30 to 99% by weight, preferably 50 to 95% by weight of the total amount of the resin composition. Of course, it is possible to use a range outside these amounts.

(Thermosetting resin composition)
The thermosetting resin composition of the present invention can be formed by mixing the above components. The mixing method is not particularly limited, and the mixing is performed by mixing with a mixer used when mixing paint or the like. The composition in which the above components are mixed usually becomes a one-component curable type, but the component of the compound having a silicone acrylic resin and a fluorene skeleton, the component of the alkoxysilane compound and the metal chelating agent may be divided into a two-component type. it can. A curable mold that is easy to use can be used depending on the application.

(Application to the original version)
The thermosetting resin composition of the present invention is applied to the original plate by applying it as a protective film to the original plate (one having a predetermined pattern formed on a glass substrate). There are various coating methods such as spray coating, spin coating, dip coating, and roll coating, and any method may be used. A practical application method is spin coating. The film thickness after coating and drying is preferably 1 to 5 μm. The original plate may be either an emulsion mask or a chrome mask, but the protective film formed from the thermosetting resin composition of the present invention is highly suitable for a protective film of a chrome mask because it has high resistance to electrostatic breakdown. It is.

(Application to base materials)
The thermosetting resin composition of the present invention can be applied to a normal substrate other than the above-mentioned original plate to exhibit its performance. As the substrate, various plastic films, plastic plates, glass and the like can be used. Examples of plastic films include triacetyl cellulose (TAC) film, polyethylene phthalate (PET) film, diacetylene cellulose film, acetate petitrate cellulose film, polyethersulfone film, polyacrylic resin film, polyurethane resin film, polyester Examples include films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyetherketone films, (meth) acrylonitrile films, and the like. As the plastic plate, for example, a polyacrylic resin plate, a polycarbonate resin plate, a polyurethane resin plate, or the like can be used. Moreover, a silicon substrate can also be used as a base material.

  After applying the thermosetting resin composition of the present invention, it is usually cured at an elevated temperature. Curing is carried out at a temperature of 60 to 210 ° C., preferably 100 to 180 ° C., for 10 to 120 minutes, preferably 30 to 60 minutes. Curing is usually performed in an oven, but is not limited to this, and curing is performed by various apparatuses known to those skilled in the art.

  The invention is explained in more detail by means of examples. The present invention should not be construed as being limited to the examples.

Examples 1 and 2 and Comparative Examples 1 and 2
A paint for a protective film was formed by mixing the formulations shown in Table 1 below.

  The formed coating material for protective film was spin-coated on the substrate, and cured by heating at 150 ° C. for 30 minutes. About the obtained coating film, film hardness, contact angle, interference fringe unevenness, electrostatic breakdown characteristics, light transmittance, glass adhesion, acetone resistance, storage stability and scratch strength were tested by the methods described below. The results are shown in Table 2.

^＊１ 富士化成工業（株）製、アルコキシシリル基及びヒドロキシル基含有のアクリル系シリコーン樹脂。
^＊２ 大阪ガスケミカル（株）製、高屈折率材料。

（式中、R=（CH_２）_ｎで、ｎは１〜４の整数を示す。）
^＊３ コルコート（株）製、硬化剤、メチルポリシリケート。
^＊４ 東レ・ダウコーニング（株）製、硬化剤、ジメチルフェニルメトキシシロキサン。
^＊５ 川研ファインケミカル（株）製、アルキルアセトアセテートアルミニウムジイソプロピレート。
^＊６ 日本乳化剤（株）製、溶剤、プロピレングリコールモノメチルエーテルアセテート。
^＊７ 日本乳化剤（株）製、溶剤、ジエチレングリコールモノメチルエーテル。

^{* 1} An acrylic silicone resin containing alkoxysilyl groups and hydroxyl groups, manufactured by Fuji Chemical Industry Co., Ltd.
^{* 2} Osaka Gas Chemical Co., Ltd., high refractive index material.

(Wherein R = (CH ₂ ) _n , n represents an integer of 1 to 4)
^{* 3} Colcoat Co., Ltd., curing agent, methyl polysilicate.
^{* 4} Toray Dow Corning Co., Ltd., curing agent, dimethylphenylmethoxysiloxane.
^{* 5} Alkyl acetoacetate aluminum diisopropylate manufactured by Kawaken Fine Chemicals Co., Ltd.
^{* 6} Nippon Emulsifier Co., Ltd., solvent, propylene glycol monomethyl ether acetate.
^{* 7} Nippon Emulsifier Co., Ltd., solvent, diethylene glycol monomethyl ether.

Film hardness was measured based on JIS K 5400.

The contact angle of pure water was measured using a CA-XP type manufactured by Kyowa Interface Science Co., Ltd.

The interference fringe unevenness protective film glass substrate was visually observed with a sodium lamp.
◎… Radial and contoured patterns are not visible at all ○… Radial and contoured patterns are visible only at the corners of the substrate △… Radial and contoured patterns are slightly visible ×… Radial and contoured patterns Can see

Electrostatic breakdown characteristics ELECTROSTATIC DISCHARGE SIMULATOR (discharge test apparatus) was used to visually evaluate the film surface when the chrome pattern film surface was discharged at 10 kV.
○: No chrome pattern destruction.
X: Chrome pattern is broken.

UV transmittance MPC-3100 manufactured by Shimadzu Corporation was used to measure the transmittance of the thermosetting resin composition based on the transmittance of air.

The adhesion between the glass adhesion protective film agent and the glass was evaluated by a grid cellophane tape peeling test (cross-cut method).

Using a felt impregnated with acetone- resistant acetone , visually observing the surface after rubbing 100 times with a rubbing tester under a load of 500 g. did.

Storage stability The state of the coating film for protective film after 1 month storage at room temperature was visually observed.

Since Examples 1 and 2 of the present invention include a high refractive index material (a compound having a fluorene skeleton), interference fringe unevenness does not occur and other performances are excellent. On the other hand, in the examples of Comparative Examples 1 and 2, since the high refractive index material is not included, the electrostatic breakdown characteristics are poor, the interference fringe unevenness is generated, and the solvent resistance is also poor. In Comparative Example 1, since it is not an acrylic silicone resin but a normal acrylic resin, storage stability and other performances are also poor.

Claims (6)

A thermosetting resin composition comprising a silicone acrylic resin having an alkoxysilyl group and a hydroxyl group, a compound having a fluorene skeleton, an alkoxysilane compound and a metal chelating agent ,
In addition to the monomer (a) having a polysiloxane group, the monomer (b) having an alkoxysilyl group, the monomer (c) having a hydroxyl group, and the above-described monomer and radical polymerization. A resin formed by radical polymerization of a monomer (d) having a functional group that does not react; and
The compound having a fluorene skeleton is a compound having an epoxy group as a functional group.
Thermosetting resin composition . The compound having a fluorene skeleton has the formula:

(R ₁ in the formula represents hydrogen, methyl or ethyl, R ₂ is

R ₃ in R ₂ represents an alkylene group having 1 to 4 carbon atoms. )
The thermosetting resin composition according to claim 1, which is a compound represented by the formula:   The thermosetting resin composition according to claim 1, wherein the solid content of the silicone acrylic resin has 5 to 55 wt% of the alkoxysilyl group and 3 to 30 wt% of the hydroxyl group.   The thermosetting resin composition according to claim 1, further comprising a monovalent or divalent alcohol solvent.   A protective film coating material obtained by coating an original plate with the thermosetting resin composition according to claim 1. The protective film coating material of Claim 5 whose film thickness of the layer which the said thermoplastic resin composition coat | covered is 1-5 micrometers.