JP5181968B2 - Positive photosensitive composition, method for producing cured film, cured film, and element having cured film - Google Patents

Description

  The present invention relates to a photosensitive composition for forming a planarization film for a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element, an interlayer insulating film of a semiconductor element, or a core or cladding material of an optical waveguide, and The present invention relates to a formed cured film and an element having the cured film.

  In recent years, a method for increasing the aperture ratio of a display device is known as a method for realizing higher definition and higher resolution in a liquid crystal display, an organic EL display, and the like (see Patent Document 1). This is a method in which the data line and the pixel electrode can be overlapped by providing a transparent flattening film as a protective film on the TFT substrate, and the aperture ratio is increased as compared with the prior art.

  As a material for such a planarization film for a TFT substrate, a material having high heat resistance and high transparency and having positive photosensitivity is required. Furthermore, excellent alkali resistance is required for cured films. As typical materials, materials in which an acrylic resin is combined with a quinonediazide compound are known (see Patent Documents 2 and 3). However, these materials have insufficient heat resistance, and are cured by high-temperature treatment of the substrate. There is a problem of strong coloring.

  Polyimide is known as a material having high heat resistance, and a positive type material using this is also known (Patent Document 4). However, these materials did not have sufficient initial transmittance.

  Further, as another material having high heat resistance and high transparency, polysiloxane is known, and a material in which a quinonediazide compound is combined in order to impart positive photosensitivity (see Patent Document 5). )It has been known. These materials are highly transparent, and a highly transparent cured film can be obtained without lowering the transparency even when the substrate is treated at high temperature. Further, by using polysiloxane and a (meth) acrylic polymer in combination, it has higher heat resistance and transparency than a material using an acrylic resin, and is more sensitive than using a siloxane resin. When the (meth) acrylic polymer contains a carboxylic acid, it is soluble in a low-concentration developer such as a 0.2 to 0.8 wt% tetramethylammonium hydroxide (TMAH) aqueous solution and forms a good pattern. It has been found that a material is possible.

  Incidentally, in recent years, with an increase in the size of a glass substrate used for production of a liquid crystal display, there has been a demand for higher sensitivity of a transparent positive photosensitive composition. However, it has been difficult to achieve high sensitivity especially with a low-concentration developer.

In addition, a positive photosensitive composition containing a quinonediazide compound having a specific structure has been reported so far (Patent Document 6). Many of these have improved heat resistance of quinonediazide or solubility in a solvent. It is being studied as a purpose.
JP-A-9-152625 (Claim 1) JP 2001-281853 A (Claim 1) Japanese Patent Laid-Open No. 2001-281861 (Claim 1) JP 2001-5179 A (Claims 1 to 5) JP 2006-178436 A (Claim 1) JP 2004-117999 A (Claim 1)

The present invention has been made based on the circumstances as described above, has high heat resistance and high transparency, has good sensitivity even when a low concentration developer is used, and is excellent in a cured film. The present invention provides a positive photosensitive composition having alkali resistance.

  Another object of the present invention is to provide a planarized film for TFT substrate, an interlayer insulating film, a cured film such as a core and a clad material, and a display element and a semiconductor having the cured film formed from the photosensitive composition. An element such as an element or an optical waveguide is provided.

  That is, the present invention comprises (a) polysiloxane, (b) (meth) acrylic polymer, (c) a quinonediazide compound represented by the general formula (1), and (d) a solvent. Composition.

(In the formula, R ¹ represents hydrogen or an alkyl group selected from 1 to 8 carbon atoms. R ² , R ³ and R ⁴ represent a hydrogen atom, an alkyl group selected from 1 to 8 carbon atoms, an alkoxyl group and a carboxyl group. Each of R ² , R ³ and R ⁴ may be the same or different, Q represents either a 5-naphthoquinonediazidosulfonyl group or a hydrogen atom, (Not all become hydrogen atoms. A, b, c, α, and β are integers of 0 to 4, provided that α + β ≧ 3.)

  According to the positive photosensitive composition of the present invention, a cured film having a high sensitivity and a high heat resistance and a high transparency can be obtained even when a low concentration developer is used. The obtained cured film has excellent alkali resistance, and can be suitably used as a planarizing film for TFT substrate or an interlayer insulating film.

  The present invention is a positive photosensitive composition containing (a) polysiloxane, (b) (meth) acrylic polymer, (c) a quinonediazide compound represented by the general formula (1), and (d) a solvent.

(In the formula, R ¹ represents hydrogen or an alkyl group selected from 1 to 8 carbon atoms. R ² , R ³ and R ⁴ represent a hydrogen atom, an alkyl group selected from 1 to 8 carbon atoms, an alkoxyl group and a carboxyl group. Each of R ² , R ³ and R ⁴ may be the same or different, Q represents either a 5-naphthoquinonediazidosulfonyl group or a hydrogen atom, (Not all become hydrogen atoms. A, b, c, α, and β are integers of 0 to 4, provided that α + β ≧ 3.)
The photosensitive composition containing a quinonediazide compound forms a positive type in which the exposed portion is removed with a developer. The quinonediazide compound used in the present invention desirably has a structure represented by the general formula (1). By using such a quinonediazide compound having a rigid and asymmetric skeleton, it is possible to reduce the dissolution inhibiting effect due to the interaction between the quinonediazide and the silanol group of the polysiloxane.

  As a result, when using a low-concentration developer such as a 0.2 to 0.8 wt% TMAH aqueous solution, the effect of increasing sensitivity is obtained by using the quinonediazide compound having the structure represented by the general formula (1). Get higher. In particular, when a 0.2 to 0.5 wt% TMAH aqueous solution is used, the effect of increasing sensitivity is higher.

In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. When the number of carbon atoms is larger than 8, the hydrophobicity becomes too large, so that the solubility of the exposed portion in the alkaline developer is lowered, and there is a possibility that the sensitivity is lowered. From such points, R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

In the general formula (1), R ² , R ³ , and R ^{4 each} represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group, a carboxyl group, or an ester group, and each R ² , R ³ , R ⁴ may be the same or different. When the number of carbon atoms is larger than 8, the hydrophobicity becomes too large, so that the solubility of the exposed portion in the alkaline developer is lowered, and there is a possibility that the sensitivity is lowered. From such points, R ² , R ³ and R ⁴ are preferably any one of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group, a carboxyl group, and an ester group. a, b, c, α, and β are integers from 0 to 4. However, α + β ≧ 3. When α + β is 1 or 2, the interaction with the polysiloxane does not occur effectively, so there is a possibility that the difference in dissolution rate between the exposed part and the unexposed part does not occur and the sensitivity is lowered.

  Examples of the (c) quinonediazide compound represented by the general formula (1) include, but are not limited to, those shown below.

  In the general formula (1), Q represents either a 5-naphthoquinonediazidosulfonyl group or a hydrogen atom. In the present invention, not all of Q are hydrogen atoms.

  Although the addition amount of the quinonediazide compound is not particularly limited, it is preferably 6 to 25 parts by weight, more preferably 8 to 18 parts by weight with respect to 100 parts by weight of the resin (polysiloxane + (meth) acrylic polymer). When the addition amount of the quinonediazide compound is less than 6 parts by weight, the remaining film ratio in the unexposed part is lowered. On the other hand, when the addition amount of the quinonediazide compound is more than 25 parts by weight, the light transmittance of the cured film is lowered.

The photosensitive composition of the present invention contains (a) polysiloxane. The structure of the polysiloxane is not particularly limited, but a preferred embodiment includes a polysiloxane obtained by mixing and reacting at least one organosilane represented by the general formula (2).

R ⁵ represents any one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ⁵ may be the same or different. . R ⁶ represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ⁵ may be the same or different. . m represents an integer of 0 to 3.

Any of the alkyl group, alkenyl group, and aryl group listed as R ⁵ in the general formula (2) may have a substituent, or may have an unsubstituted form having no substituent. It can be selected according to the characteristics of the composition. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 2,2 , 2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, 3-mercaptopropyl Group, 3-isocyanatopropyl group. Specific examples of the alkenyl group include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group. Specific examples of the aryl group include phenyl group, tolyl group, p-hydroxyphenyl group, 1- (p-hydroxyphenyl) ethyl group, 2- (p-hydroxyphenyl) ethyl group, 4-hydroxy-5- (p -Hydroxyphenylcarbonyloxy) pentyl group, naphthyl group.

Any of the alkyl group and the acyl group listed as R ⁶ in the general formula (2) may have a substituent, or may be an unsubstituted form having no substituent. It can be selected according to the characteristics. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Specific examples of the acyl group include an acetyl group. Specific examples of the aryl group include a phenyl group.

  M in the general formula (2) represents an integer of 0 to 3. A tetrafunctional silane when m = 0, a trifunctional silane when m = 1, a bifunctional silane when m = 2, and a monofunctional silane when n = 3.

  Specific examples of the organosilane represented by the general formula (2) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and methyl. Triisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyl Trimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methyl Acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ) Ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxy Silane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimeth Trifunctional silanes such as silane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Examples thereof include bifunctional silanes such as dimethyldiacetoxysilane, di n-butyldimethoxysilane, and diphenyldimethoxysilane, and monofunctional silanes such as trimethylmethoxysilane and tri n-butylethoxysilane.

  Of these organosilanes, trifunctional silanes are preferably used from the viewpoint of crack resistance and hardness of the cured film. Moreover, these organosilanes may be used alone or in combination of two or more.

  In order to improve the alkali resistance after the formation of the cured film, the polysiloxane (a) of the present invention preferably contains an epoxy group, and is used for the synthesis of the polysiloxane of the organosilane represented by the general formula (2). At least one is preferably 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, or 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Furthermore, in order to improve the alkali resistance after forming the cured film, it is preferable that (a) the polysiloxane contains an ethylenically unsaturated group. In particular, at least one of the organosilanes represented by the general formula (2) used for polysiloxane synthesis is vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltri It is preferably either ethoxysilane or 3-acryloxypropyltrimethoxysilane. More preferably, the content of ethylenically unsaturated groups in the polysiloxane is preferably 5 to 45 mol% with respect to Si atoms. If the content of the ethylenically unsaturated group is larger than 50 mol%, a residue is likely to be generated in the removal pattern during development. If the ethylenically unsaturated group is smaller than 5 mol%, sufficient alkali resistance cannot be obtained.

Further, in the polysiloxane, the content of the phenyl group in the polysiloxane is preferably 20 to 70 mol%, more preferably 40 to 60 mol%, from the viewpoint of achieving both crack resistance and hardness of the film. Mol%. When the phenyl group content is higher than 70 mol%, the hardness decreases, and when the phenyl group content is lower than 20 mol%, crack resistance decreases. The phenyl group content is determined, for example, by measuring the ²⁹ Si-nuclear magnetic resonance spectrum of polysiloxane and determining the ratio of the peak area of Si bonded to the phenyl group and the peak area of Si bonded to no phenyl group. Can do.

  The weight average molecular weight (Mw) of the polysiloxane used in the present invention is not particularly limited, but is preferably 1000 to 100,000, more preferably 2000 to 50,000 in terms of polystyrene measured by GPC (gel permeation chromatography). . When Mw is less than 1000, the coating properties are deteriorated, and when it is more than 100,000, the solubility in a developing solution during pattern formation is deteriorated.

  The polysiloxane in the present invention can be obtained by hydrolysis and partial condensation of the above organosilane. A general method can be used for hydrolysis and partial condensation. For example, a solvent, water and, if necessary, a catalyst are added to the mixture, and the mixture is heated and stirred. During stirring, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) may be distilled off by distillation as necessary.

  Although there is no restriction | limiting in particular as said reaction solvent, Usually, the thing similar to (d) solvent mentioned later is used. The amount of the solvent added is preferably 10 to 1000% by weight based on 100% by weight of the total amount of organosilane or organosilane and silica particles. 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.

  Although there is no restriction | limiting in particular in the catalyst added as needed, An acid catalyst and a base catalyst are used preferably. Specific 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 anhydride thereof, and ion exchange resin. Specific examples of the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, amino Examples include alkoxysilanes having groups and ion exchange resins. The addition amount of the catalyst is preferably 0.01 to 10% by weight with respect to 100% by weight of the organosilane.

  Further, from the viewpoint of coating properties and storage stability, it is preferable that the polysiloxane solution after hydrolysis and partial condensation does not contain alcohol, water, and catalyst as by-products. These removals may be performed as necessary. The removal method is not particularly limited. Preferably, as a method for removing alcohol or water, a method of diluting a polysiloxane solution with an appropriate hydrophobic solvent and then washing it several times with water can be concentrated using an evaporator. As a method for removing the catalyst, a method of treating with an ion exchange resin alone or in addition to the above water washing can be used.

  The positive photosensitive composition of the present invention contains (b) (meth) acrylic polymer. By using polysiloxane and a (meth) acrylic polymer in combination, a material having higher heat resistance and transparency than a material using a (meth) acrylic polymer and a higher sensitivity than a material using a polysiloxane can be obtained. . Furthermore, when the (meth) acrylic polymer contains a carboxyl group, a positive photosensitive composition that is soluble in a low-concentration developer such as a 0.2 to 0.8 wt% TMAH aqueous solution can be obtained. The (meth) acrylic polymer having a carboxyl group can be obtained by polymerizing an unsaturated carboxylic acid.

  Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides. These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds. Specific examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, and methacrylic acid. Isopropyl, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, N-pentyl acrylate, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, and other unsaturated carboxylic acid alkyl esters, styrene, p-methyls Rene, aromatic vinyl compounds such as o-methylstyrene, m-methylstyrene and α-methylstyrene, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, aliphatic conjugated dienes such as 1,3-butadiene and isoprene, acryloyl groups at the terminals, Alternatively, macromonomers such as polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and polysilicone having a methacryloyl group Etc. Although the like, but is not limited to these.

  (B) Although there is no restriction | limiting in particular in the molecular weight of a (meth) acrylic polymer, 5000-40000 are preferable and, as for a weight average molecular weight (Mw), 7000-20000 are more preferable. If the molecular weight is 5000 or less, pattern formation is hindered, and if the molecular weight is 40000 or more, a residual residue in the exposed portion is likely to occur during patterning. Furthermore, the resin acid value of the (meth) acrylic polymer is preferably 50 to 150 mgKOH / g, more preferably 70 to 130 mgKOH / g. When the resin acid value is less than 50 mgKOH / g, the sensitivity in a low-concentration developer is lowered.

  The (meth) acrylic polymer containing a carboxyl group may have an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacryl group. As a method for adding such a side chain to an acrylic (co) polymer, an ethylenically unsaturated compound having a glycidyl group or acrylic acid or methacrylic acid chloride is added to the carboxylic acid group of the acrylic (co) polymer. A reaction method is general. In addition, a compound having an ethylenically unsaturated group can be added using isocyanate. Examples of the ethylenically unsaturated compound having glycidyl group and acrylic acid or methacrylic acid chloride include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonic acid, and glycidyl isocrotonate. Examples include ether, acrylic acid chloride, and methacrylic acid chloride.

  The content ratio of (a) polysiloxane and (b) (meth) acrylic polymer is preferably 20/80 to 80/20 by weight. When the polysiloxane content ratio is less than 20, the transmittance of the cured film is not sufficiently improved. On the other hand, if the polysiloxane content ratio is greater than 80, high sensitivity is not sufficient.

  The positive photosensitive composition of the present invention contains (d) a solvent. The solvent is not particularly limited, but a compound having an alcoholic hydroxyl group is preferably used. When a compound having an alcoholic hydroxyl group is used as the solvent, the polysiloxane and the quinonediazide compound are uniformly dissolved, and even when the composition is coated and formed, high transparency can be achieved without whitening the film.

  The compound having an alcoholic hydroxyl group is not particularly limited, but is preferably a compound having a boiling point of 100 to 250 ° C. under atmospheric pressure. When the boiling point is higher than 250 ° C., the amount of residual solvent in the film increases, and the film shrinkage at the time of thermosetting increases, and good flatness cannot be obtained. On the other hand, if the boiling point is lower than 100 ° C., the coating properties deteriorate, for example, the drying at the time of coating is too fast and the film surface becomes rough.

  Specific 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, 4-hydroxy- 4-methyl-2-pentanone (diacetone alcohol), 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- Examples include butyl ether, 3-methoxy-1-butanol, and 3-methyl-3-methoxy-1-butanol. Among these, a compound further having a carbonyl group is preferable, and diacetone alcohol is particularly preferably used. These compounds having an alcoholic hydroxyl group may be used alone or in combination of two or more.

  Moreover, the positive photosensitive composition of this invention may contain another solvent, unless the effect of this invention is impaired. Other solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1- Examples include esters such as butyl acetate, ketones such as methyl isobutyl ketone, diisopropyl ketone and diisobutyl ketone, and ethers such as diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol methyl ethyl ether and dipropylene glycol dimethyl ether. .

  A method for forming a cured film using the positive photosensitive composition of the present invention will be described. The positive photosensitive composition of the present invention is applied onto a glass substrate by a known method such as a spinner, dipping, or slit, and prebaked with a heating device such as a hot plate or 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 prebaking, stepper, a mirror projection mask aligner (MPA), using an ultraviolet-visible exposure machine, such as a parallel light mask aligner (PLA), 10~200mJ / cm ² (wavelength 365nm exposure) is performed through a desired mask pattern Exposure.

After patterning exposure, the exposed portion is dissolved by development, and a pattern can be obtained. As a developing method, it is preferable to immerse in a developer for 5 seconds to 10 minutes by a method such as showering, dipping or paddle. As the developer, a known alkali developer can be used. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates, borates, amines such as 2-diethylaminoethanol, monoethanolamine, diethanolamine, TMAH, choline, etc. And an aqueous solution containing one or more quaternary ammonium salts. Among these, a TMAH aqueous solution that is an organic alkali that is free from the risk of contamination with metal ions and that is a strong alkali is preferably used. The TMAH aqueous solution is generally preferably used at a concentration of 0.20 to 2.38 wt% from the viewpoint of solubility of phenolic hydroxyl groups, silanol groups, and carboxyl groups in alkali. Among these, materials that can be developed with a low-concentration alkaline developer from the viewpoint of cost and safety are also demanded, more preferably 0.20 to 0.80 wt%, and still more preferably 0.20 to 0.50 wt% TMAH aqueous solution. Is more preferably used.
After development, it is preferable to rinse with water, followed by drying and baking in the range of 50 to 150 ° C.

Thereafter, it is preferable to perform bleaching exposure. By performing bleaching exposure, the unreacted quinonediazide compound remaining in the film is photodegraded, and the light transparency of the film is further improved. As a bleaching exposure method, an entire surface is exposed to about 100 to 400 mJ / cm ² (converted to a wavelength of 365 nm exposure) using an ultraviolet-visible exposure machine such as PLA.

  Next, the film is thermally cured at 150 to 300 ° C. for about 1 hour by a heating device such as a hot plate or an oven. The resolution is preferably 10 μm or less.

Further, the positive photosensitive composition of the present invention, it is preferred that the sensitivity at patterning exposure by PLA is 150 mJ / cm ² or less, more preferably 80 mJ / cm ² or less. When the sensitivity is required to be 150 mJ / cm ² or more, the radiation exposure time at the time of pattern formation becomes long, and thus the productivity is lowered.

  The sensitivity in patterning exposure using the PLA is determined by the following method. The composition is spin-coated on glass at an arbitrary rotation number using a spin coater, and prebaked at 100 ° C. for 2 minutes using a hot plate to produce a film having a thickness of 3 μm. The prepared film was exposed to an ultra-high pressure mercury lamp through a gray scale mask for sensitivity measurement using PLA (PLA-501F manufactured by Canon Inc.), and then an automatic developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.). ) With a TMAH aqueous solution of an arbitrary concentration for 80 seconds, and then rinse with water for 30 seconds. In the formed pattern, an exposure amount for resolving a 10 μm line and space pattern with a one-to-one width is obtained as sensitivity.

  The positive photosensitive composition of the present invention can form a cured film having a transmittance of 90% or more per 2 μm thickness at a wavelength of 400 nm, more preferably 95% or more. When the light transmittance is lower than 90%, when it is used as a planarizing film for a TFT substrate of a liquid crystal display element, a color change occurs when the backlight passes, and the white display becomes yellowish.

  The transmittance at a wavelength of 400 nm is determined by measuring an ultraviolet-visible absorption spectrum of a cured film obtained on glass using MultiSpec-1500 manufactured by Shimadzu Corporation.

This cured film is suitably used for a TFT planarizing film in a display element, an interlayer insulating film in a semiconductor element, or a core or cladding material in an optical waveguide.
Examples of the element of the present invention include a display element, a semiconductor element, and an optical waveguide material. In addition, since the element of the present invention has the above-described cured film of high resolution, high hardness, high transparency, and high heat resistance of the present invention, in particular, a liquid crystal display or an organic EL display element used as a planarizing film for TFT. Is excellent in screen brightness and reliability.

  The present invention will be described below with reference to examples thereof, but the embodiment of the present invention is not limited to these examples. Of the compounds used in the examples and the like, those using abbreviations are shown below.

DAA: diacetone alcohol PGMEA: propylene glycol monomethyl ether acetate The solid content concentration and the weight average molecular weight (Mw) of the polysiloxane solution and the (meth) acrylic polymer solution were determined as follows.

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

(2) Weight average molecular weight of (meth) acrylic polymer The weight average molecular weight of the polymer was determined in terms of polystyrene by GPC (Waters 996 type detector, developing solvent: tetrahydrofuran).

Synthesis Example 1 Synthesis of Polysiloxane (PS-1) Solution In a 500 ml three-necked flask, 54.48 g (0.40 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane (24.64 g, 0.10 mol) and diacetone alcohol (hereinafter abbreviated as DAA) (166.07 g) were charged, and phosphoric acid was added to 55.80 g of water with stirring at room temperature. A phosphoric acid aqueous solution in which 0.089 g (0.05% by weight based on the charged monomers) 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 2 hours (the internal temperature was 100 to 110 ° C.) to obtain a polysiloxane (PS-1) solution. During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 123 g of methanol and water as by-products were distilled out. The resulting polysiloxane (PS-1) solution had a solid content concentration of 40% by weight.

Synthesis Example 2 Synthesis of Polysiloxane (PS-2) Solution In a 500 ml three-necked flask, 54.48 g (0.40 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 24.64 g (0.10 mol) and DAA 166.07 g were charged, and the mixture was stirred at room temperature with 55.80 g of water and 0.535 g of phosphoric acid (0. 3% by weight) of phosphoric acid aqueous solution 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 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane (PS-2) solution (PS-2). . During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 123 g of methanol and water as by-products were distilled out. The resulting polysiloxane (PS-2) solution had a solid content concentration of 40% by weight.

Synthesis Example 3 Synthesis of Polysiloxane (PS-3) Solution In a 500 ml three-necked flask, 47.67 g (0.35 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane 24.64 g (0.10 mol), 3-acryloxypropyltrimethoxysilane 11.72 g (0.05 mol) and DAA 166.07 g were charged with stirring at room temperature. An aqueous phosphoric acid solution in which 0.092 g of phosphoric acid (0.05 wt% with respect to the charged monomer) was dissolved in 55.80 g of water 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 2 hours (the internal temperature was 100 to 110 ° C.) to obtain a polysiloxane (PS-3) solution. During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 123 g of methanol and water as by-products were distilled out. The resulting polysiloxane (PS-3) solution had a solid content concentration of 40% by weight.

Synthesis Example 4 Synthesis of Polysiloxane (PS-4) Solution In a 500 ml three-necked flask, 20.43 g (0.15 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane 24.64 g (0.10 mol), 3-acryloxypropyltrimethoxysilane 58.60 g (0.25 mol) and DAA 166.07 g were charged with stirring at room temperature. A phosphoric acid aqueous solution in which 0.101 g of phosphoric acid (0.05 wt% with respect to the charged monomer) was dissolved in 55.80 g of water 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 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane (PS-4) solution. During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 123 g of methanol and water as by-products were distilled out. The resulting polysiloxane (PS-4) solution had a solid content concentration of 40% by weight.

Synthesis Example 5 Synthesis of polysiloxane (PS-5) solution 99.15 g (0.50 mol) of phenyltrimethoxysilane and 24.64 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane in a 500 ml three-necked flask (0.10 mol), 93.76 g (0.40 mol) of 3-acryloxypropyltrimethoxysilane, and 166.07 g of DAA were charged, and 0.092 g of phosphoric acid was added to 55.80 g of water while stirring at room temperature. An aqueous phosphoric acid solution in which 0.05% by weight) 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 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane (PS-5) solution. During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 123 g of methanol and water as by-products were distilled out. The resulting polysiloxane (PS-5) solution had a solid content concentration of 40% by weight.

Synthesis Example 6 Synthesis of quinonediazide compound (QD-1) Under dry nitrogen stream, Ph-cc-AP-MF (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 15.32 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl 37.62 g (0.14 mol) of acid chloride was dissolved in 450 g of 1,4-dioxane 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 quinonediazide compound (QD-1) having the following structure.

Synthesis Example 7 Synthesis of quinonediazide compound (QD-2) Similar to Synthesis Example 3, except that the amount of 5-naphthoquinonediazidesulfonyl acid chloride was changed to 33.59 g (0.125 mol), a quinonediazide compound (QD) having the following structure: -2) was obtained.

Synthesis Example 8 Synthesis of quinonediazide compound (QD-3) Similar to Synthesis Example 3, except that the amount of 5-naphthoquinonediazidesulfonyl acid chloride added was changed to 30.90 g (0.115 mol), quinonediazide compound (QD) having the following structure: -3) was obtained.

Synthesis Example 9 Synthesis of quinonediazide compound (QD-4) Under a dry nitrogen stream, TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 21.23 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 37. 62 g (0.14 mol) was dissolved in 450 g of 1,4-dioxane 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 quinonediazide compound (QD-4) having the following structure.

Synthesis Example 10 Synthesis of quinonediazide compound (QD-5) 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 26. 87 g (0.1 mol) was dissolved in 450 g of 1,4-dioxane 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 in 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 quinonediazide compound (QD-5) having the following structure.

Synthesis Example 11 Synthesis of (meth) acrylic polymer (AP-1) solution In a 500 ml flask, 5 g of 2,2′-azobis (isobutyronitrile), 5 g of t-dodecanethiol, propylene glycol monomethyl ether acetate (hereinafter, 150 g) was abbreviated as PGMEA. Thereafter, 30 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 and stirred for a while at room temperature. The mixture was stirred with heating at 5 ° C for 5 hours. Next, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, and 0.2 g of p-methoxyphenol were added to the obtained solution, and the mixture was heated and stirred at 100 ° C. for 4 hours to obtain a (meth) acrylic polymer (AP-1). A solution was obtained. The obtained (meth) acrylic polymer (AP-1) solution had a solid content concentration of 40% by weight, and the obtained (meth) acrylic polymer (AP-1) had a weight average molecular weight (Mw) of 10600 and an acid value. Was 118 mg KOH / g.

Synthesis Example 12 Synthesis of (Meth) acrylic polymer (AP-2) solution A 500 ml flask was charged with 3 g of 2,2′-azobis (isobutyronitrile), 3 g of t-dodecanethiol, and 154 g of PGMEA. Thereafter, 30 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 and stirred for a while at room temperature. The mixture was stirred with heating at 5 ° C 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 100 ° C. for 4 hours to obtain a (meth) acrylic polymer (AP-2). A solution was obtained. The obtained (meth) acrylic polymer (AP-2) solution has a solid content concentration of 40% by weight, and the obtained (meth) acrylic polymer (AP-2) has a weight average molecular weight (Mw) of 17,600, an acid value. Was 116 mg KOH / g.

Example 1
Under a yellow light, 0.10 g (5 parts by weight) of a quinonediazide compound (QD-1) was dissolved in 1.65 g of DAA and 1.65 g of PGMEA, and then 2.50 g of a polysiloxane (PS-1) solution, (meth) acrylic. 2.50 g of polymer (AP-1) solution was added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained positive type photosensitive composition (PP-1).
Spin the produced positive photosensitive composition (PP-1) on a glass substrate (OA-10 manufactured by JEOL Glass Co., Ltd.) using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at any rotational speed. After coating, prebaking was performed at 100 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) to prepare a prebaked film having a thickness of 3.0 μm. The prepared pre-baked film was irradiated using a parallel light mask aligner (PLA-501F manufactured by Canon Inc., hereinafter referred to as PLA) and a gray scale mask at 200 mJ / cm ² (wavelength 365 nm exposure amount conversion). Note that a gray scale mask is a mask that can be exposed in steps from 1% to 100% under the mask by exposing from above the mask. After that, using an automatic developing device (AD-2000, manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed with a 0.4 wt% tetramethylammonium hydroxide aqueous solution for 80 seconds, followed by rinsing with water for 30 seconds. Next, the surface of the film was exposed to 300 mJ / cm ² (wavelength 365 nm exposure amount conversion) using PLA. Then, it cured in 220 degreeC in air for 1 hour using oven (Espec Co., Ltd. product IHPS-222), and produced the cured film.

  The evaluation results are shown in Table 1. The evaluation in the table was performed by the following method.

(1) Film thickness measurement Using Dainippon Screen Manufacturing Co., Ltd. Lambda Ace STM-602, the thickness of the prebaked film and the cured film was measured with a refractive index of 1.55.

(2) Residual film ratio The residual film ratio is determined by coating the composition on a glass substrate, pre-baking on a hot plate at 100 ° C. for 120 seconds, and developing, pre-baked film thickness (i), unexposed after development. Assuming the partial thickness (ii),
Residual film rate (%) = (ii) × 100 / (i)
Is calculated by

(3) Sensitivity Exposure amount for forming a line-and-space pattern of 10 μm in a one-to-one width in a pattern obtained by shower development with a TMAH aqueous solution of a specified concentration for 80 seconds and rinsing with water for 30 seconds (hereinafter referred to as this) The optimum exposure amount) was defined as sensitivity.

(4) Measurement of light transmittance The cured film is measured with a single beam using MultiSpec-1500 (manufactured by Shimadzu Corporation), the light transmittance at a wavelength of 400 nm is obtained, and the transmittance per 2 μm thickness is calculated. did.

Examples 2 to 8, Comparative Examples 1 and 2
7, 10, 15, 20 or 25 parts by weight of quinonediazide compound (QD-1), or quinonediazide compound (QD-2), (QD-3), (QD-4) or (QD-5) 15 Except having changed to the weight part, it carried out similarly to Example 1 and obtained positive photosensitive composition (PP-2)-(PP-10). Each composition was evaluated in the same manner as in Example 1 using each obtained composition. The evaluation results are shown in Table 1.

Examples 9 to 12, Comparative Examples 3 and 4
The addition amount of polysiloxane (PS-1) solution / (meth) acrylic polymer (AP-1) is 10 parts by weight / 90 parts by weight, 30 parts by weight / 70 parts by weight, 70 parts by weight / 30 parts by weight, 90 parts by weight. Except having changed to / 10 weight part, it carried out similarly to Example 1 and obtained positive photosensitive composition (PP-11)-(PP-16). Each composition was evaluated in the same manner as in Example 1 using each obtained composition. The evaluation results are shown in Table 2.

Examples 13-16
Examples except that the positive photosensitive composition (PP-4) is used and the developer concentration is changed to TMAH 0.10%, 0.25%, 0.40%, 0.70%, or 0.90%. Each composition was evaluated in the same manner as in 1. The evaluation results are shown in Table 3.

Comparative Examples 5-8
Example except that the positive photosensitive composition (PP-9) is used and the developer concentration is changed to TMAH 0.10%, 0.25%, 0.40%, 0.70%, or 0.90%. Each composition was evaluated in the same manner as in 1. The evaluation results are shown in Table 3.

Example 17
Under a yellow light, 0.30 g (15 parts by weight) of a quinonediazide compound (QD-1) was dissolved in 1.65 g of DAA and 1.65 g of PGMEA, and then 2.50 g of a polysiloxane (PS-1) solution, (meth) acrylic. 2.50 g of polymer (AP-1) solution was added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained positive type photosensitive composition (PP-17).

  Using the composition (PP-17), each composition was evaluated in the same manner as in Example 1 except that the developer concentration was changed to 2.38% TMAH. The evaluation results are shown in Table 3.

Comparative Example 9
Under a yellow light, 0.30 g (15 parts by weight) of a quinonediazide compound (QD-4) was dissolved in 1.65 g of DAA and 1.65 g of PGMEA, and then 2.50 g of a polysiloxane (PS-1) solution, (meth) acrylic. 2.50 g of polymer (AP-1) solution was added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained positive type photosensitive composition (PP-18).

  Each composition was evaluated in the same manner as in Example 1 except that the composition (PP-18) was used and the developer concentration was changed to 2.38% TMAH. The evaluation results are shown in Table 3.

Example 18
Under a yellow light, 0.30 g (15 parts by weight) of a quinonediazide compound (QD-1) was dissolved in 1.65 g of DAA and 1.65 g of PGMEA, and then 2.50 g of a polysiloxane (PS-3) solution, (meth) acrylic. 2.50 g of polymer (AP-1) solution was added and stirred. Subsequently, it filtered with a 0.45 micrometer filter and obtained positive type photosensitive composition (PP-19).

  Using the composition (PP-19), the photosensitive properties were evaluated in the same manner as in Example 1 to prepare a cured film.

  The obtained cured film was immersed in alkaline solvent monoethanolamine / 2-butoxyethoxy) ethanol = 15/65/20 (weight ratio) at 60 ° C. for 5 minutes, then rinsed with pure water for 5 minutes, Removed with nitrogen blow.

  The evaluation results are shown in Table 4. In addition to the evaluation similar to Example 1, the evaluation in the table was performed by the following method.

(5) Film thickness change rate Using a Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., the thickness of the film obtained with a refractive index of 1.55 was measured. The rate of change in film thickness is defined as the film thickness (iii) before soaking with the alkali solvent and the film thickness (iii) after soaking.
Film thickness change rate (%) = (iii) × 100 / (iii)
Is calculated by

Examples 19-20, Comparative Example 10
A positive photosensitive composition was prepared in the same manner as in Example 17 except that the polysiloxane solution (PS-3) was replaced with the polysiloxane solution (PS-4), (PS-5), or (PS-1). (PP-20) to (PP-23) were obtained. Each composition was evaluated in the same manner as in Example 18 using each obtained composition. The evaluation results are shown in Table 4.

Claims (6)

A positive photosensitive composition comprising (a) polysiloxane, (b) (meth) acrylic polymer, (c) a quinonediazide compound represented by the general formula (1), and (d) a solvent.

(In the formula, R ¹ represents hydrogen or an alkyl group selected from 1 to 8 carbon atoms. R ² , R ³ and R ⁴ represent a hydrogen atom, an alkyl group selected from 1 to 8 carbon atoms, an alkoxyl group and a carboxyl group. Each of R ² , R ³ and R ⁴ may be the same or different, Q represents either a 5-naphthoquinonediazidosulfonyl group or a hydrogen atom, (Not all become hydrogen atoms. A, b, c, α, and β are integers of 0 to 4, provided that α + β ≧ 3.) 2. The positive photosensitive composition according to claim 1, wherein the weight ratio of (a) polysiloxane to (b) (meth) acrylic polymer is 20/80 to 80/20. 3. The photosensitive composition according to claim 1, wherein (a) the polysiloxane is a polysiloxane having an ethylenically unsaturated group. The developer used for pattern formation using the positive photosensitive composition according to any one of claims 1 to 3, is a 0.2 to 0.8 wt% tetramethylammonium hydroxide aqueous solution. A method for producing a cured film. The cured film formed from the positive photosensitive composition in any one of Claims 1-3. An element comprising the cured film according to claim 5.