TWI470349B - Photosensitive composition, cured film obtained from the composition, and display device having the cured film - Google Patents

Description

Photosensitive composition, cured film obtained from the composition, and display element having the cured film

The present invention relates to a photosensitive composition for producing a display element such as a liquid crystal display element or an EL display element, a cured film such as a transparent film produced from the composition, and a display element having the cured film.

The patterned transparent film is used in a large number of liquid crystal display elements such as a spacer, an insulating film, and a protective film. Heretofore, various photosensitive compositions have been used for display elements such as liquid crystal display elements and EL display elements (for example, refer to Japanese Patent Laid-Open Publication No. 2004-287232). The patterned transparent film can be formed by a negative photosensitive material which is a photocurable polymer composition coated on a substrate, and a pattern pair coating The film is irradiated with light, and the film irradiated with the light is washed to remove the unhardened portion which is not irradiated with light, thereby forming a patterned film; the positive photosensitive material is a film which is irradiated with light. Development is carried out in an alkaline developing solution to remove a portion which is solubilized by light irradiation, thereby forming a patterned film. A photocurable polymer composition and a photosensitive composition for forming a patterned transparent film are also proposed (for example, refer to Japanese Laid-Open Patent Publication No. 2001-261761).

On the other hand, various types of patterning by the inkjet method have been proposed in recent years (for example, refer to Japanese Laid-Open Patent Publication No. Hei 10-12377). Further, in the patterning by the inkjet method, in order to perform precise inkjet patterning, a wall (barrier material) between the pixels is formed before the application by the inkjet method.

The barrier material can be formed into a patterned film by a known method using the photocurable polymer composition and the photosensitive composition as described above. In the barrier material, the characteristics of the liquid substance which is not attached to the nozzle head of the ink jet apparatus, that is, the ink repellency, are required (for example, refer to Japanese Patent Laid-Open No. Hei 11-281815 and Japanese Patent Laid-Open No. 2004-- Bulletin No. 149699). Further, in a semiconductor manufacturing process or an LCD manufacturing process or the like, a UV ozone ashing treatment step is performed to improve the coating property or wettability of the ink to be applied to the opening of the liquid material. At this time, since the surface of the barrier material is also treated, it is required to reduce the liquid repellency of the barrier material, but it is resistant to such a treatment, and the barrier material which can reduce the surface repellency can be suppressed.

As described above, the use of the photocurable polymer composition and the photosensitive composition is not only a material constituting a layer in the display element but also a film which functions as an auxiliary function in the production of the display element. With the expansion of such use, the photocurable polymer composition and the photosensitive composition are required to have more performance than before.

An object of the present invention is to provide a positive photosensitive composition which can form a cured film excellent in liquid repellency and UV ozone ashing resistance. Further, an object of the present invention is to provide a cured film of such a positive photosensitive composition and a display element having the film.

The present inventors have conducted intensive studies to solve the above problems, and as a result, it has been found that, by using a polymer obtained by copolymerizing a monomer containing a polyfunctional siloxane in a photosensitive composition, it is possible to obtain liquid repellency and resistance. The cured film having excellent UV ozone ashing properties, thereby completing the present invention as shown below.

[1] A photosensitive composition comprising: a polymer (A) comprising a decane structure and a 1,2-quinonediazide compound (B), wherein the polymer (A) comprising a decane structure is included A radical polymer of a monomer of the following formula: a oxoxane compound represented by the formula (1), an alkali-soluble radical polymerizable monomer having an alkali solubility and a radical polymerizability imparting alkali solubility to the polymer,

In the formula (1), R ¹ to R ⁴ each independently represent hydrogen, or any hydrogen which may be substituted by fluorine and which is not continuous, may be substituted with an oxygen group having an alkyl group having 1 to 30 carbon atoms. A ¹ and A ² each represent a radical polymerizable functional group, and n represents an integer of 1 to 1,000.

[2] The photosensitive composition according to [1], wherein the alkali-soluble radically polymerizable monomer comprises a radical polymerization selected from a radically polymerizable monomer having an unsaturated carboxylic acid and having an unsaturated carboxylic anhydride. One or more of the group consisting of a monomer and a radical polymerizable monomer having a phenolic hydroxyl group.

[3] The photosensitive composition according to the above [1], wherein the alkali-soluble radical polymerizable monomer comprises a radical polymer monomer represented by the formula (2),

In the formula (2), R ⁵ to R ⁷ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may be substituted by fluorine, and R ⁸ to R ¹² respectively represent hydrogen, halogen, -CN, - CF ₃ , -OCF ₃ , a hydroxyl group, an arbitrary methylene group may be substituted by -COO-, -OCO-, -CO-, and any hydrogen may be substituted by halogen with a carbon number of 1 to 5, or any The hydrogen may also be substituted with a halogen to have an alkoxy group having 1 to 5 carbon atoms. Wherein at least one of R ⁸ to R ¹² is a hydroxyl group.

[4] The photosensitive composition according to any one of [1], wherein the polymer (A) comprising a siloxane structure further comprises a siloxane compound represented by the formula (1). And a radical polymer of a monomer other than the radically polymerizable monomer other than the alkali-soluble radical polymerizable monomer.

[5] The photosensitive composition according to [4], wherein the other radical polymerizable monomer comprises a siloxane compound represented by the formula (3),

In the formula (3), R ¹³ to R ¹⁷ each independently represent an arbitrary alkyl group which may be substituted by fluorine, and any methylene group may be substituted with an oxygen group having an alkyl group having 1 to 30 carbon atoms or a number of turns 1~. 500 tris(alkyl/alkoxy)decyloxy, A ³ represents a radical polymerizable functional group, and n represents an integer of 0 to 1,000.

[6] The photosensitive composition according to [5], wherein the other radical polymerizable monomer is a oxoxane compound represented by the formula (3) wherein n is 0.

[7] The photosensitive composition according to [6], wherein R ¹³ to R ^{15 of the} formula (3) are each represented by the following formula (5),

In the formula (5), R ²¹ to R ²³ each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms (wherein at least one of R ²¹ to R ²³ at the terminal) Is the alkyl group or the alkoxy group), and m represents an integer of from 1 to 500.

[8] The photosensitive composition according to any one of [4], wherein the other radical polymerizable monomer contains a (meth)acrylic acid derivative.

[9] The photosensitive composition according to any one of [1] to [8] further comprising an alkali-soluble polymer (C) represented by the formula (1) A radical polymer of a monomer other than a oxoxane compound, and having an alkali solubility.

[10] The photosensitive composition according to [9], wherein the alkali-soluble polymer (C) is a radical polymerization comprising a radically polymerizable monomer having an unsaturated carboxylic acid and having an unsaturated carboxylic anhydride. A radical polymer of one or more monomers of a group consisting of a monomer and a radical polymerizable monomer having a phenolic hydroxyl group.

[11] The photosensitive composition according to any one of [1] to [10] further comprising a solvent.

[12] A cured film obtained by calcining a film of the photosensitive composition according to any one of [1] to [11].

[13] A display element having the cured film according to [12].

The photosensitive composition of the present invention is an alkali-soluble radical polymer containing a monomer of a oxoxane compound represented by the formula (1), and thus can be formed in a UV ozone ash by being applied to a positive type resist. A cured film excellent in liquid repellency in any case after the treatment.

1. The photosensitive composition of the present invention

The photosensitive composition of the present invention comprises a polymer (A) comprising a decane structure and a 1,2-quinonediazide compound (B). The polymer (A) having a siloxane structure may be one type or two or more types, and the 1,2-quinonediazide compound (B) may be one type or two or more types. The photosensitive composition can be obtained by mixing a polymer (A) containing a decane structure and a 1,2-quinonediazide compound (B).

1-1. Polymer containing a siloxane structure (A)

The polymer (A) comprising a oxoxane structure is a radical polymer comprising a monomer of a compound having a linear oxime structure of 2 or more and two radically polymerizable functional groups (1) The alkoxysilane compound (hereinafter also referred to as "radical polymerizable monomer (a-1)"), and the alkali-soluble radical polymerization having alkali solubility and radical polymerizability imparting alkali solubility to the polymer (A) A monomer (hereinafter also referred to as "radical polymerizable monomer (a-2)").

The polymer (A) having a siloxane structure has an alkali solubility imparted by the radical polymerizable monomer (a-2). The alkali solubility of the polymer (A) containing a oxoxane structure means a thickness of 0.01 by spin coating a solution of the polymer (A) containing a decane structure and heating at 100 ° C for 2 minutes. The film of μm to 100 μm was immersed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at about 25 ° C for 5 minutes, and then washed with pure water, the film remained.

The radically polymerizable monomer (a-1) and the radically polymerizable monomer (a-2) may be used alone or in combination of two or more. The content of the radical polymerizable monomer (a-1) in all the monomers constituting the polymer (A) containing a decane structure is preferably 0.1 wt% from the viewpoint of exhibiting the liquid repellency of the cured film. From 100% by weight to 50% by weight, more preferably from 0.5% by weight to 30% by weight, still more preferably from 1% by weight to 20% by weight. Further, the content of the radical polymerizable monomer (a-2) in all the monomers constituting the polymer (A) containing a siloxane chain structure is considered from the viewpoint of exhibiting sufficient developability in the production of the cured film. It is preferably from 0.1% by weight to 50% by weight, more preferably from 0.5% by weight to 30% by weight, still more preferably from 1% by weight to 20% by weight.

1-1-1. Radical polymerizable monomer (a-1)

The radically polymerizable monomer (a-1) is a compound having a linear oxime structure having a number of turns of 2 or more and two radical polymerizable functional groups, and is represented by the formula (1).

In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms which may be substituted by fluorine and which is not continuous, and which may be substituted with oxygen. Such an alkyl group includes, for example, a fluorinated alkyl group or an alkoxy group having 1 to 20 carbon atoms.

In the formula (1), A ¹ and A ² each represent a radical polymerizable functional group. A ¹ and A ² may be the same or different. The radical polymerizable functional group can be used for a radical having a radically polymerizable structure in the radically polymerizable monomer (a-1). Examples of such a radical polymerizable functional group include a known radical polymerizable functional group, and examples thereof include a vinyl group, a 1,2-vinylene group, a vinylidene group, and a methyl group. An acrylonitrile group, a styryl group, and the like.

The radical polymerizable functional group may further have a substituent within a range in which radical polymerizability is obtained. Examples of such a substituent include an alkylene group having 2 to 10 carbon atoms; an alkoxy group such as a methoxy group or an ethoxy group; and an isopropyl group and a different Branched alkyl such as butyl.

In the formula (1), n represents an integer of 1 to 1,000. From the viewpoint of obtaining good alkali developability, n is preferably from 2 to 500, more preferably from 5 to 300, still more preferably from 10 to 150.

The radically polymerizable monomer (a-1) is, for example, a naphthenic monomer having a methacrylinyl group at both terminals represented by the formula (1-1). Since the initial transparency is high, and there is almost no deterioration in transparency due to calcination at a high temperature, and the solubility in an alkaline aqueous solution during development is high (that is, high developability), a pattern-like transparent film is easily obtained. Further, in view of solvent resistance, high water resistance, acid resistance, alkali resistance, and heat resistance, and a photosensitive composition having a high adhesion to a substrate or a cured film, it is preferably a radical polymerizable single. A siloxane-based monomer is used in the body (a-1). Further, in the formula (1-1), n represents an integer of 1 to 1,000.

Commercially available products are also available as the radical polymerizable monomer (a-1). The compound represented by the formula (1-1) is, for example, Silaplane FM7711 (trade name, manufactured by CHISSO CORPORATION).

1-1-2. Radical polymerizable monomer (a-2)

The radical polymerizable monomer (a-2) has alkali solubility and radical polymerizability which impart alkali solubility to the polymer (A). Radical polymerizable monomer (a-2) The alkali solubility is a salt which forms a water-soluble salt by a base even in the form of radical polymerization of the radical polymerizable monomer (a-2). Such alkali solubility is imparted by a structure having a site which forms a water-soluble salt by a base independently of a radical polymerization site, such as a carboxyl group or a phenolic hydroxyl group. Further, the radical polymerizable property of the radical polymerizable monomer (a-2) means a property of radical polymerization with another monomer including the radical polymerizable monomer (a-1). Such radical polymerizability is imparted by the above-mentioned radical polymerizable functional group. Therefore, the radical polymerizable monomer (a-2) includes the moiety soluble in the base and the radical polymerizable functional group.

Examples of the radically polymerizable monomer (a-2) include a radical polymerizable monomer containing an unsaturated carboxylic acid, a radical polymerizable monomer containing an unsaturated carboxylic acid anhydride, and a free phenolic hydroxyl group. Base polymerizable monomer. The radically polymerizable monomer containing an unsaturated carboxylic acid is, for example, (meth)acrylic acid, and the radically polymerizable monomer containing an unsaturated carboxylic acid anhydride is, for example, maleic anhydride, and a radical polymerizable single containing a phenolic hydroxyl group. Examples of the compound include a vinyl ketone having a phenolic hydroxyl group and a styrene derivative having a phenolic hydroxyl group.

The vinyl ketone having a phenolic hydroxyl group may, for example, be a compound represented by the formula (2).

In the formula (2), R ⁵ to R ⁷ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may be substituted by fluorine, and R ⁸ to R ¹² respectively represent hydrogen, halogen, -CN, - CF ₃ , -OCF ₃ , a hydroxyl group, an arbitrary methylene group may be substituted by -COO-, -OCO-, -CO-, and any hydrogen may be substituted by halogen with a carbon number of 1 to 5, or any The hydrogen may also be substituted with a halogen to have an alkoxy group having 1 to 5 carbon atoms. Wherein at least one of R ⁸ to R ¹² is a hydroxyl group.

From the viewpoint of improving alkali solubility, it is preferred that R ⁵ to R ⁷ and R ⁸ to R ¹² other than the hydroxyl group are hydrogen. The compound represented by the formula (2) is, for example, 4-hydroxyphenyl vinyl ketone.

The vinyl ketone having a phenolic hydroxyl group can be obtained by a known method, or can be obtained in the form of a commercially available product. For example, 4-hydroxyphenyl vinyl ketone can be obtained by the following method as described in Japanese Patent Laid-Open Publication No. 2004-189715: dichlorochloride of 2-chloroethyl-4-methoxyphenyl ketone Aluminium chloride is added to the methane solution, and the resulting mixture is refluxed and cooled. The organic phase is extracted with ethyl acetate. The organic phase is extracted with aqueous NaOH, acidified with hydrochloric acid, and then ethyl acetate. Perform extraction.

The styrene derivative having a phenolic hydroxyl group has a polymerizable double bond of styrene in addition to a phenolic hydroxyl group. Examples of the styrene derivative having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene.

1-1-3. Other radical polymerizable monomers (a-3)

From the viewpoint of increasing or increasing the properties of the polymer (A) containing a decane structure, it is preferred that the polymer (A) comprising a siloxane structure further contains a radical polymerizable monomer (a). -1) and free radicals A radical polymer of a monomer other than the polymerizable monomer (a-2) (hereinafter also referred to as "radical polymerizable monomer (a-3)"). The radically polymerizable monomer (a-3) may be one type or two or more types. A polymer comprising a siloxane structure (A) is considered from the viewpoint of improving the properties of the polymer (A) containing a siloxane structure or imparting further properties to the polymer (A) containing a siloxane structure. The content of the radical polymerizable monomer (a-3) in all the monomers is preferably from 50.0% by weight to 99.9% by weight, more preferably from 70.0% by weight to 99.5% by weight, still more preferably 80.0% by weight. %~99.0wt%.

Examples of the radically polymerizable monomer (a-3) include a decyl alkane compound represented by the formula (3), a radical polymerizable monomer containing an epoxy group, a (meth)acrylic acid derivative, and an N-substituted Malay. A quinone imine and a radical polymerizable monomer containing a dicyclopentyl group.

In the formula (3), R ¹³ to R ¹⁷ each independently represent an alkyl group in which any hydrogen may be substituted by fluorine and an arbitrary methylene group may be substituted by oxygen, an alkyl group having 1 to 30 carbon atoms, or an alkyl group. The number 1 to 20 is 1 to 500 tris (alkyl/alkoxy) nonyloxy group, A ³ is a radical polymerizable functional group, and n is an integer of 0 to 1,000. Among them, it is preferred that when n is 0, R ¹³ to R ¹⁵ are each a group represented by the formula (5). Further, the radical polymerizable functional group A ³ has the same meaning as the radical polymerizable functional group in the above formula (1). Further, "tris(alkyl/alkoxy)" means three groups including one or both of an alkyl group and an alkoxy group.

In the formula (5), R ²¹ to R ²³ each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms (wherein at least one of R ²¹ to R ²³ at the terminal is The alkyl group or the alkoxy group). m represents an integer from 1 to 500.

The alkane compound represented by the formula (3) is, for example, α-butyl-ω-(3-methylpropenyloxypropyl)polydimethyloxane represented by the formula (3-1). Product name: FM0711, manufactured by CHISSO CORPORATION). It is preferable from the viewpoint that it is free from the enthalpy contained therein to improve the surface liquid repellency.

Further, a oxoxane compound represented by the formula (3) and having n is 0, for example 3-methylacryloxypropyltrimethoxydecane (trade name: S710, manufactured by CHISSO CORPORATION), 3-methacryloxypropyltris(trimethyldecyloxy)decane (trade name) : TM0701T, manufactured by CHISSO CORPORATION), and 3-methacryloxypropylmethyldimethoxydecane (trade name: KBM-502, manufactured by Shin-Etsu Chemical Co., Ltd.). Among them, 3-methylpropenyloxypropyltrimethoxydecane is preferred from the viewpoint of improving the solubility in an alkaline developer.

Examples of the epoxy group-containing radical polymerizable monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate. And 3-ethyl-3-(meth)acryloxymethyl propylene oxide. These compounds are preferable from the viewpoint of easy availability and improvement in solvent resistance, water resistance, acid resistance, alkali resistance, heat resistance and transparency of the resulting patterned transparent film.

The (meth)acrylic acid derivative may be a derivative having a polymerizable double bond of (meth)acrylic acid. Examples of the (meth)acrylic acid derivative include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate. An alkyl methacrylate such as butyl methacrylate, hexyl methacrylate or ethylhexyl methacrylate; a methyl group having an aromatic ring such as benzyl methacrylate or phenoxyethyl methacrylate; Alkyl acrylate; hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, hydroxyamyl methacrylate, A An alkyl methacrylate having a hydroxyl group such as hydroxyhexyl acrylate; a dialkylaminoalkyl methacrylate such as dimethylaminoethyl methacrylate An ester; and an aryl methacrylate such as phenyl methacrylate.

Examples of the N-substituted maleimide include N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-(4-ethylmercaptophenyl)maleimide, N-(2,6-diethylphenyl) Maleic imine, N-(4-dimethylamino-3,5-dinitrophenyl)maleimide, N-(1-anilinophthyl-4)maleimide, N-[4-(2-benzoxazolyl)phenyl]maleimide, and N-(9-acridinyl)maleimide.

Examples of the radical polymerizable monomer containing a dicyclopentyl group include dicyclopentyl acrylate and dicyclopentyl methacrylate.

From the viewpoint of improving the heat resistance of the cured film formed of the photosensitive composition, it is preferred that the radical polymerizable monomer (a-3) contains an N-substituted maleimide and a free radical containing a dicyclopentyl group. One or both of the base polymerizable monomers.

The monomer of the polymer (A) having a siloxane structure is preferably selected from the group consisting of hydroxyethyl (meth) acrylate from the viewpoint of improving the alkali solubility of the polymer (A) containing a decane structure. One or more groups of the (meth)acrylic acid derivative and the styrene derivative having a phenolic hydroxyl group are contained in the monomer.

The polymer (A) containing a decane structure can be obtained by adding a radical polymerizable monomer (a-1) and a radical polymerizable monomer (a-2), and further adding as needed The base polymerizable monomer (a-3) is subjected to radical polymerization of the compounds. The radical polymerization can be carried out by a known method.

The polymerization method of the polymer (A) containing a decane structure is not particularly limited, but is preferably a radical polymerization in a solution using a solvent. The polymerization temperature is not particularly limited as long as it is a radical which sufficiently generates a radical by the polymerization initiator to be used, and is usually in the range of 50 ° C to 150 ° C. The polymerization time is also not particularly limited and is usually in the range of 1 hour to 24 hours. Moreover, the polymerization can be carried out under any pressure of pressure, reduced pressure or atmospheric pressure.

The solvent used in the radical polymerization is preferably a solvent which can dissolve the radical polymerizable monomer and the product to be used. The solvent may be one type or two or more types. Examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, acetone, 2-butanone, ethyl acetate, propyl acetate, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, and cyclohexanone. Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, methyl 3-methoxypropionate, 3-ethyl Ethyl oxypropionate and N,N-dimethylformamide.

Examples of the polymerization initiator to be used in the radical polymerization include a compound which generates a radical by heat, an azo initiator such as azobisisobutyronitrile, and a peroxide such as benzamidine peroxide. Starting agent. The amount of the polymerization initiator to be used is preferably from 1 part by weight to 30 parts by weight, more preferably from 5 parts by weight to 25 parts by weight, per 100 parts by weight of the total amount of the monomers to be used as the raw material.

Further, in the radical polymerization, a chain transfer agent such as thioglycolic acid may be added in order to adjust the molecular weight. The amount of the chain transfer agent to be added is preferably 0.001 part by weight to 0.05 part by weight, more preferably 0.005 part by weight to 0.03 part by weight, per 100 parts by weight of the total amount of the monomer to be used as the raw material.

Suitable for the development time from the exposure portion to the alkaline developer until the dissolution When the surface of the film is hard to be roughened at the time of development, it is preferred that the polymer (A) having a siloxane structure has a weight average molecular weight of 1,000 to 100,000. Further, the weight average molecular weight is more preferably from 1,500 to 50,000, and still more preferably from 2,000 to 20,000, from the viewpoint that the amount of the self-developing residue becomes extremely small.

The weight average molecular weight can be determined by GPC analysis using polystyrene as a standard, and for example, polystyrene having a molecular weight of 500 to 150,000 (for example, PL2010-0102 (S-M2-10) standard manufactured by Polymer Laboratories) can be used. As the column for the measurement, Shodex PLgel MIXED-D (manufactured by Polymer Laboratories) can be used, and the mobile phase at the time of the measurement can be THF. The weight average molecular weight can be determined under such conditions.

Further, the monomer of the polymer (A) containing a decane structure can be confirmed by a specific structure containing a ruthenium atom in the polymer (A) containing a siloxane structure and a radical polymerizable functional group. It is confirmed by a known analysis method of the structure, for example, by detecting the peak of Si-CH _{3 which} detects ¹ H-NMR and detecting the peak of ethylene or propylene.

1-2.1,2-醌diazide compound (B)

The 1,2-quinonediazide compound (B) can be used, for example, as a compound used as a photosensitizer in the field of resists. Examples of the 1,2-quinonediazide compound (B) include a hydroxybenzophenone compound and 1,2-benzoquinonediazide-4-sulfonic acid or 1,2-benzoquinonediazide-5-. Ester of sulfonic acid, hydroxybenzophenone compound and 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid ester, phenol An ester of a compound with 1,2-benzoquinonediazide-4-sulfonic acid or 1,2-benzoquinonediazide-5-sulfonic acid, a phenolic compound and 1,2-naphthoquinonediazide-4-sulfonate An acid or an ester of 1,2-naphthoquinonediazide-5-sulfonic acid, a compound in which a hydroxyl group of a phenol compound is substituted with an amine group, and 1,2-benzoquinonediazide-4-sulfonic acid or 1,2- a sulfonamide of phenylhydrazine diazide-5-sulfonic acid, a compound in which a hydroxyl group of a phenol compound is substituted with an amine group, and a 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinone Sulfonamide of nitrogen-5-sulfonic acid.

Examples of the hydroxybenzophenone compound include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, and 2,2',4,4'-tetrahydroxybenzophenone. Ketone, 2,3,3',4-tetrahydroxybenzophenone, and 2,3,4,4'-tetrahydroxybenzophenone.

Examples of the phenol compound include bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)B. Alkane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-tris(2,5-dimethyl 4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene Bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1,1'-spirobifluorene -5,6,7,5',6',7'-hexanol, and 2,2,4-trimethyl-7,2',4'-trihydroxyflavone.

From the viewpoint of improving the transparency of the photosensitive composition, it is preferred that the 1,2-quinonediazide compound (B) is selected from the group consisting of 2,3,4-trihydroxybenzophenone and 1,2-naphthalene. An ester of quinonezide-4-sulfonic acid, an ester of 2,3,4-trihydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonic acid, 2,3,4,4' - ester of tetrahydroxybenzophenone with 1,2-naphthoquinonediazide-4-sulfonic acid, 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinonediazide -5-sulfonic acid ester, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol with 1,2 -naphthoquinone diazide-4-sulfonic acid Ester, and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinone One or more groups consisting of esters of nitrogen-5-sulfonic acid.

1-3. Other ingredients

The photosensitive composition may further contain other components other than the above-described polymer (A) having a oxoxane structure and the 1,2-quinonediazide compound (B) within a range in which the effects of the present invention are sufficiently obtained. Examples of such other components include an alkali-soluble polymer (C), a solvent, an additive, and a polycarboxylic acid anhydride.

1-3-1. Alkali soluble polymer (C)

A cured film obtained by further improving the alkali solubility of the photosensitive composition to easily obtain a patterned transparent film, and improving solvent resistance, high water resistance, high acid resistance, high alkali resistance, and high heat resistance From the viewpoint of characteristics, it is preferred that the photosensitive composition further contains an alkali-soluble polymer (C). The alkali-soluble polymer (C) may be one type or two or more types. Further, the "alkali-soluble" in the alkali-soluble polymer (C) means a film having a thickness of 0.01 μm to 100 μm formed by spin-coating a solution of the alkali-soluble polymer (C) and heating at 100 ° C for 2 minutes. After immersing in an aqueous solution of 2.38 wt% of tetramethylammonium hydroxide at about 25 ° C for 5 minutes, for example, after washing with pure water, no film remains.

A radical polymer which is a radically polymerizable monomer (a-2), or a free radical in a manner that the obtained polymer has alkali solubility can be used in the alkali-soluble polymer (C) Two or more kinds of radicals contained in the base polymerizable monomer (a-2) and the radical polymerizable monomer (a-3) The conjugated monomer is formed by radical polymerization. Such a radical polymerizable monomer can be used for an alkali-soluble polymer in consideration of the amount of the polymer (A) having a decane structure in the photosensitive composition of the present invention to obtain a desired function. C).

Among the monomers of the alkali-soluble polymer (C), a radical polymerizable monomer (a-2) can be used as the radical polymerizable monomer having a phenolic hydroxyl group. From the viewpoint of improving the alkali solubility of the photosensitive composition, it is preferred that the monomer of the alkali-soluble polymer (C) comprises a solvent selected from the group consisting of (meth)acrylic acid, maleic anhydride, hydroxystyrene, and 4-hydroxyphenyl group. One or more groups of vinyl ketones.

It is preferred that the weight-average molecular weight of the alkali-soluble polymer (C) and the oxymethane are contained from the viewpoint that the exposure portion is in the alkaline developing solution until the development time of the dissolution is appropriate, and the surface of the film is hard to be roughened at the time of development. The polymer (A) of the structure is similarly 1,000 to 100,000; further, from the viewpoint that the amount of the self-developing residue becomes extremely small, it is more preferably 1,500 to 50,000, still more preferably 2,000 to 20,000. The weight average molecular weight of the alkali-soluble polymer (C) can be determined, for example, by GPC analysis under the same conditions as the polymer (A) containing a decane structure.

The alkali-soluble polymer (C) can be obtained, for example, by the same polymerization method as the polymer (A) containing a decane structure. Further, the monomer of the alkali-soluble polymer (C) can be estimated, for example, by measuring the gas generated by thermal decomposition by GC-MS when the alkali-soluble polymer (C) is thermally decomposed.

1-3-2. Solvent

The photosensitive composition preferably further contains a solvent. The solvent is preferably a solvent which can dissolve the polymer (A), the 1,2-quinonediazide compound (B), and the alkali-soluble polymer (C) which are formulated in the photosensitive composition. . Further, the solvent is preferably a solvent having a boiling point of from 100 ° C to 300 ° C. The solvent may be one type or two or more types.

Examples of the solvent having a boiling point of 100 ° C to 300 ° C include butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, and the like. Ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3-methoxy Methyl propyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropane Ethyl acetate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxypropionic acid Methyl ester, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropanoate, ethyl 2-oxy-2-methylpropanoate, 2-methoxy-2-methyl Methyl propyl propionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, 2- Methyl acetobutanoate, ethyl 2-oxobutanoate, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4- Glycol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol single Butyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, two Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, toluene, xylene, γ-butyrolactone, and N,N-dimethylacetamide.

From the viewpoint of improving coating uniformity when forming a film of the photosensitive composition, it is preferred that the solvent be selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methyl Methyl oxypropionate, ethyl 3-ethoxypropionate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol One or more groups of methyl ethyl ether, ethyl lactate, and butyl acetate. Further, from the viewpoint of safety of the human body, it is more preferred that the solvent is selected from the group consisting of propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and diethyl ether. One or more groups of diol methyl ethyl ether, ethyl lactate, and butyl acetate.

The solvent may also be a mixed solvent containing 20% by weight or more of a solvent having a boiling point of 100 ° C to 300 ° C. A solvent other than the solvent having a boiling point of from 100 ° C to 300 ° C in the mixed solvent may be one or two or more kinds of known solvents.

1-3-3. Additives

From the viewpoint of further improving the characteristics of the photosensitive composition such as the resolution, the coating uniformity, the developability, and the adhesion, and the cured film formed, it is preferred that the photosensitive composition further contains an additive. The additive can be used in various additives used in the field of resists for improving the characteristics of a photosensitive composition or a cured film. The additive may be one type or two or more types. Examples of such an additive include acrylic acid, styrene-based, polyethyleneimine-based or polyurethane-based polymer dispersing agents, anionic, cationic, nonionic or fluorine-based surfactants, and epoxy resin-based coating properties. A curing agent, an adhesion improving agent such as a decane coupling agent, an ultraviolet absorber such as an alkoxybenzophenone, a coacervation inhibitor such as sodium polyacrylate, or a thermal crosslinking agent such as an epoxy compound, a melamine compound or a double azide. And an alkali soluble accelerator such as an organic carboxylic acid.

More specifically, examples of the additive include Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, and Polyflow No. 95 (all of which are trade names, manufactured by Kyoeisha Chemical Co., Ltd.). Disperbyk 161, Disperbyk 162, Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 170, Disperbyk 180, Disperbyk 181, Disperbyk 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK344, BYK346 (all of the above are trade names, BYK-CHEMIE JAPAN KK), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (all of which are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (all of which are trade names, manufactured by AGC SEIMI CHEMICAL Co., Ltd.), Ftergent 222F, Ftergent 251, FTX-218 (all of which are trade names, manufactured by Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (all of which are trade names, manufactured by Mitsubishi Material Co., Ltd.), Megafac F-171, Megafac F-177, Megafac F-475, Megafac R-08, Megafac R-30 (all of the above are trade names, DIC Manufactured by the company, fluoroalkylbenzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, halothane sulfonate, diglycerin Tetrakis(fluoroalkyl polyoxyethylene ether), halothane Trimethylammonium salt, fluoroalkylamine sulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oil base Ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, poly Oxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitol Anhydride laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonate, And an alkyl diphenyl ether disulfonate. Preferably, the additive is one or more selected from the group consisting of these compounds.

From the viewpoint of improving the coating uniformity of the photosensitive composition, it is more preferable that the additive is one or both of a fluorine-based surfactant and a silicone resin-based coating property improving agent. More specifically, from the viewpoint of improving coating uniformity of the photosensitive composition, it is more preferred that the additive is selected from the group consisting of fluoroalkylbenzenesulfonate, fluoroalkylcarboxylate, and fluoroalkylpolyoxyethylene. Ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkanesulfonate, diglycerol tetrakis(fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, One or more of the groups consisting of BYK306, BYK344, BYK346, KP-341, KP-358, and KP-368.

1-3-4. Polycarboxylic anhydride

From the viewpoint of improving the heat resistance and chemical resistance of the cured film formed of the photosensitive composition having an epoxy group, and preventing decomposition of the 1,2-quinonediazide compound (B) by storage. Photosensitive composition From the viewpoint of color, it is preferred that the photosensitive composition further contains a polycarboxylic acid anhydride. The polycarboxylic acid anhydride can be reacted with an epoxy group in the photosensitive composition having an epoxy group by heating. The polycarboxylic acid anhydride may be one type or two or more types. Examples of the polyvalent carboxylic anhydride include trimellitic anhydride, phthalic anhydride, and 4-methylcyclohexane-1,2-dicarboxylic anhydride. Preferred among the polycarboxylic acid anhydrides is trimellitic anhydride.

1-4. Content of each component in the photosensitive composition

The content of the polymer (A) containing a oxoxane structure in the photosensitive composition is preferably from 20% by weight to 80% by weight, more preferably from 30% by weight to 70% by weight from the viewpoint of exhibiting the liquid repellency of the cured film. %, further preferably 40% by weight to 60% by weight.

From the viewpoint of forming a fine pattern in the cured film, the content of the 1,2-quinonediazide compound (B) in the photosensitive composition is relative to the polymer (A) containing a siloxane structure and alkali-soluble polymerization. The total amount of the component (C) is preferably from 5 parts by weight to 50 parts by weight, more preferably from 10 parts by weight to 40 parts by weight, still more preferably from 15 parts by weight to 30 parts by weight.

In the photosensitive composition, the content of the alkali-soluble polymer (C) when the content of the polymer (A) containing a siloxane structure is 100 parts by weight from the viewpoint of sufficiently exhibiting an effect of improving alkali solubility It is preferably 20 parts by weight to 150 parts by weight, more preferably 50 parts by weight to 120 parts by weight, still more preferably 70 parts by weight to 100 parts by weight.

From the viewpoint of improving the uniformity of coating of the photosensitive composition, and from the viewpoint of safety of the human body, it is preferred to be in the photosensitive composition. The content of the solvent is such that the content of all the solid components in the photosensitive composition is from 5 wt% to 50 wt%, more preferably from 10 wt% to 45 wt%, still more preferably from 15 wt% to 40 wt%. the amount.

From the viewpoint of imparting and improving the characteristics of the photosensitive composition and the cured film, the content of the additive in the photosensitive composition is based on the total amount of the polymer (A) containing the siloxane structure and the alkali-soluble polymer (C). It is preferably 0.01 parts by weight to 1 part by weight, more preferably 0.03 parts by weight to 0.7 parts by weight, still more preferably 0.05 parts by weight to 0.5 parts by weight, per 100 parts by weight.

The content of the polycarboxylic acid anhydride in the photosensitive composition is relative to the polymer (A) containing a siloxane structure and the alkali-soluble polymer (C) from the viewpoint of improving the characteristics of the cured film and preventing coloring of the photosensitive composition. The total amount of 100 parts by weight is preferably from 1 part by weight to 30 parts by weight, more preferably from 2 parts by weight to 20 parts by weight, still more preferably from 3 parts by weight to 15 parts by weight.

1-5. Preservation of photosensitive components

From the viewpoint of stably storing the photosensitive composition, it is preferred that the photosensitive composition is stored in a light-shielding manner at -30 ° C to 25 ° C, and it is more preferable that the storage temperature is -20 ° C from the viewpoint of preventing the occurrence of precipitates. ~10 °C.

2. The cured film of the present invention

The cured film of the present invention can be obtained by calcining a film of the photosensitive composition of the present invention described above. The photosensitive composition is suitable for forming a transparent cured film, and has a relatively high resolution when patterned, and thus is suitable for forming an insulating film having a small hole of 10 μm or less. Here, the insulating film is used, for example, to make A film (interlayer insulating film) or the like which is provided as a layered wiring between the wirings.

A cured film such as a transparent film or an insulating film can be formed by a usual method of forming a cured film in the field of a resist, and can be formed, for example, in the following manner.

First, a film of a photosensitive composition is formed. The film of the photosensitive composition can be formed by applying a photosensitive composition to a substrate such as glass by a known method such as spin coating, roll coating, or slit coating. Preferred coating methods include spin coating, roll coating, and slit coating. Examples of the substrate include transparent glass substrates such as white glass, blue glass, and ceria coated green glass, and polycarbonate, polyether oxime, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, and poly A synthetic resin sheet such as amidoxime or a polyimide, a film or a substrate, a metal substrate such as an aluminum plate, a copper plate, a nickel plate or a stainless steel plate, and another ceramic plate having a semiconductor substrate of a photoelectric conversion element. Pretreatment such as chemical treatment, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum evaporation, etc. of a decane coupling agent may be performed on the substrates as needed.

Next, the film of the photosensitive composition is dried. The film of the photosensitive composition can be dried, for example, by heating a substrate having a film of a photosensitive composition by a hot plate or an oven. Drying is usually carried out at 60 ° C to 120 ° C for 1 minute to 5 minutes.

Next, the film of the dried photosensitive composition is irradiated with radiation through a mask of a desired pattern shape. Irradiation of the radiation of the film of the photosensitive composition can be performed, for example, by irradiating the film of the dried photosensitive composition on the substrate with ultraviolet rays by means of a mask. The irradiation condition depends on the kind of the photosensitizer in the photosensitive composition. For example, the photosensitive composition contains the 1,2-quinonediazide compound (B), so the i line is suitably ⁵ mJ/cm ² to 1,000 mJ/cm. ² . Further, in the case of forming a cured film having no pattern, the irradiation step of the radiation is not required.

Next, development is carried out by washing a film of the photosensitive composition irradiated with radiation by a developing solution. The 1,2-quinonediazide compound (B) in the film of the photosensitive composition irradiated with radiation rapidly becomes a hydrazine carboxylic acid and is dissolved in the developing solution. By this development, the portion irradiated with radiation in the film is quickly dissolved in the developer. The development method is not particularly limited, and any of various known methods such as immersion development, dip development, and shower development can be used. Further, in the case of forming a cured film having no pattern, the development step is not required.

The developer is preferably an alkali solution. As the developer, an aqueous solution of a base can be suitably used. Examples of the base contained in the alkali solution include tetramethylammonium hydroxide, tetraethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, and potassium hydrogencarbonate. Sodium hydroxide, and potassium hydroxide. More preferably, the developing solution is preferably an aqueous solution of an organic base such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or 2-hydroxyethyltrimethylammonium hydroxide, or sodium carbonate or hydrogen. An aqueous solution of an inorganic base such as sodium oxide or potassium hydroxide.

In order to reduce the development residue or to optimize the shape of the pattern, methanol, ethanol or a surfactant may be added to the developer. As the surfactant, for example, an anionic, cationic, or nonionic surfactant can be used. Among these, in particular, when a nonionic polyoxyethylene alkyl ether is added, it is preferable from the viewpoint of improving the resolution.

Next, the developed film is cleaned. Membrane cleaning can be done, for example, by pure Water is applied to the film and the substrate together with sufficient washing.

Next, the front surface of the film to be cleaned is irradiated with radiation. The residual 1,2-quinonediazide compound (B) is deactivated by irradiation of the radiation. When the radiation is irradiated with ultraviolet rays, for example, when the radiation is ultraviolet rays, the film is irradiated with ultraviolet rays at an exposure amount of 100 mJ/cm ² to 1,000 mJ/cm ² .

Next, the film irradiated with radiation is calcined to obtain a cured film. The calcination of the film can be carried out, for example, by heating the substrate having the film at 180 ° C to 250 ° C for 10 minutes to 120 minutes. By this step, a cured film is obtained as a desired patterned transparent film.

The pattern-like transparent film thus obtained can also be used as a pattern-like insulating film. The shape of the hole formed in the insulating film is preferably square, rectangular, circular or elliptical when viewed from above. Further, a transparent electrode may be formed on the insulating film, and after patterning by etching, a film subjected to alignment treatment may be formed. Since the insulating film has high sputtering resistance, wrinkles are not formed on the insulating film even when a transparent electrode is formed, and high transparency can be maintained.

3. Display element of the present invention

The display element of the present invention has the above-described cured film of the present invention. Examples of the use of the cured film in the display element include a transparent film, an insulating film, and a barrier film for preventing liquid from adhering to the periphery of the pattern.

The display element has the same configuration as the known display element except that the cured film of the present invention is used for the above-described use, and can be produced in the same manner as the known display element. The display element can be, for example, as described above on the substrate The element substrate having the patterned cured film and the color filter substrate as the opposite substrate are bonded to each other at positions marked with marks attached to the respective substrates, and then heat-treated to separate the other members from the substrate. In combination, liquid crystal is injected between the opposing substrates, and the injection port is sealed to form a liquid crystal display element.

In the manufacture of the liquid crystal display device, the sealing of the liquid crystal may be performed by dispersing the liquid crystal on the element substrate, superimposing the element substrate on the color filter substrate, and sealing the liquid crystal so as not to leak. The display element can also be a liquid crystal display element fabricated as such.

The liquid crystal, that is, the liquid crystal compound and the composition containing the same are not particularly limited, and any liquid crystal compound and liquid crystal composition can be used.

The photosensitive composition of the present invention can be formed, for example, to have high solvent resistance, high water resistance, high acid resistance, high alkali resistance, high heat resistance, high transparency, and the like, which are generally required for a patterned transparent film and an insulating film. A cured film having various properties such as adhesion to a substrate and excellent liquid repellency.

Further, in addition to the above-described high liquid repellency and UV ozone ashing resistance, the photosensitive composition of the present invention has normal characteristics required as a resist material in terms of developability, chemical resistance, and adhesion. It also has at least sufficient performance as a resist material. Therefore, the photosensitive composition of the present invention can form a cured film excellent in pattern formability in addition to liquid repellency. Moreover, the film can be used as a transparent film, an insulating film or a protective film, and thus can be used as a display element.

Since the cured film of the present invention is formed from the photosensitive composition of the present invention, it is subjected to immersion, contact, and heat treatment even in a solvent, an acid, an alkali solution or the like. It is also difficult to produce surface roughness by equal treatment. Therefore, the light transmittance in the cured film of the display element of the present invention is high, and high display quality can be obtained.

Further, since the cured film of the present invention is formed of a photosensitive composition, it is excellent in liquid repellency, and the liquid material supplied to the pattern (opening) of the cured film is prevented from adhering to portions other than the pattern during the production of the display element. And the desired desired liquid is easily moved to the opening. Therefore, the display element of the desired performance can be efficiently obtained, and further improvement in the productivity of the display element is expected.

[Example]

Hereinafter, the present invention will be further illustrated by way of examples, but the invention is not limited to the examples.

[Synthesis Example 1] Synthesis of polymer (A1) containing a siloxane structure

Into a four-necked flask equipped with a stirrer, 16 g of diethylene glycol methyl ethyl ether as a solvent was placed, and on the other hand, 11 g of diethylene glycol methyl ethyl ether was mixed as the following weight. α,ω-bis(3-methylpropenyloxypropyl)polydimethyloxane represented by the formula (1-1) of the radical polymerizable monomer (a-1) (manufactured by CHISSO CORPORATION) FM7711, number average molecular weight: 1,000), 4-hydroxyphenyl vinyl ketone as a radical polymerizable monomer (a-2), glycidyl methacrylate as a radical polymerizable monomer (a-3) , 3-methacryloxypropyltrimethoxydecane, 2,2'-azobis(2-methylpropionate) dimethyl ester as a polymerization initiator, and the obtained mixed solution is 1 The mixture was added dropwise to the solvent in a 4-neck flask maintained at 110 ° C, and further heated at 110 ° C for 2 hours after the dropwise addition.

The obtained reaction liquid was cooled to room temperature to obtain a 33.3 wt% solution of a polymer (A1) containing no oxoxane structure containing no dimethyl 2,2'-azobis(2-methylpropionate) dimethyl ester. . A portion of the reaction solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the polymer (A1) containing a siloxane structure was 4,000.

[Synthesis Example 2] Synthesis of polymer (A2) containing a siloxane structure

The mixed solution was prepared by using the following components under the following weight, and polymerization was carried out in the same manner as in Synthesis Example 1.

The obtained reaction liquid was cooled to room temperature to obtain a 33.3 wt% solution of a polymer (A2) containing no oxoxane structure containing no dimethyl 2,2'-azobis(2-methylpropionate) dimethyl ester. . A portion of the reaction solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the polymer (A2) containing a siloxane structure was 3,100.

[Synthesis Example 3] Synthesis of alkali-soluble polymer (C1)

Α-butyl-ω-(3-methacryloxypropyl)polydimethyloxane represented by the formula (3-1) (FM0711 manufactured by CHISSO CORPORATION, number average molecular weight: 1,000) was used. The mixed solution was prepared by using the following components in the following weight instead of α,ω-bis(3-methylpropenyloxypropyl)polydimethyloxane, and polymerization was carried out in the same manner as in Synthesis Example 1.

The resulting reaction solution was cooled to room temperature to obtain a 33.3 wt% solution of an alkali-soluble polymer (C1) containing no dimethyl 2,2'-azobis(2-methylpropionate). A portion of the reaction solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the alkali-soluble polymer (C1) was 2,800.

[Synthesis Example 4] Synthesis of alkali-soluble polymer (C2)

The mixed solution was prepared by using the following components under the following weight, and polymerization was carried out in the same manner as in Synthesis Example 1.

The resulting reaction solution was cooled to room temperature to obtain a 33.3 wt% solution of an alkali-soluble polymer (C2) containing no dimethyl 2,2'-azobis(2-methylpropionate). A portion of the reaction solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the alkali-soluble polymer (C2) was 3,500.

[Synthesis Example 5] Synthesis of alkali-soluble polymer (C3)

The mixed solution was prepared by using the following components under the following weight, and polymerization was carried out in the same manner as in Synthesis Example 1.

Diethylene glycol methyl ethyl ether 11.0g

The resulting reaction solution was cooled to room temperature to obtain a 33.3 wt% solution of an alkali-soluble polymer (C3) containing no dimethyl 2,2'-azobis(2-methylpropionate). A portion of the reaction solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the alkali-soluble polymer (C3) was 2,800.

[Synthesis Example 6] Synthesis of alkali-soluble polymer (C4)

The mixed solution was prepared by using the following components under the following weight, and polymerization was carried out in the same manner as in Synthesis Example 1.

The resulting reaction solution was cooled to room temperature to obtain a 33.3 wt% solution of an alkali-soluble polymer (C4) containing no dimethyl 2,2'-azobis(2-methylpropionate). A portion of the reaction solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the alkali-soluble polymer (C4) was 2,800.

[Comparative Synthesis Example 1] Synthesis of polymer (D1) containing a siloxane structure

The mixed solution was prepared by using the following components in the following manner, and the same procedure as in Synthesis Example 1 was carried out except that the mixed solution was prepared in the same manner as in Synthesis Example 1 except that the temperature of the solvent in the four-necked flask in the reaction of the mixed solution and the subsequent reaction was 90° C. polymerization.

The obtained reaction liquid was cooled to room temperature to obtain a 33.3 wt% solution of a polymer (D1) containing no oxoxane structure containing no dimethyl 2,2'-azobis(2-methylpropionate) dimethyl ester. . A portion of the reaction solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the polymer (D1) containing a decane structure was 2,700.

[Example 1]

[Manufacture of positive photosensitive composition]

The copolymer (A1) obtained in Synthesis Example 1, the copolymer (C4) obtained in Synthesis Example 6, and 4,4'-[1-[4-[1- as a 1,2-quinonediazide compound. a condensate of [4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol with 1,2-naphthoquinonediazide-5-sulfonyl chloride (average esterification rate is 58 %, hereinafter referred to as "PAD"), 矽-based surfactant BYK344 (product name: BYK-CHEMIE JAPAN KK, hereinafter abbreviated as "BYK344"), and diethylene glycol methyl ethyl ether as solvent Description The weight was mixed and dissolved to obtain a positive photosensitive composition 1 having a solid concentration of 35 wt%.

[Evaluation method of positive photosensitive composition]

1) Method for forming patterned transparent film

The photosensitive composition 1 was spin-coated on a glass substrate at 600 rpm for 10 seconds, and dried on a hot plate at 100 ° C for 2 minutes. The substrate was used in a mask for forming an air-intervening pattern, and a proximity exposure machine TME-150PRC manufactured by TOPCON Co., Ltd. was used to emit light, g, h, and i lines through a wavelength cut-off filter that cuts off light of 350 nm or less. Exposure was performed with an exposure gap of 100 μm. The exposure amount was set to 150 mJ/cm ² . The exposure amount was measured by an integrated light meter UIT-102 manufactured by Ushio Inc. and a light receiver UVD-365PD. The exposed glass substrate was immersed and developed in a 0.4 wt% aqueous solution of tetramethylammonium hydroxide for 60 seconds to remove the resin composition of the exposed portion. The developed substrate was washed in pure water for 60 seconds, and then dried on a hot plate at 100 ° C for 2 minutes. The substrate was exposed to the entire surface at 300 mJ/cm ² without interposing a mask in an exposure machine, and then baked in an oven at 230 ° C for 30 minutes to form a pattern-like transparent film having a film thickness of 3 μm. .

2) Residual film rate after development

The film thickness was measured before and after development, and was calculated according to the following formula.

(film thickness after development / film thickness before development) × 100 (%)

The film thickness was measured by using a stylus type film thickness meter P-15 manufactured by KLA-Tencor Japan Co., Ltd., and the average value was taken.

3) Resolution

The substrate of the patterned transparent film obtained in the above 1) was observed under an optical microscope at 400 times, and it was confirmed that the mask size of the glass was exposed at the bottom of the hole pattern. The case where the hole pattern was not formed was described as defective (NG).

4) Adhesion

The substrate of the pattern-like transparent film obtained in the above 1) was evaluated by a grid peeling test (cross-cut test). The evaluation was carried out by attaching an adhesive tape to a patterned transparent film having 100 grids of 1 mm square formed by cutting ("PET tape No. 56: adhesive force; 5.5 N/cm" manufactured by Sumitomo 3M Co., Ltd. ), expressed as the number of remaining grids after tape peeling.

5) UV/O ₃ ashing treatment

A transparent film was formed in the same manner as in the above 1) except that the film was not formed, and the obtained transparent film was treated under the following conditions by the following apparatus.

Device: PL2003N-12 (PHOTO SURFACE PROCESSOR manufactured by SEN LIGHTS Co., Ltd.)

Setting values: ultraviolet wavelength (254 nm), exposure (525 mJ/cm ² )

Further, the exposure amount at 254 nm was measured using UVC-254 manufactured by CUSTOM Co., Ltd.

6) Contact angle

The contact angle of the pure water of the transparent film before and after the UV/O ₃ ashing treatment of the above 5) was measured at 25 ° C by a Drop Master 500 manufactured by Kyowa Interface Chemical Co., Ltd. The value after attaching pure water for 1 second was taken as the contact angle value.

The composition of the photosensitive composition 1 and the results obtained by the above evaluation methods are shown in Table 1.

[Example 2 to Example 5 and Comparative Example 1 to Comparative Example 4]

In the same manner as in Example 1, the photosensitive composition 2 to the photosensitive composition 5 and the comparative soluble composition 1 to the comparative soluble composition 4 were prepared in the same manner as in Example 1 in the same manner as in Example 1. Evaluation. The composition and evaluation results of the photosensitive compositions are shown in Table 1.

As is clear from Table 1, in Examples 1 to 5, a high contact angle was obtained even after the UV/O ₃ ashing treatment as compared with Comparative Examples 1 to 4.

[Industrial availability]

As described above, the photosensitive composition of the present invention can be treated by a known lithography method, and the obtained cured film has sufficient liquid repellency as a barrier material. Further, in the circuit board manufacturing process or the like, it is possible to suppress a decrease in the liquid repellency of the surface of the barrier material due to the UV/O ₃ ashing treatment for improving the wettability, and to maintain sufficient liquid repellency after the treatment.

Claims (13)

A photosensitive composition comprising: a polymer comprising a oxoxane structure (A) and a 1,2-quinonediazide compound (B), wherein the polymer (A) comprising a decane structure is a formula (1) a radical polymer of a halogenated alkane compound and a monomer of an alkali-soluble radically polymerizable monomer having an alkali solubility which imparts alkali solubility to the polymer (A) Free radical polymerizability, (In the formula (1), R ¹ to R ⁴ each independently represent hydrogen, or an arbitrary alkyl group which may be substituted by fluorine and which is not continuous, or an alkyl group having 1 to 30 carbon atoms which may be substituted by oxygen. A ¹ and A ² each represent a radical polymerizable functional group, and n represents an integer of 1 to 1,000). The photosensitive composition according to claim 1, wherein the alkali-soluble radically polymerizable monomer contains a radically polymerizable monomer having an unsaturated carboxylic acid, and has an unsaturated carboxylic anhydride. One or more of the group consisting of a base polymerizable monomer and a radical polymerizable monomer having a phenolic hydroxyl group. The photosensitive composition according to the first aspect of the invention, wherein the alkali-soluble radical polymerizable monomer comprises a radical polymer monomer represented by the formula (2), (In the formula (2), R ⁵ to R ⁷ each represent hydrogen, or an arbitrary hydrogen may be substituted by fluorine to have an alkyl group having 1 to 3 carbon atoms, and R ⁸ to R ¹² represent hydrogen, halogen, -CN, respectively. -CF ₃ , -OCF ₃ , hydroxy group, any methylene group may be substituted by -COO-, -OCO-, -CO- and any hydrogen may be substituted by halogen with a C 1~5 alkyl group, or Any hydrogen may be substituted with a halogen to have an alkoxy group having 1 to 5 carbon atoms; wherein at least one of R ⁸ to R ¹² is a hydroxyl group). The photosensitive composition according to claim 1, wherein the polymer (A) comprising a oxoxane structure further comprises a oxoxane compound represented by the formula (1) and an alkali-soluble radical polymerization. A radical polymer of a monomer other than a radical polymerizable monomer other than a monomer. The photosensitive composition according to claim 4, wherein the other radical polymerizable monomer comprises a siloxane compound represented by the formula (3), (In the formula (3), R ¹³ to R ¹⁷ each independently represent an arbitrary alkyl group which may be substituted by fluorine and an arbitrary methylene group may be substituted by an oxygen group having an alkyl group having 1 to 30 carbon atoms or a number of turns 1 ~500 tris(alkyl/alkoxy)decyloxy, A ³ represents a radical polymerizable functional group, and n represents an integer of 0 to 1,000). The photosensitive composition according to claim 5, wherein the other radical polymerizable monomer is a oxoxane compound represented by the formula (3) wherein n is 0. The photosensitive composition according to claim 6, wherein R ¹³ to R ^{15 of the} formula (3) are each represented by the following formula (5). (In the formula (5), R ²¹ to R ²³ each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, and m represents an integer of 1 to 500). The photosensitive composition according to any one of claims 4 to 7, wherein the other radical polymerizable monomer comprises a (meth)acrylic acid derivative. The photosensitive composition according to any one of claims 1 to 7, further comprising an alkali-soluble polymer (C) represented by formula (1) A radical polymer of a monomer other than a oxoxane compound, and having an alkali solubility. The photosensitive composition according to claim 9 of the patent application, The alkali-soluble polymer (C) is a radical polymerization comprising a radically polymerizable monomer selected from the group consisting of a radically polymerizable monomer having an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, and a phenolic hydroxyl group. A radical polymer of one or more monomers of a group consisting of monomers. The photosensitive composition according to any one of claims 1 to 7, further comprising a solvent. A cured film obtained by calcining a film of the photosensitive composition according to any one of claims 1 to 11. A display element having a cured film as described in claim 12 of the patent application.