JP6318634B2 - Photosensitive siloxane composition, cured film and device - Google Patents

Description

  The present invention relates to a photosensitive siloxane composition, a cured film, and a device.

  In recent years, a method for increasing the aperture ratio of a display device has been known in order to realize a liquid crystal display or an organic EL display with higher definition and higher resolution (Patent Document 1). In this method, a transparent planarizing film is provided as a protective film on the TFT substrate, and the data line and the pixel electrode are overlapped to increase the aperture ratio.

  As a material for such a flattening film for a TFT substrate, a photosensitive acrylic composition that is a combination of an acrylic resin and a naphthoquinonediazide compound that has high transparency and can ensure conduction between the TFT substrate electrode and the ITO electrode (Patent Document) 2-4) are known.

  However, the photosensitive acrylic composition is inferior in heat resistance, and it has been pointed out that transparency and electrical conductivity are lowered by high-temperature treatment.

  On the other hand, photosensitive siloxane compositions combining polysiloxane and naphthoquinone diazide compounds are known as materials with high transparency and excellent heat resistance (Patent Documents 5 and 6), and further, high sensitivity and shortened development time. A photosensitive siloxane composition to which a hydroxyimide compound is added is also known (Patent Document 7).

JP 9-152625 A JP 2001-281853 A JP-A-5-165214 JP 2002-341521 A JP 2006-178436 A JP 2009-211033 A JP 2007-174781 A

  However, the conventional photosensitive siloxane composition has a poor development margin, and the occurrence of scum when the development time is shortened is regarded as a problem. In addition, the addition of hydroxyimide compounds alleviates these problems, but the adhesion to highly hydrophobic substrates such as metal substrates is not sufficient, and new problems such as film peeling during development occur. Met.

  Therefore, the present invention can form a highly accurate pattern even in a short development time while satisfying essential properties such as high transparency and high heat resistance, has a good development margin, and is excellent for a metal substrate or the like. An object of the present invention is to provide a photosensitive siloxane composition that exhibits excellent adhesion.

  As a result of intensive studies, the present inventors have found that (a) a composition comprising a component including a polysiloxane having an epoxy structure and / or an oxetane structure is extremely effective in solving the above problems. The invention has been completed.

That is, the present invention includes (a) a polysiloxane having an epoxy structure and / or an oxetane structure, (b) a naphthoquinone diazide compound, (c) a solvent, and (d) a hydroxyimide compound represented by the general formula (2), (A) The ratio of the epoxy structure and the oxetane structure in the polysiloxane having the epoxy structure and / or the oxetane structure is (a) the polysiloxane having the epoxy structure and / or the oxetane structure. The polysiloxane having 5 mol% or more based on Si atoms and having the above-mentioned (a) epoxy structure and / or oxetane structure is a reactant of a monomer containing an organosilane represented by the general formula (1). A photosensitive siloxane composition is provided.

(In the formula, each R ¹ independently represents an organic group having 1 to 15 carbon atoms having an epoxy structure or an oxetane structure, and each R ² independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, Represents an alkenyl group having 2 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and each R ³ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or carbon. Represents an aryl group of formulas 6 to 15, n represents an integer of 1 to 3, m represents an integer of 0 to 2 (where n + m is an integer of 1 to 3))

(Wherein R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group, an aryl group or an alkenyl group. R ⁴ and R ⁵ may be condensed with each other to form a ring structure. .)

  According to the photosensitive siloxane composition of the present invention, a high-precision pattern can be formed with a good development margin and a short development time, and the transparency, heat resistance, adhesion to a metal substrate, etc. are remarkably excellent. Moreover, it is possible to form a cured film.

  The photosensitive siloxane composition of the present invention comprises (a) a polysiloxane having an epoxy structure and / or an oxetane structure (hereinafter referred to as “(a) polysiloxane”), (b) a naphthoquinonediazide compound, (c) a solvent, and (D) A photosensitive siloxane composition containing a hydroxyimide compound represented by the general formula (2), wherein the (a) polysiloxane comprises a monomer containing an organosilane represented by the general formula (1). It is obtained by reacting.

(In the formula, each R ¹ independently represents an organic group having 1 to 15 carbon atoms having an epoxy structure or an oxetane structure, and each R ² independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, carbon Represents an alkenyl group having 2 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and each R ³ independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or 6 carbon atoms. -15 represents an aryl group, n represents an integer of 1 to 3, m represents an integer of 0 to 2 (where n + m is an integer of 1 to 3))
When R ^{1 to} R ³ in the general formula (1) are an organic group having an epoxy structure or an oxetane structure, an alkyl group, an alkenyl group, an aryl group, or an acyl group, these organic groups, alkyl groups, alkenyl groups, and aryl groups And the acyl group may be either unsubstituted or substituted. Examples of the organic group having an epoxy structure or an oxetane structure include a 3-glycidoxypropyl group, a 2- (3,4-epoxycyclohexyl) ethyl group, and a [(3-ethyl-3-oxetanyl) methoxy] propyl group. Can be mentioned. Examples of the alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 3, 3, A 3-trifluoropropyl group, a 3-aminopropyl group, a 3-mercaptopropyl group, or a 3-isocyanatopropyl group may be mentioned. Examples of the alkenyl group include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group. As an aryl group, a phenyl group, a tolyl group, or a naphthyl group is mentioned, for example. Examples of the acyl group include an acetyl group.

  When n + m = 1, it is a trifunctional silane, when n + m = 2, it is a bifunctional silane, and when n + m = 3, it is a monofunctional silane.

  (A) By containing polysiloxane, the development adhesiveness with respect to a board | substrate with high hydrophobicity, such as a metal substrate, improves, and the film peeling at the time of image development is suppressed.

  Examples of the organosilane represented by the general formula (1) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltrimethoxysilane or [(3-ethyl-3-oxetanyl) methoxy] propyltriethoxysilane, etc. A bifunctional silane such as 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propylmethyldimethoxysilane, or the like 3-Glycidoxypropyldimethylmeth Although monofunctional silanes such as silane, 3-glycidoxypropyldimethylethoxysilane, or [(3-ethyl-3-oxetanyl) methoxy] propyldimethylmethoxysilane can be mentioned, crack resistance and hardness of the obtained cured film From the viewpoint, trifunctional silane is preferable.

  (A) The polysiloxane may be synthesized by reacting only the organosilane represented by the general formula (1). For example, the polysiloxane may be synthesized with another organosilane such as an organosilane represented by the general formula (3). You may synthesize | combine by making a mixture react.

(In the formula, each R ⁶ independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and R ⁷ each independently. And a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and x represents an integer of 0 to 3).
When R ⁶ and R ⁷ in the general formula (3) are an alkyl group, an alkenyl group, an aryl group, or an acyl group, these organic groups, alkyl groups, alkenyl groups, aryl groups, and acyl groups are unsubstituted or substituted. It can be any body. Examples of R ⁶ that is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, an n-decyl group, a trifluoromethyl group, 3,3,3-trifluoropropyl group, 3-aminopropyl group, 3-mercaptopropyl group or 3-isocyanatopropyl group may be mentioned. Examples of R ⁶ that is an alkenyl group include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group. Examples of R ⁶ that is an aryl group include a phenyl group, a tolyl group, a p-hydroxyphenyl group, a p-methoxyphenyl group, a 1- (p-hydroxyphenyl) ethyl group, and a 2- (p-hydroxyphenyl) ethyl group. 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl group or naphthyl group. Examples of R ⁷ that is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Examples of R ⁷ that is an acyl group include an acetyl group. Examples of R ⁷ that is an aryl group include a phenyl group.

  A tetrafunctional silane when x = 0, a trifunctional silane when x = 1, a bifunctional silane when x = 2, and a monofunctional silane when x = 3.

  Examples of the organosilane represented by the general formula (3) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraacetoxysilane, and tetraphenoxysilane, methyltrimethoxysilane, and methyltriethoxy. Silane, methyltriisopropoxysilane, methyltrin-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyl Triethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, p -Methoxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxy Silane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropro Trifunctional silanes such as rutrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane or 3-trimethoxysilylpropylsuccinic acid, dimethyldimethoxysilane, dimethyldiethoxy Examples include bifunctional silanes such as lan, dimethyldiacetoxysilane, di-n-butyldimethoxysilane or diphenyldimethoxysilane, or monofunctional silanes such as trimethylmethoxysilane or tri-n-butylethoxysilane. From the viewpoint of properties and hardness, trifunctional silane is preferable.

  As a mixing ratio of the organosilane represented by the general formula (1) and the organosilane represented by the general formula (3), the general formula (1) / general formula (3) = 1 to 50/99 to 50 A molar ratio of 5 to 30/95 to 70 is more preferable. When the organosilane represented by the general formula (1) is less than 1 mol%, the development adhesion to the metal substrate becomes insufficient. On the other hand, when it exceeds 50 mol%, the film reduction of the unexposed part at the time of development will become large, and the film thickness uniformity of a cured film will deteriorate.

  (A) The polysiloxane may be synthesized by reacting the organosilane represented by the general formula (1) with the silicate compound represented by the general formula (4) and a mixture. The pattern resolution is improved by mixing the silicate compound. This is presumably because the glass transition temperature of the cured film obtained is increased by incorporating a polyfunctional silicate compound into the polysiloxane, and the pattern dripping at the time of thermosetting can be suppressed.

(Wherein R ^{8 to} R ¹¹ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and p is 2) Represents an integer of 10 to 10.)
Examples of the silicate compound represented by the general formula (4) include methyl silicate 51 (manufactured by Fuso Chemical Industry Co., Ltd.), M silicate 51, silicate 40, silicate 45 (manufactured by Tama Chemical Industry Co., Ltd.), and methyl silicate. 51, methyl silicate 53A, ethyl silicate 40 or ethyl silicate 48 (manufactured by Colcoat Co., Ltd.).

(A) The ratio of the structure derived from the silicate compound in the polysiloxane is preferably 50% or less in terms of the number of Si atoms. When the number of Si atoms derived from the silicate compound exceeds 50%, the compatibility between (a) polysiloxane and (b) naphthoquinonediazide compound is deteriorated, and the transparency of the resulting cured film is lowered. In addition, (a) The ratio of the number of Si atoms derived from the silicate compound to the number of Si atoms in the entire polysiloxane can be obtained from the integral ratio of the peak derived from the Si—C bond and the peak derived from the Si—O bond in IR. it can. When there is much overlap of peaks and an accurate integration ratio cannot be obtained, the structure of the monomer other than the silicate compound is determined by ¹ H-NMR, ¹³ C-NMR, IR, TOF-MS, etc. It can be determined from the ratio between the gas generated and the remaining ash (assuming all SiO ₂ ).

  In order to improve the compatibility between (a) polysiloxane and (b) naphthoquinonediazide compound and obtain a uniform cured film without phase separation, (a) the content ratio of phenyl group-substituted silane in polysiloxane is Si atom The molar ratio is preferably 30% or more, and more preferably 40% or more. When the content ratio of the phenyl group-substituted silane is less than 30 mol%, the compatibility between (a) polysiloxane and (b) naphthoquinonediazide compound is deteriorated, and phase separation occurs during coating, drying, thermosetting, etc. Becomes cloudy and the transmittance of the cured film decreases. When the content ratio of the phenyl group-substituted silane exceeds 70%, the crosslinking at the time of thermosetting does not sufficiently occur, and the chemical resistance of the obtained cured film is lowered.

(A) The content ratio of the phenyl group-substituted silane in the polysiloxane is determined by measuring ²⁹ Si-NMR of the (a) polysiloxane, and the peak area of Si to which the phenyl group is bonded and the phenyl group is not bonded. It can be determined from the ratio of the peak area of Si.

  (A) The weight average molecular weight (Mw) of the polysiloxane is preferably from 1,000 to 100,000, more preferably from 2,000 to 50,000 in terms of polystyrene measured by GPC (gel permeation chromatography). When the weight average molecular weight is less than 1000, the coating property is deteriorated. On the other hand, when it exceeds 100,000, the solubility with respect to the developing solution at the time of development will worsen.

  (A) Polysiloxane is obtained by hydrolyzing and partially condensing a monomer such as organosilane represented by the general formula (1). Examples of the hydrolysis and partial condensation method include a method in which a solvent and water are added to the monomer, a catalyst is added as necessary, and the mixture is heated and stirred at 50 to 150 ° C. for 0.5 to 100 hours. . During heating and stirring, hydrolysis by-products (alcohol such as methanol) or condensation by-products (water) may be distilled off by distillation.

  As the solvent used for hydrolysis and partial condensation, the same solvent as the solvent (c) can be used. As for the quantity of the solvent to be used, 10-1000 mass parts is preferable with respect to 100 mass parts of monomers. The amount of water used for the hydrolysis reaction is preferably 0.5 to 2 mol with respect to 1 mol of the hydrolyzable group.

  As a catalyst added as needed, an acid catalyst or a base catalyst is preferable. Examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyvalent carboxylic acid or anhydrides thereof, and ion exchange resins. Examples of the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, amino group An alkoxysilane or ion exchange resin having The addition amount of the catalyst is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the monomer.

  From the viewpoint of storage stability, it is preferable that the (a) polysiloxane solution after hydrolysis and partial condensation does not contain a catalyst, and the catalyst can be removed if necessary. Examples of the catalyst removal method include water washing and treatment with an ion exchange resin. Here, the water washing means (a) a method of concentrating an organic layer obtained by diluting a polysiloxane solution with an appropriate hydrophobic solvent and then washing several times with water with an evaporator. The treatment with an ion exchange resin means (a) a method of bringing a polysiloxane solution into contact with an appropriate ion exchange resin.

  The photosensitive siloxane composition of the present invention contains (b) a naphthoquinonediazide compound. (B) By containing a naphthoquinonediazide compound, it is possible to form a positive pattern in which the exposed portion is removed with a developer. (B) As the naphthoquinone diazide compound, a compound in which naphthoquinone diazide sulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group is preferable, and the ortho-position and para-position of the phenolic hydroxyl group of the compound are each independently a hydrogen atom, hydroxyl group Or the compound which is a substituent represented by General formula (5) is more preferable. When the ortho-position and para-position of the phenolic hydroxyl group are, for example, a methyl group, oxidative decomposition occurs due to thermal curing, a conjugated compound typified by a quinoid structure is formed, and the resulting cured film is colored and colorless and transparent May decrease.

(In the formula, R ^{12 to} R ¹⁴ each independently represents an alkyl group having 1 to 10 carbon atoms, a carboxyl group, or a phenyl group. R ^{12 to} R ¹⁴ are condensed with each other to form a ring structure. It doesn't matter.)
When R ^{12 to} R ¹⁴ in the general formula (5) are alkyl groups or phenyl groups, these alkyl groups and phenyl groups may be either unsubstituted or substituted. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-heptyl group, and n-octyl group. Group, trifluoromethyl group or 2-carboxyethyl group. Examples of the ring structure in which R ^{12 to} R ¹⁴ are condensed with each other include a cyclopentane ring, a cyclohexane ring, an adamantane ring, and a fluorene ring.

  A compound in which naphthoquinone diazide sulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group can be synthesized by a known esterification reaction between a compound having a phenolic hydroxyl group and naphthoquinone diazide sulfonic acid chloride.

  Examples of the compound having a phenolic hydroxyl group include the following compounds (all manufactured by Honshu Chemical Industry Co., Ltd.).

  Examples of naphthoquinone diazide sulfonic acid chloride include 4-naphthoquinone diazide sulfonic acid chloride and 5-naphthoquinone diazide sulfonic acid chloride. Since 4-naphthoquinonediazide sulfonic acid ester compound has absorption in the i-line (wavelength 365 nm) region, it is suitable for i-line exposure. Further, 5-naphthoquinonediazide sulfonic acid ester compounds are suitable for exposure in a wide range of wavelengths because of their absorption in a wide range of wavelengths. For this reason, it is preferable to appropriately select a 4-naphthoquinone diazide sulfonic acid ester compound or a 5-naphthoquinone diazide sulfonic acid ester compound depending on the wavelength to be exposed. On the other hand, a 4-naphthoquinone diazide sulfonic acid ester compound and a 5-naphthoquinone diazide sulfonic acid ester compound may be mixed and used.

  (B) 2-30 mass parts is preferable with respect to 100 mass parts of polysiloxane, and, as for content of a naphthoquinone diazide compound, 3-15 mass parts is more preferable. (B) When content of a naphthoquinone diazide compound is less than 2 mass parts, the melt | dissolution contrast of an exposed part and an unexposed part is too low, and the photosensitivity sufficient for practical use is not expressed. On the other hand, if the content of the naphthoquinone diazide compound exceeds 30 parts by mass, the coating film may be whitened due to poor compatibility between the polysiloxane and the naphthoquinone diazide compound, or may be caused by decomposition of the naphthoquinone diazide compound that occurs during thermal curing. Coloring occurs and the colorless transparency of the cured film decreases.

  The photosensitive siloxane composition of the present invention contains (c) a solvent. (C) As a solvent, a compound having an alcoholic hydroxyl group, in which polysiloxane and naphthoquinonediazide compound are uniformly dissolved and high transparency can be achieved without whitening of the film even when the composition is applied to form a film. The compound whose boiling point under atmospheric pressure is 110-250 degreeC is more preferable. If the boiling point exceeds 250 ° C., the amount of residual solvent in the film increases and film shrinkage during curing increases, and good flatness cannot be obtained. On the other hand, when the boiling point is less than 110 ° C., the coating properties deteriorate, for example, the drying at the time of coating is too fast and the film surface becomes rough.

  Examples of the compound having an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, and 4-hydroxy-4. -Methyl-2-pentanone (diacetone alcohol), methyl lactate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, propylene glycol mono t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 3-methyl Carboxymethyl-1-butanol, 3-methyl-3-methoxy-1-butanol, n- butanol, 1-pentanol or 2-heptanol.

  Examples of the solvent (c) other than the compound having an alcoholic hydroxyl group include, for example, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate. , Esters such as 3-methyl-3-methoxy-1-butyl acetate or ethyl acetoacetate, ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone or acetylacetone, diethyl ether, diisopropyl ether, di n-butyl ether, diphenyl ether , Ethers such as diethylene glycol ethyl methyl ether or diethylene glycol dimethyl ether, γ-butyrolactone, γ-valerolactone, δ-valerolactone, carbonic acid Propylene, N- methylpyrrolidone, cyclopentanone, cyclohexanone, cycloheptanone or 2-heptanone and the like.

  (C) As for content of a solvent, 100-2000 mass parts is preferable with respect to 100 mass parts of (a) polysiloxane.

  The photosensitive siloxane composition of the present invention contains (d) a hydroxyimide compound represented by the general formula (2) (hereinafter, “(d) hydroxyimide compound”). (D) By containing a hydroxyimide compound, generation | occurrence | production of a scum can be suppressed in a image development process, and image development time can be shortened.

(Wherein R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group, an aryl group or an alkenyl group. R ⁴ and R ⁵ may be condensed with each other to form a ring structure. .)
When R ⁴ and R ⁵ in the general formula (2) are an alkyl group, an aryl group or an alkenyl group, these alkyl group, aryl group and alkenyl group may be either unsubstituted or substituted. . Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. As an aryl group, a phenyl group, a tolyl group, or a naphthyl group is mentioned, for example. Examples of the alkenyl group include a vinyl group, an acryloxypropyl group, and a methacryloxypropyl group. In addition, R ⁴ and R ⁵ are condensed with each other as a ring structure, such as cyclopentane ring, cyclohexane ring, norbornene ring or adamantane ring or imide ring, cyclopentane ring, cyclohexane ring, norbornene ring, adamantane ring, fluorene ring, benzene Examples include a structure in which a ring, a naphthalene ring, a pyridine ring, a piperazine ring, or the like is bonded. In order to suppress film shrinkage during curing, it is preferable that the (d) hydroxyimide compound does not have these ring structures.

  (D) As the hydroxyimide compound, for example, N-hydroxysuccinimide (NHS), N-hydroxyphthalimide, N-hydroxy-5-norbornene-2,3-dicarboximide (NHI), N-hydroxy-4-nitro Examples thereof include phthalimide or N-hydroxy-1,8-naphthalimide, N, N′-1,2,3,4-cyclobutanetetracarboxydiimide.

(D) As for content of a hydroxyimide compound, 0.01-20 mass parts is preferable with respect to 100 mass parts of (a) polysiloxane, and 0.1-10 mass parts is more preferable. (D) When a hydroxyimide compound is less than 0.01 mass part, high sensitivity may not be expressed. On the other hand, if the amount exceeds 20 parts by mass, the dissolution rate of not only the exposed portion but also the unexposed portion with respect to the developer increases, and as a result, the difference in dissolution rate between the exposed portion and the unexposed portion decreases. The remaining film rate is greatly reduced. Here, the residual film ratio is obtained by applying the composition onto a substrate, pre-baking, and developing the film to obtain a film thickness (I) before development and a film thickness (II) after development. It is a numerical value calculated in 1).
Remaining film ratio (%) = (II) × 100 / (I) (1)
The photosensitive siloxane composition of the present invention preferably contains an epoxy compound and / or an oxetane compound. By containing an epoxy compound and / or an oxetane compound, a cross-linked structure is introduced into the resin after thermosetting, improving hardness and chemical resistance, and developing adhesion to highly hydrophobic substrates such as metal substrates Will improve.

  Examples of the epoxy compound having one epoxy group include KBM303 or KBM403 (both manufactured by Shin-Etsu Chemical Co., Ltd.), Epolite M-1230 or Epolite EHDG-L (all manufactured by Kyoeisha Chemical Co., Ltd.), PP-101. (Manufactured by Tohto Kasei Co., Ltd.) or NK Oligo EA-1010 / ECA (Shin Nakamura Chemical). Examples of the epoxy compound having two epoxy groups include Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 80MF, Epolite 4000 or Epolite 3002 (all of which are Kyoeisha Chemical) Kogyo Co., Ltd.), NC6000 (Nippon Kayaku Co., Ltd.), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L or Denacol EX-850L (all manufactured by Nagase ChemteX Corporation), Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd.), GAN or GOT (both manufactured by Nippon Kayaku Co., Ltd.), Epicoat 828, Epicoat 1002, Epicoat 1750, Epicoat 007, YX8100-BH30, E1256, E4250 or E4275 (all manufactured by Japan Epoxy Co., Ltd.), BPFG, BPEFG or Ogsol PG100 (all manufactured by Osaka Gas Chemical Co., Ltd.), Epicron EXA-9583 or HP4032 (all large) Nippon Ink Chemical Co., Ltd.), EP-4088S, EP-4085S or EP-4080S (all are Adeka Co., Ltd.). Examples of the epoxy compound having three epoxy groups include VG3101 (manufactured by Mitsui Chemicals), Tepic S, Tepic G or Tepic P (manufactured by Nissan Chemical Industries, Ltd.) or Denacol EX-321L (Nagase ChemteX ( Co., Ltd.). Examples of the epoxy compound having four or more epoxy groups include Epototo YH-434L (manufactured by Toto Kasei Co., Ltd.), EPPN502H, NC3000 or NC6000 (all manufactured by Nippon Kayaku Co., Ltd.), Epicron N695 or HP7200 (any (Manufactured by Dainippon Ink & Chemicals, Inc.).

  As the oxetane compound, for example, etanacol EHO, etanacol OXBP, etanacol OXTP or etanacol OXMA (all manufactured by Ube Industries, Ltd.), OX-SC, TMSOX, OX-SQ-H or TEOX-D (all Co., Ltd.) or oxetaneated phenol novolac.

  As for content of an epoxy compound and / or an oxetane compound, 0.1-10 mass parts is preferable with respect to 100 mass parts of (a) polysiloxane. When the epoxy compound and / or the oxetane compound is less than 0.1 part by mass, effects such as improvement in development adhesion are small. On the other hand, when it exceeds 10 mass parts, the colorless transparency of the obtained cured film will fall or the storage stability of a composition will fall.

  If necessary, the photosensitive siloxane composition of the present invention may further include a silane coupling agent, a crosslinking agent, a crosslinking accelerator, a sensitizer, a thermal radical generator, a dissolution inhibitor, a dissolution accelerator, a surfactant, and a stabilizer. Or you may contain additives, such as an antifoamer.

  Adhesiveness with a board | substrate improves because the photosensitive siloxane composition of this invention contains a silane coupling agent.

  Examples of the silane coupling agent include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxy Silane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylene Methyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltri Ethoxysilane, 3-trimethoxysilylpropyl succinic acid, Nt-butyl-3- (3-trimethoxysilylpropyl) succinimide, cyclohexylmethyldimethoxysilane or dicyclopentyldi Tokishishiran and the like.

  As for content of a silane coupling agent, 0.1-10 mass parts is preferable with respect to 100 mass parts of (a) polysiloxane. When the silane coupling agent is less than 0.1 parts by mass, the effect of improving the adhesion is not sufficient. On the other hand, if it exceeds 10 parts by mass, the silane coupling agents may undergo a condensation reaction during storage, which may cause undissolved residue during development.

  When the photosensitive siloxane composition of the present invention contains a crosslinking agent, the degree of crosslinking of the resulting cured film is increased, the chemical resistance and heat-and-moisture resistance of the resulting cured film are improved, and pattern reflow during thermal curing is achieved. The reduction in pattern resolution due to the is suppressed.

  Examples of the crosslinking agent include a compound having a plurality of methylol-based structures represented by the general formula (6), and a compound having a plurality of the same methylol-based structures is preferable.

(In the formula, each R ¹⁵ independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, and an n-decyl group.

  Examples of the compound having two methylol-based structures represented by the general formula (6) include DM-BI25X-F, 46DMOC, 46DMOIPP or 46DMOEP (all manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, dimethylol-Bis-C, dimethylol-BisOC-P, DML- BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL or DML-Bis25X-PCHP (all manufactured by Honshu Chemical Industry Co., Ltd.), Nicarak MX-290 (Sanwa Co., Ltd.) Michal Ltd.), 2,6-dimethoxy-methyl -4-t-butylphenol, and 2,6-dimethoxymethyl -p- cresol or 2,6-acetoxymethyl -p- cresol. Examples of the compound having three methylol-based structures represented by the general formula (6) include TriML-P, TriML-35XL, or TriML-TrisCR-HAP (all manufactured by Honshu Chemical Industry Co., Ltd.). Examples of the compound having four methylol-based structures represented by the general formula (6) include TM-BIP-A (manufactured by Asahi Organic Materials Co., Ltd.), TML-BP, TML-HQ, TML-pp- BPF, TML-BPA or TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), Nikarac MX-280 or Nicalak MX-270 (manufactured by Sanwa Chemical Co., Ltd.) and the like can be mentioned. Examples of the compound having six methylol structures represented by the general formula (6) include HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA or HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.) or Nicarac. MW-390, Nicarak MW-100LM or Nicarac 30-HM (all manufactured by Sanwa Chemical Co., Ltd.) can be used.

  As for content of a crosslinking agent, 0.1-20 mass parts is preferable with respect to 100 mass parts of polysiloxane. If the crosslinking agent is less than 0.1 parts by mass, the resin may be insufficiently crosslinked and may have little effect. On the other hand, when it exceeds 20 mass parts, the colorless transparency of a cured film may fall or the storage stability of a composition may fall.

  When the photosensitive siloxane composition of the present invention contains a crosslinking accelerator, crosslinking of the polysiloxane at the time of thermosetting is promoted. Examples of the crosslinking accelerator include a thermal acid generator that generates an acid during thermal curing, bleaching exposure (exposure wavelength: 365 nm (i-line), 405 nm (h-line), 436 nm (g-line)), or these. A photoacid generator that generates an acid during irradiation of the mixed line). The presence of the acid in the film at the time of thermosetting promotes the condensation reaction of unreacted silanol groups and epoxy groups in the polysiloxane, and increases the degree of crosslinking of the cured film. As a result, the chemical resistance of the cured film is improved, and a decrease in pattern resolution due to pattern reflow during thermosetting is suppressed, or chemical resistance is improved.

  As the thermal acid generator, a compound that does not generate acid (or generates only a small amount) during pre-baking after coating the composition is preferable, and a compound that generates acid at a pre-baking temperature or higher is more preferable. When an acid is generated at a temperature lower than the pre-baking temperature, crosslinking of the alkali-soluble resin is liable to occur during pre-baking, and sensitivity may be lowered, or undissolved residue may be generated during development.

  Examples of the thermal acid generator include Sun-Aid SI-60, SI-80, SI-100, SI-200, SI-110, SI-145, SI-150, SI-60L, and SI-60L. SI-80L, SI-100L, SI-110L, SI-145L, SI-150L, SI-150L, SI-160L, or SI-180L (above, trade name, manufactured by Sanshin Chemical Industry Co., Ltd.) or 4- Hydroxyphenyldimethylsulfonium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenyldimethylsulfonium trifluoromethanesulfonate, 4 -Acetoxy Benzylbenzylmethylsulfonium trifluoromethanesulfonate, 4-methoxycarbonyloxyphenyldimethylsulfonium trifluoromethanesulfonate or benzyl-4-methoxycarbonyloxyphenylmethylsulfonium trifluoromethanesulfonate (trade name, manufactured by Sanshin Chemical Industry Co., Ltd.) Is mentioned.

  As the photoacid generator, a compound that generates a strong acid such as perfluoroalkylsulfonic acid or p-toluenesulfonic acid is preferable.

  Examples of the photoacid generator include SI-100, SI-101, SI-105, SI-106, SI-109, PI-105, PI-106, PI-109, NAI-100, NAI-1002, and NAI. -1003, NAI-1004, NAI-101, NAI-105, NAI-106, NAI-109, NDI-101, NDI-105, NDI-106, NDI-109, PAI-01, PAI-101, PAI-106 Or PAI-1001 (all manufactured by Midori Chemical Co., Ltd.), SP-077 or SP-082 (all manufactured by ADEKA), TPS-PFBS (manufactured by Toyo Gosei Co., Ltd.), CGI-MDT or CGI -NIT (all manufactured by Ciba Japan) or WPAG-281, WPAG-336, WPAG-33 , WPAG-342, WPAG-344, WPAG-350, WPAG-370, WPAG-372, WPAG-449, WPAG-469, WPAG-505 or WPAG-506 (all manufactured by Wako Pure Chemical Industries, Ltd.) It is done.

  The content of the crosslinking accelerator is preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of (a) polysiloxane. If the crosslinking accelerator is less than 0.01 parts by mass, the effect may not be sufficient. On the other hand, if it exceeds 5 parts by mass, polysiloxane may be crosslinked during pre-baking or pattern exposure.

  When the photosensitive siloxane composition of the present invention contains a sensitizer, the reaction of the naphthoquinonediazide compound, which is a photosensitive agent, is promoted to improve sensitivity, and a photoacid generator is contained as a crosslinking accelerator. In this case, the reaction during bleaching exposure is promoted, and the solvent resistance and pattern resolution of the cured film are improved.

  The sensitizer is preferably a sensitizer that vaporizes by heat treatment or a sensitizer that fades by light irradiation in order to prevent a decrease in colorless transparency due to the sensitizer.

  Examples of the sensitizer include coumarins such as 3,3′-carbonylbis (diethylaminocoumarin), anthraquinones such as 9,10-anthraquinone, benzophenone, 4,4′-dimethoxybenzophenone, acetophenone, 4-methoxyacetophenone, benzaldehyde. Aromatic ketones such as biphenyl, 1,4-dimethylnaphthalene, 9-fluorenone, fluorene, phenanthrene, triphenylene, pyrene, anthracene, 9-phenylanthracene, 9-methoxyanthracene, 9,10-diphenylanthracene, 9,10- Bis (4-methoxyphenyl) anthracene, 9,10-bis (triphenylsilyl) anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxy And condensed aromatics such as nthracene, 9,10-dibutoxyanthracene, 9,10-dipentaoxyanthracene, 2-t-butyl-9,10-dibutoxyanthracene, and 9,10-bis (trimethylsilylethynyl) anthracene. It is done.

  As a vaporization temperature of a sensitizer, 130-400 degreeC is preferable and 150-250 degreeC is more preferable. If the vaporization temperature of the sensitizer is less than 130 ° C., the sensitizer is vaporized during pre-baking and is not present during the exposure process, and the sensitivity may not be increased. On the other hand, if the vaporization temperature of the sensitizer exceeds 400 ° C., the sensitizer does not vaporize during thermal curing and remains in the cured film, and the colorless transparency may be lowered.

  The sensitizer that fades by light irradiation is preferably dimerized by light irradiation. By dimerization, the molecular weight increases to insolubilize, and it becomes possible to improve chemical resistance, heat resistance and reduce the extract from the transparent cured film. Such a sensitizer is preferably an anthracene compound, more preferably a 9,10-disubstituted anthracene compound having higher stability, and a 9,10-dialkoxyanthracene compound represented by the general formula (7). Is more preferable.

(In the formula, R ^{16 to} R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. Or an aryl group having 1 to 20 carbon atoms, and R ²⁴ and R ²⁵ each independently represents an alkoxy group having 1 to 20 carbon atoms).

When R ^{16 to} R ²³ in the general formula (7) are an alkyl group, an alkoxy group, an alkenyl group, an aryl group or an acyl group, these alkyl group, alkoxy group, alkenyl group, aryl group and acyl group are unsubstituted. It may be either a body or a substituted body. Examples of the alkyl group include a methyl group, an ethyl group, and an n-propyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group. Examples of the alkenyl group include a vinyl group, an acryloxypropyl group, and a methacryloxypropyl group. As an aryl group, a phenyl group, a tolyl group, or a naphthyl group is mentioned, for example. Examples of the acyl group include an acetyl group. R ^{16 to} R ²³ are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms from the viewpoint of the vaporization property of the compound and the photodimerization reactivity, and R ¹⁶ , R ¹⁹ , R ²⁰ and R ²³ are More preferably, it is a hydrogen atom.

The alkoxy group as R ²⁴ and R ²⁵ in the general formula (7) may be either unsubstituted or substituted. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group or a pentyloxy group. From the viewpoint of excellent solubility of the compound and facilitating a fading reaction due to photodimerization, a propoxy group or a butoxy group. Is preferred.

  As for content of a sensitizer, 0.01-5 mass parts is preferable with respect to 100 mass parts of polysiloxane. If it is out of this range, the transparency may be lowered or the sensitivity may be lowered.

  When the photosensitive siloxane composition of the present invention contains a surfactant, coating unevenness is improved and a uniform coating film is obtained.

  As the surfactant, a fluorine-based surfactant or a silicone-based interface chemical is preferable.

  Examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,1) 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8, 8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- 3- (Perfluorooctanesulfonamido) propyl] -N, N′-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine salt, bisphosphate (N-perfluorooctylsulfonyl-N-ethylaminoethyl) or monoperfluoroalkylethyl phosphate ester. Examples of commercially available fluorosurfactants include Megafac F142D, F172, F173, F183, F183, F410, F430, F444, 445, F475, 477, F552, F553, F554, F555 or R-08 (all manufactured by DIC Corporation), F-top EF301, 303 or 352 (all manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC-430 or FC -431 (both manufactured by Sumitomo 3M)), "Asahi Guard" AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, or SC-105 SC-106 (all manufactured by Asahi Glass Co., Ltd.), BM-1000 or BM-1100 (all ) Ltd.) or NBX-15, FTX-218 or DFX-218 (both include Corp. Neos).

  Examples of commercially available silicone surfactants include SH28PA, SH7PA, SH21PA, SH30PA or ST94PA (all manufactured by Toray Dow Corning Silicone Co., Ltd.) or BYK-333 (manufactured by Big Chemie Japan Co., Ltd.). Can be mentioned.

  The surfactant content is generally 0.0001 to 1% by mass in the photosensitive composition.

  A method for forming a cured film using the photosensitive siloxane composition of the present invention will be described.

  The photosensitive siloxane composition of the present invention is applied onto a base substrate by a known method such as a spinner or a slit, and prebaked with a heating device such as a hot plate or an oven. Pre-baking is performed in the range of 50 to 150 ° C. for 30 seconds to 30 minutes, and the film thickness after pre-baking is preferably 0.1 to 15 μm.

After pre-baking, about 10 to 4000 J / m ² (wavelength 365 nm exposure amount conversion) is desired using an ultraviolet-visible exposure machine such as a stepper, mirror projection mask aligner (MPA) or parallel light mask aligner (hereinafter referred to as “PLA”). The pattern is exposed through the mask.

  After exposure, the exposed portion is dissolved by development, and a positive pattern can be obtained. As a developing method, it is preferable to immerse in a developing solution by a method such as shower, dipping or paddle for 5 seconds to 10 minutes. As the developer, a known alkali developer can be used. Examples of known alkali developers include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates, and borates, and amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine. Alternatively, an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or choline can be used. Moreover, it is preferable to rinse with water after development, and if necessary, dehydration drying baking can be performed in a range of 50 to 150 ° C. with a heating device such as a hot plate or an oven.

Thereafter, it is preferable to perform bleaching exposure. By performing bleaching exposure, the unreacted naphthoquinonediazide compound remaining in the film is photodecomposed, and the light transparency of the film is further improved. As a bleaching exposure method, an entire surface is exposed to about 100 to 20000 J / m ² (wavelength 365 nm exposure amount conversion) using an ultraviolet-visible exposure machine such as PLA.

  The film subjected to bleaching exposure is soft-baked for 30 seconds to 30 minutes in a range of 50 to 150 ° C. with a heating device such as a hot plate or an oven, if necessary, and then 150 to about 150 to about 150 with a heating device such as a hot plate or an oven. By curing at 450 ° C. for about 1 hour, a flattened film for TFT in the liquid crystal display element, an interlayer insulating film in the semiconductor element, or a core or cladding material in the optical waveguide is formed.

  The cured film formed using the photosensitive siloxane composition of the present invention preferably has a light transmittance of 90% or more per film thickness of 3 μm at a wavelength of 400 nm, more preferably 95% or more. When the light transmittance is less than 90%, when used as a planarizing film for a TFT substrate in a liquid crystal display element, a color change occurs when the backlight passes, and the white display becomes yellowish.

The transmittance per film thickness of 3 μm at a wavelength of 400 nm of the cured film is determined by the following method. First, the composition is spin-coated on a Tempax glass plate at an arbitrary rotational speed using a spin coater, and prebaked at 100 ° C. for 2 minutes using a hot plate. Then, as bleaching exposure, using PLA, the whole surface of the film was exposed to an ultrahigh pressure mercury lamp at 3000 J / m ² (wavelength 365 nm exposure amount conversion), and thermally cured at 220 ° C. for 1 hour in air using an oven. A 3 μm cured film is formed. The ultraviolet-visible absorption spectrum of the obtained cured film is measured using an ultraviolet-visible spectrophotometer (MultiSpec-1500; manufactured by Shimadzu Corporation) to determine the transmittance at a wavelength of 400 nm.

  The element having the cured film of the present invention refers to a display element, a semiconductor element or an optical waveguide material having the cured film of the present invention. Among them, a liquid crystal display element having the cured film of the present invention as a planarizing film for TFT, organic An EL display element or a display element with a touch panel function is preferable.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. Here, Example 6 is to be read as Comparative Example 4. In addition, it shows below about what used the abbreviation among the used compounds.
DAA: diacetone alcohol PGMEA: propylene glycol monomethyl ether acetate EDM: diethylene glycol ethyl methyl ether DPM: dipropylene glycol methyl ether 1-PA: 1-pentanol In addition, solid content concentration of polysiloxane solution and acrylic resin solution, polysiloxane The weight average molecular weight (Mw) of the acrylic resin and the content ratio of the phenyl group-substituted silane in the polysiloxane were determined by the following methods.

(1) Solid content concentration 1 g of a polysiloxane solution or an acrylic resin solution was weighed in an aluminum cup and heated at 250 ° C. for 30 minutes using a hot plate to evaporate the liquid content. The solid content remaining in the heated aluminum cup was weighed to determine the solid content concentration of the polysiloxane solution or acrylic resin.

(2) Weight average molecular weight The weight average molecular weight was determined by GPC (410 type RI detector; manufactured by Waters; fluidized bed: tetrahydrofuran) in terms of polystyrene.

(3) Content ratio of phenyl group-substituted silane in polysiloxane
²⁹ Si-NMR was measured, and the ratio of the integrated value of the phenyl group-substituted silane was calculated from the total integrated value, and the ratio was calculated. The sample (liquid) was injected into a Teflon (registered trademark) NMR sample tube having a diameter of 10 mm and used for measurement. The measurement conditions for ²⁹ Si-NMR are shown below.
Device: JNM GX-270 (manufactured by JEOL Ltd.)
Measurement method: Gated decoupling method Measurement nuclear frequency: 53.6669 MHz ( ²⁹ Si nucleus)
Spectrum width: 20000Hz
Pulse width: 12μsec (45 ° pulse)
Pulse repetition time: 30.0 sec
Solvent: acetone-d6
Reference material: Tetramethylsilane Measurement temperature: Room temperature Sample rotation speed: 0.0 Hz
(Synthesis Example 1 Synthesis of Polysiloxane Solution (a))
In a 500 mL three-necked flask, 13.62 g (0.10 mol) of methyltrimethoxysilane, 118.98 g (0.60 mol) of phenyltrimethoxysilane, 73 of (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 73 .92 g (0.3 mol) and 195.89 g of DAA were charged, and an aqueous phosphoric acid solution prepared by dissolving 0.54 g of phosphoric acid in 55.8 g of water was added over 10 minutes while stirring at room temperature. After stirring for 30 minutes, the oil bath was heated to 115 ° C. over 30 minutes, 1 hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and then heated and stirred for 3 hours. (Inner temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (a), with 0.05 L / min of nitrogen flowing during heating and stirring. Methanol, water issued total 125g distillate is formed thereof.

  The obtained polysiloxane solution (a) had a solid content concentration of 41% by mass, and the polysiloxane had a weight average molecular weight of 3000. The content ratio of the phenyl group-substituted silane in the polysiloxane was 60% in terms of Si atom molar ratio.

(Synthesis Example 2 Synthesis of Polysiloxane Solution (b))
In a 500 mL three-necked flask, 13.62 g (0.10 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, and 98 of (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were added. .56 g (0.4 mol) and 179.5 g of DAA were charged, and an aqueous phosphoric acid solution containing 0.54 g of phosphoric acid dissolved in 55.8 g of water was added over 10 minutes while stirring at room temperature. After stirring for 30 minutes, the oil bath was heated to 115 ° C. over 30 minutes 1 hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and then heated and stirred for 2 hours. (Inner temperature is 100 to 110 ° C.) to obtain a polysiloxane solution (b) Nitrogen was allowed to flow at 0.05 L / min during heating and stirring. Methanol, water has issued a total of 121g distillate is.

  The resulting polysiloxane solution (b) had a solid content concentration of 42% by mass and a polysiloxane weight average molecular weight of 3,200. The content ratio of the phenyl group-substituted silane in the polysiloxane was 50% in terms of Si atom molar ratio.

(Synthesis Example 3 Synthesis of Polysiloxane Solution (c))
In a 500 mL three-necked flask, 27.24 g (0.37 mol) of methyltrimethoxysilane, 118.98 g (0.60 mol) of phenyltrimethoxysilane, 49 of (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane .28 g (0.03 mol) and 195.89 g of DAA were charged, and an aqueous phosphoric acid solution in which 0.54 g of phosphoric acid was dissolved in 55.8 g of water was added over 10 minutes while stirring at room temperature. After stirring for 30 minutes, the oil bath was heated to 115 ° C. over 30 minutes, 1 hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and then heated and stirred for 3 hours. (Inner temperature is 100 to 110 ° C.) to obtain a polysiloxane solution (c) Nitrogen was allowed to flow at 0.05 L / min during heating and stirring. Methanol is a product, water has issued a total 125g distilled.

  The resulting polysiloxane solution (c) had a solid content concentration of 41% by mass, and the polysiloxane had a weight average molecular weight of 3000. In addition, the content ratio of the phenyl group-substituted silane in the polysiloxane was 60% in terms of Si atom molar ratio.

(Synthesis Example 4 Synthesis of Polysiloxane Solution (d))
In a 500 mL three-necked flask, 40.86 g (0.30 mol) of methyltrimethoxysilane, 99.15 g (0.5 mol) of phenyltrimethoxysilane, 12 of (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane .32 g (0.05 mol), 17.63 g (0.15 mol) of M silicate 51 (manufactured by Tama Chemical Co., Ltd.) and 170.77 g of PGMEA were charged, and phosphoric acid was added to 53.55 g of water while stirring at room temperature. An aqueous phosphoric acid solution containing 51 g was added over 10 minutes, and then the flask was immersed in an oil bath at 40 ° C. and stirred for 30 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. After 1 hour, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.). To obtain a solution (d). Note that, in heating and stirring, methanol, water gave a total 125g distillate is nitrogen was flowed 0.05 L / min. By-products during the reaction.

  The obtained polysiloxane solution (d) had a solid content concentration of 43% by mass, and the polysiloxane had a weight average molecular weight of 8,500. The content ratio of the phenyl group-substituted silane in the polysiloxane was 50% in terms of Si atom molar ratio.

(Synthesis Example 5 Synthesis of Polysiloxane Solution (e))
In a 500 mL three-necked flask, 13.62 g (0.10 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, 24 of (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane .64 g (0.10 mol), 35.25 g (0.30 mol) of M silicate 51 (manufactured by Tama Chemical Co., Ltd.) and 181.89 g of PGMEA were charged, and phosphoric acid was added to 62.64 g of water while stirring at room temperature. An aqueous phosphoric acid solution in which 60 g was dissolved was added over 10 minutes, and then the flask was immersed in an oil bath at 40 ° C. and stirred for 30 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. After 1 hour, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.). To obtain a down solution (e). Note that, in heating and stirring, methanol, water gave a total 150g distillate is nitrogen was flowed 0.05 L / min. By-products during the reaction.

  The obtained polysiloxane solution (e) had a solid content concentration of 44% by mass, and the polysiloxane had a weight average molecular weight of 11,400. The content ratio of the phenyl group-substituted silane in the polysiloxane was 50% in terms of Si atom molar ratio.

(Synthesis Example 6 Synthesis of Polysiloxane Solution (f))
In a 500 mL three-necked flask, 20.43 g (0.15 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, 61 of (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 61 .58 g (0.25 mol), 11.76 g (0.10 mol) of M silicate 51 (manufactured by Tama Chemical Co., Ltd.) and 181.89 g of PGMEA were charged, and phosphoric acid was added to 62.64 g of water while stirring at room temperature. An aqueous phosphoric acid solution in which 60 g was dissolved was added over 10 minutes, and then the flask was immersed in an oil bath at 40 ° C. and stirred for 30 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. After 1 hour, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.). Down to give solution (f). In addition, during heating and stirring, methanol, water gave a total 150g distillate is nitrogen was flowed 0.05 L / min. By-products during the reaction.

  The resulting polysiloxane solution (f) had a solid content concentration of 44% by mass, and the polysiloxane had a weight average molecular weight of 11400. The content ratio of the phenyl group-substituted silane in the polysiloxane was 50% in terms of Si atom molar ratio.

(Synthesis Example 7 Synthesis of Polysiloxane Solution (g))
A 500 mL three-necked flask was charged with 81.72 g (0.60 mol) of methyltrimethoxysilane, 79.32 g (0.40 mol) of phenyltrimethoxysilane, and 163.1 g of PGMEA, and stirred at room temperature to 55.8 g of water. A phosphoric acid aqueous solution in which 0.54 g of phosphoric acid was dissolved was added over 10 minutes. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 30 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 1.5 hours (the internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (g). During the heating and stirring, nitrogen was flowed at 0.05 L / min. During the reaction, a total of 131 g of methanol and water as by-products were distilled out.

  The obtained polysiloxane solution (g) had a solid content concentration of 43% by mass, and the polysiloxane had a weight average molecular weight of 4,200. The content ratio of the phenyl group-substituted silane in the polysiloxane was 40% in terms of Si atom molar ratio.

(Synthesis Example 8 Synthesis of Acrylic Resin Solution (a))
A 500 mL flask was charged with 5 g of 2,2′-azobis (isobutyronitrile), 5 g of t-dodecanethiol, and 180 g of PGMEA. Thereafter, 40 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged, stirred at room temperature, and the atmosphere in the flask was replaced with nitrogen. And stirred for 5 hours. Next, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine and 0.2 g of p-methoxyphenol were added to the resulting solution, and the mixture was heated and stirred at 90 ° C. for 4 hours to obtain an acrylic resin solution (a). .

  The resulting acrylic resin solution (a) had a solid content concentration of 40% by mass, the acrylic resin had a weight average molecular weight of 12,000, and an acid value of 91 mgKOH / g.

(Synthesis Example 9 Synthesis of Naphthoquinonediazide Compound (a))
Under a nitrogen stream, 21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 26.87 g (0.10 mol) of 5-naphthoquinone diazide sulfonyl chloride were added to 1,4-dioxane. Dissolved in 450 g and brought to room temperature. Here, 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a naphthoquinonediazide compound (a) having the following structure.

(Synthesis Example 10 Synthesis of Naphthoquinonediazide Compound (b))
Under a dry nitrogen stream, TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 15.32 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 22.84 g (0.085 mol) were added to 1,4-dioxane. Dissolved in 450 g and brought to room temperature. Here, 11.13 g (0.11 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a naphthoquinonediazide compound (b) having the following structure.

(Synthesis Example 11 Synthesis of Naphthoquinonediazide Compound (c))
Under a dry nitrogen stream, 15.32 g (0.05 mol) of Ph-cc-AP-MF (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 37.62 g (0.14 mol) of 5-naphthoquinone diazide sulfonyl chloride 1 , 4-Dioxane was dissolved in 450 g and brought to room temperature. Here, 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a naphthoquinonediazide compound (c) having the following structure.

(Synthesis Example 12 Synthesis of Naphthoquinonediazide Compound (d))
A naphthoquinonediazide compound (d) having the following structure was obtained in the same manner as in Synthesis Example 9 except that the amount of 5-naphthoquinonediazidesulfonyl acid chloride was changed to 33.59 g (0.125 mol).

Example 1
35.51 g of the polysiloxane solution (a) obtained in Synthesis Example 1, 1.02 g of the naphthoquinone diazide compound (d) obtained in Synthesis Example 12, DAA 6.50 g, PGMEA 4.84 g as a solvent, NHI 0. 73 g, 0.44 g of KBM303 as an epoxy compound, 0.73 g of OX-SC as an oxetane compound, and 0.03 g of BYK333 as a surfactant were mixed and stirred under a yellow light to obtain a uniform solution, and then filtered through a 0.45 μm filter. Thus, composition 1 was prepared.

The composition 1 was spin-coated at an arbitrary number of revolutions using a silicon wafer and an OA-10 glass plate (manufactured by Nippon Electric Glass Co., Ltd. using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.), and then a hot plate ( Daiwa Screen Manufacturing Co., Ltd. SCW-636) was pre-baked at 90 ° C. for 2 minutes to form a film with a thickness of 3 μm. The formed film was PLA) (PLA-501F; manufactured by Canon Inc.). Using an ultra-high pressure mercury lamp through pattern exposure through a gray scale mask for sensitivity measurement, 2.38 mass% tetramethylammonium hydroxide using an automatic developing device (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.) Shower development was performed for 90 seconds with ELM-D (Mitsubishi Gas Chemical Co., Ltd.) which is an aqueous solution, and then rinsed with water for 30 seconds. Then, as bleaching exposure, using PLA, the whole surface of the film was exposed to 3000 J / m ² (wavelength 365 nm exposure amount conversion) with an ultrahigh pressure mercury lamp.

  Then, it soft-baked at 110 degreeC for 2 minute (s) using the hotplate, and then cured for 1 hour at 230 degreeC in air using oven (IHPS-222; product made by Tabai Espec Co., Ltd.), and formed the cured film.

  Table 2 shows the evaluation results of the photosensitive characteristics and the cured film characteristics. The evaluation in the table was performed by the following method.

(4) Film thickness measurement A lambda ace STM-602 (manufactured by Dainippon Screen) was used to measure at a refractive index of 1.50.

(5) Film thickness reduction in unexposed area during development The film thickness reduction in the unexposed area during development was calculated according to the following equation (1).
Reduction in film thickness at unexposed area = film thickness before development-film thickness after development at unexposed rear part (1)
(6) Calculation of sensitivity After exposure and development, the exposure amount (hereinafter referred to as “optimum exposure amount”) for forming a 10 μm line-and-space pattern in a one-to-one width was defined as sensitivity.

(7) Calculation of resolution The minimum pattern size after development at the optimum exposure amount was taken as post-development resolution, and the minimum pattern size after cure was taken as post-cure resolution.

(8) Heat resistance The cured film formed by the method described in Example 1 is scraped from the substrate, about 10 mg is put into an aluminum cell, and nitrogen is used using a thermogravimetric apparatus (TGA-50; manufactured by Shimadzu Corporation). In the atmosphere, the mixture was heated to 150 ° C. at a temperature rising rate of 10 ° C./min, held at 150 ° C. for 1 hour, and then heated to 400 ° C. at a temperature rising rate of 10 ° C./min. At this time, the temperature Td1% at which the mass reduction was 1% was measured and compared. The higher the Td1%, the better the heat resistance.

(9) Measurement of light transmittance First, only the OA-10 glass plate was measured using MultiSpec-1500, and the ultraviolet-visible absorption spectrum was used as a reference. Next, a cured film of the composition is formed on the OA-10 glass plate (pattern exposure is not performed), this sample is measured with a single beam, and the light transmittance at a wavelength of 400 nm per 3 μm is obtained. The difference was the light transmittance of the cured film.

(10) Evaluation of development margin Composition 1 was spin-coated on a silicon wafer at an arbitrary number of revolutions using a spin coater and then pre-baked at 90 ° C. for 2 minutes using a hot plate to form a film having a thickness of 3 μm. . The formed film was exposed using PLA (PLA-501F; manufactured by Canon Inc.) at an exposure amount corresponding to the sensitivity value determined by the above sensitivity calculation, and then 2.38 mass% hydroxylated. Shower development was carried out using ELM-D, which is an aqueous tetramethylammonium solution, with different development times, followed by rinsing with water for 30 seconds. At this time, the development time required to form a 10 μm line-and-space pattern with a one-to-one width was defined as the optimum development time. Further, when the development was further shortened from the optimum development time, the time until the occurrence of scum in the 10 μm line pattern was measured and used as a development margin. When this value is 30 seconds or more, it can be said that the development margin is good.

(11) Adhesion to metal substrate The composition 1 was spin-coated on the metal substrate at an arbitrary rotation number using a spin coater, and then pre-baked at 90 ° C. for 2 minutes using a hot plate to form a film having a thickness of 3 μm. Formed. The formed film was exposed to an exposure amount corresponding to the sensitivity value determined by the above-described sensitivity calculation using PLA, and then ELM-D, which is an aqueous 2.38 mass% tetramethylammonium hydroxide solution. Shower development was carried out while changing the development time, followed by rinsing with water for 30 seconds. At this time, the development time required to form a 10 μm line-and-space pattern with a one-to-one width was defined as the optimum development time. Further, when the development was further continued from the optimum development time, the time until the 10 μm line pattern was peeled was measured to evaluate the adhesion to the metal substrate. The case where this value was 30 seconds or more was judged as 値, the case where it was 15 seconds or more and less than 30 seconds, ○, and the case where it was less than 15 seconds was judged as ×.

(Examples 2-9 and Comparative Examples 1-3)
Similar to Composition 1, Compositions 2 to 12 were prepared with the compositions shown in Table 1. NHI and NHS used as the hydroxyimide compound are N-hydroxy-5-norbornene-2, 3-dicarboximide and N-hydroxysuccinimide manufactured by Osaka Synthetic Organic Chemistry Laboratory Co., Ltd. KBM303 and KBM403 used as the epoxy compounds are 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd. NC6000 (Nippon Kayaku Co., Ltd.) used as an epoxy compound and OX-SC (Toagosei Co., Ltd.) used as an oxetane compound are compounds having the structures shown below. KBM-04 and CHMS-112 used as silane coupling agents are tetramethoxysilane and cyclohexylmethyldimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd. F477 (manufactured by DIC Corporation) used as a surfactant is a perfluoroalkyl group-containing oligomer (structure not disclosed), and BYK333 (manufactured by Big Chemie Japan Co., Ltd.) is a polyether-modified polydimethylsiloxane and poly (polysiloxane). It is a mixture of ethers (structure not disclosed).

  Each composition was evaluated in the same manner as in Example 1 using each obtained composition. However, in the evaluation of the acrylic resin, the development was performed by shower development with a 0.4 mass% tetramethylammonium hydroxide aqueous solution for 90 seconds. The results are shown in Table 2.

  Examples 1 to 9 had high light transmittance, a good development margin, and good adhesion to the metal substrate in the development process. In Comparative Example 1, the adhesion to the metal was slightly good, but since it was an acrylic resin, it was a cured film with insufficient heat resistance and transparency. On the other hand, since Comparative Example 2 did not contain epoxy or oxetane in the polymer, the adhesion to metal was poor. On the other hand, since Comparative Example 3 did not contain a specific hydroxyimide compound, it did not have a good development margin.

  The photosensitive siloxane composition of the present invention is a flattening film for a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element, a protective film or insulating film for a touch panel, an interlayer insulating film for a semiconductor element, or a flat surface for a solid-state imaging element. It is used to form a chemical film, a microlens array pattern, or a core or cladding material of an optical waveguide.

Claims (4)

(A) a polysiloxane having an epoxy structure and / or an oxetane structure,
(B) a naphthoquinonediazide compound,
(C) a solvent, and
(D) a photosensitive siloxane composition containing a hydroxyimide compound represented by the general formula (2),
(A) The ratio of the epoxy structure and oxetane structure in the polysiloxane having an epoxy structure and / or oxetane structure is 5 mol% or more based on Si atoms in the polysiloxane having (a) the epoxy structure and / or oxetane structure. The (a) polysiloxane having an epoxy structure and / or oxetane structure is a photosensitive siloxane composition, which is a reaction product of a monomer containing an organosilane represented by the general formula (1).

(In the formula, each R ¹ independently represents an organic group having 1 to 15 carbon atoms having an epoxy structure or an oxetane structure, and each R ² independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, Represents an alkenyl group having 2 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and each R ³ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or carbon. Represents an aryl group of formulas 6 to 15, n represents an integer of 1 to 3, m represents an integer of 0 to 2 (where n + m is an integer of 1 to 3))

(Wherein R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group, an aryl group or an alkenyl group. R ⁴ and R ⁵ may be condensed with each other to form a ring structure. .) Further containing an epoxy compound and / or oxetane compound, according to claim 1 Symbol placement of photosensitive siloxane composition. Formed of claims 1 or 2, photosensitive siloxane composition according the cured film. An element comprising the cured film according to claim 3 .