JP2007334036A - Photosensitive resin composition, method for producing thin film pattern using the same, protective film for electronic device, transistor, color filter, organic el device, gate insulating film and thin film transistor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition in which the crosslinking efficiency of a condensate of an alkoxysilane can be enhanced without heat treatment at such a very high temperature as ≥500°C, and with which a thin film pattern excellent in electrical insulation can be obtained, and also to provide a method for producing a thin film pattern using the same. <P>SOLUTION: The photosensitive resin composition comprises the condensate of the alkoxysilane, a first photoacid or base generator which is activated by irradiation with light having a wavelength A to generate an acid or base, and a second photoacid or base generator which is activated by irradiation with light having a wavelength B different from the wavelength A to generate an acid or base. The method for producing a thin film pattern using the same is also provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition having photosensitivity and capable of forming a thin film pattern by alkali development, a thin film pattern manufacturing method using the same, a protective film for electronic equipment, a transistor, a color filter, The present invention relates to an organic EL element, a gate insulating film, and a thin film transistor.

  In manufacturing electronic devices such as semiconductors, a passivation film, a gate insulating film, and the like are formed by a fine pattern forming method. For forming these films, for example, a photosensitive resin composition containing an alkoxysilane condensate or the like is used.

  In Patent Document 1 below, as an example of a photosensitive resin composition used for pattern formation, (1) an alkali-soluble siloxane polymer, (2) a compound that generates a reaction accelerator by light, and (3) a solvent are mainly used. A photosensitive resin composition as a component is disclosed. In Patent Document 1, (1) an alkali-soluble siloxane polymer obtained by removing water and a catalyst from a reaction solution obtained by hydrolyzing and condensing alkoxysilane with water and a catalyst is used as the alkali-soluble siloxane polymer. Yes.

  In the method described in Patent Document 1, in forming a pattern, a photosensitive resin composition layer made of a photosensitive resin composition is formed, and the photosensitive resin composition layer is exposed through a mask. In this part, the crosslinking reaction of the alkoxysilane condensate was advanced to cure the photosensitive resin composition layer.

  Since the photosensitive resin composition of Patent Document 1 contains the above (1) to (3) as main components, it is excellent in applicability, and does not cause defects such as unevenness and streaks in the coated film. There is no change in viscosity or applicability deterioration during storage, and it is said to be excellent in storage stability.

Furthermore, Patent Document 1 discloses a pattern forming method in which the photosensitive resin composition is applied onto a substrate, dried, exposed through a mask, and subsequently developed. In addition, it is described that in this pattern formation method, after exposure through a mask, heating may be performed before development. By heating before development, polymerization in the exposed area proceeds due to the action of the reaction accelerator generated by exposure, and the difference in developer solubility from the unexposed area is widened, resulting in improved resolution contrast. It is said that.
Japanese Patent Laid-Open No. 06-148895

  However, in the method described in Patent Document 1, the crosslinking reaction of the alkoxysilane condensate may not sufficiently proceed after the photosensitive resin composition layer is cured. That is, the uncrosslinked component of the alkoxysilane condensate may remain in the photosensitive resin composition layer after the photosensitive resin composition layer is cured. Therefore, in the obtained thin film pattern, the insulating performance tends to be lowered.

  For example, a very high insulating performance is required for a semiconductor passivation film, a gate insulating film, and the like. However, since the thin film pattern comprised using the photosensitive resin composition of patent document 1 has low insulation performance, it was inadequate for using for such a use.

  Patent Document 1 also describes that the polymerization in the exposed portion can be advanced by the action of a reaction accelerator generated by exposure by heating after exposure and before development. However, since most of the reaction accelerators generated by light are consumed by exposure, it is difficult to sufficiently progress the polymerization in the exposed area with only the reaction accelerator remaining after exposure.

  In order to sufficiently advance the crosslinking reaction of the alkoxysilane condensate, it is necessary to heat-treat the photosensitive resin composition layer at a high temperature of, for example, 500 ° C. or higher after the exposure. In order to perform heat treatment at such a very high temperature of 500 ° C. or higher, it is necessary to use special heating equipment. Furthermore, when heat treatment is performed at 500 ° C. or higher, not only the substrate and the thin film pattern but also portions other than the thin film pattern on the substrate tend to deteriorate.

  The object of the present invention is to take into account the current state of the prior art described above, and can sufficiently increase the cross-linking efficiency of the alkoxysilane condensate without heat treatment at a very high temperature of, for example, 500 ° C. or more. Provided are a photosensitive resin composition capable of obtaining a thin film pattern with excellent performance, a method for producing a thin film pattern using the same, a protective film for electronic equipment, a transistor, a color filter, an organic EL element, a gate insulating film, and a thin film transistor. There is.

  The photosensitive resin composition according to the present invention includes an alkoxysilane condensate, a first photoacid or base generator that generates an acid or a base by being irradiated with light having a wavelength A, and a wavelength different from the wavelength A. It contains a second photoacid or base generator that is activated by irradiation with the B light to generate an acid or a base.

  In a specific aspect of the photosensitive resin composition according to the present invention, the first photoacid or base generator advances the crosslinking reaction of the alkoxysilane condensate by irradiation with light of wavelength A, and the photosensitive resin composition A photoacid or base generator that cures the product to form a cured photosensitive resin, and the second photoacid or base generator is a non-crosslinked alkoxysilane condensate contained in the cured photosensitive resin. It is a photoacid or base generator that causes the crosslinking reaction to proceed by irradiation with light having a wavelength B different from the wavelength A.

  In another specific aspect of the photosensitive resin composition according to the present invention, the second photoacid or base generator is a photoacid or base generator that is not activated when irradiated with light of wavelength A.

  In another specific aspect of the photosensitive resin composition according to the present invention, the wavelength λmax of light that most activates the first photoacid or base generator and the second photoacid or base generator most activated The wavelength λmax of the light beam to be generated is different.

  In still another specific aspect of the photosensitive resin composition according to the present invention, the wavelength λmax of the light beam that most activates the first photoacid or base generator and the second photoacid or base generator most active. The wavelength difference from the wavelength λmax of the light to be converted is 50 nm or more.

  In still another specific aspect of the photosensitive resin composition according to the present invention, the first photoacid or base generator is 0.05 to 50 parts by weight with respect to 100 parts by weight of the alkoxysilane condensate, and 2 photoacids or base generators are respectively contained in a proportion of 0.05 to 50 parts by weight.

  The method for producing a thin film pattern according to the present invention comprises a step of forming a photosensitive resin composition layer comprising a photosensitive resin composition configured according to the present invention on a substrate, and a wavelength A depending on the pattern to be formed. The photosensitive resin composition layer is selectively exposed with light, and an acid or base is generated from the first photoacid or base generator to cure the photosensitive resin composition layer to form a patterned latent image. A step of forming a patterned latent image, developing the photosensitive resin composition layer on which the latent image is formed with a developer, and obtaining a thin film pattern comprising the cured photosensitive resin composition layer; A step of irradiating the cured photosensitive resin composition layer with a light beam having a wavelength B different from that of the wavelength A after the step of forming a latent image, and generating an acid or a base from the second photoacid or base generator It is provided with these.

  In a specific aspect of the method for producing a thin film pattern according to the present invention, a step of generating an acid or a base from the second photoacid or base generator is performed after the step of obtaining the thin film pattern.

  The thin film formed using the photosensitive resin composition according to the present invention is used in various applications. Here, the “thin film formed using the photosensitive resin composition” means a thin film obtained by introducing energy such as heat and light to the photosensitive resin composition and introducing a crosslinked structure. To do. In a specific aspect of the present invention, the thin film is used as a protective film for electronic devices, and a transistor, a color filter, an organic EL element, and the like having such a protective film can be provided by the present invention.

  Furthermore, the thin film is preferably used as a gate insulating film or a passivation film of a thin film transistor. A thin film transistor having such a gate insulating film and / or a passivation film can also be provided by the present invention.

  The photosensitive resin composition according to the present invention includes an alkoxysilane condensate, a first photoacid or base generator that generates an acid or a base by being irradiated with light having a wavelength A, and a wavelength different from the wavelength A. Since it contains a second photoacid or base generator that generates an acid or a base that is activated by irradiation with the B light, for example, the photosensitive resin composition layer is exposed to light having a wavelength A and exposed to light. The crosslinking efficiency of the alkoxysilane condensate in the photosensitive resin composition layer can be increased by irradiating the photosensitive resin composition layer with light of wavelength B. Therefore, since the residual ratio of the uncrosslinked component of the alkoxysilane condensate contained in the photosensitive resin composition layer can be reduced, a thin film pattern having excellent insulation performance can be obtained.

  For example, when the photosensitive resin composition does not contain a second acid or base generator, in order to increase the crosslinking efficiency of the condensate of alkoxysilane, after exposure, It is necessary to heat-treat at a high temperature. In order to perform heat treatment at such a very high temperature of 500 ° C. or higher, it is necessary to use special heating equipment. Furthermore, when heat treatment is performed at 500 ° C. or higher, not only the substrate and the thin film pattern but also portions other than the thin film pattern on the substrate tend to deteriorate. However, in the present invention, in addition to the first photoacid or base generator, a second photoacid or photobase generator that generates an acid or a base upon irradiation with light having a wavelength B different from the wavelength A is further provided. Since it contains, a new acid or base can be generated from the second photoacid or base generator by irradiating the photosensitive resin composition layer with light having a wavelength B after exposure. Therefore, the crosslinking efficiency of the alkoxysilane condensate can be effectively increased by the acid or base generated from the second photoacid or base generator.

  The first photoacid or base generator causes the crosslinking reaction of the alkoxysilane condensate by irradiation with light of wavelength A to cure the photosensitive resin composition to obtain a cured photosensitive resin. The second photoacid or base generator, which is a generator, causes the crosslinking reaction of a non-crosslinked alkoxysilane condensate contained in the cured photosensitive resin to proceed by irradiation with light having a wavelength B different from the wavelength A. When the photoacid or base generator is used, the uncrosslinked component of the alkoxysilane condensate in the cured photosensitive resin can be further reduced. Therefore, the thin film pattern which consists of a hardened | cured photosensitive resin more excellent in insulation performance can be provided.

  When the second photoacid or base generator is a photoacid or base generator that is not activated when irradiated with light of wavelength A, for example, the photosensitive resin composition layer is irradiated with light of wavelength A. Then, after the exposure, irradiation with a light beam having a wavelength B can surely generate a new acid or base from the second photoacid or base generator. Therefore, the cross-linking efficiency of the condensate of alkoxysilane can be further enhanced.

  When the wavelength λmax of the light beam most activating the first photoacid or base generator is different from the wavelength λmax of the light beam most activating the second photoacid or base generator, for example, the first light After irradiating the photosensitive resin composition layer with light having a wavelength A in the vicinity of the wavelength λmax of the light beam that most activates the acid or base generator and exposing it, the light beam that most activates the second photoacid or base generator By irradiating the photosensitive resin composition layer with a light beam having a wavelength B near the wavelength λmax, an acid or a base can be effectively generated from the first and second acid or base generators, respectively. Accordingly, the crosslinking efficiency of the alkoxysilane condensate can be further enhanced.

  When the wavelength difference between the wavelength λmax of the light beam most activating the first photoacid or base generator and the wavelength λmax of the light beam most activating the second photoacid or base generator is 50 nm or more When the photosensitive resin composition layer is exposed to light having a wavelength A in the vicinity of the wavelength λmax of the light that most activates the first photoacid or base generator, exposure is performed from the second photoacid or base generator. Acids or bases are less likely to be generated. Therefore, after exposure, the photosensitive resin composition layer is irradiated with a light beam having a wavelength B near the wavelength λmax of the light beam that most activates the second photoacid or base generator. An acid or a base can be efficiently generated from the generator. Therefore, the residual ratio of the uncrosslinked component of the alkoxysilane condensate contained in the thin film pattern can be further reduced.

  A ratio of 0.05 to 50 parts by weight of the first photoacid or base generator and 0.05 to 50 parts by weight of the second photoacid or base generator with respect to 100 parts by weight of the alkoxysilane condensate. In the case where each of them is included, the condensate of alkoxysilane can be cross-linked even more efficiently. Furthermore, it can also suppress that the residue resulting from the 1st, 2nd photoacid or base generator generate | occur | produces in a thin film pattern. Therefore, a more excellent thin film pattern can be obtained due to the insulating performance.

  The method for producing a thin film pattern according to the present invention comprises a step of forming a photosensitive resin composition layer comprising a photosensitive resin composition configured according to the present invention on a substrate, and a wavelength A depending on the pattern to be formed. The photosensitive resin composition layer is selectively exposed with light, and an acid or base is generated from the first photoacid or base generator to cure the photosensitive resin composition layer to form a patterned latent image. And a step of developing a photosensitive resin composition layer on which the latent image has been formed with a developer to obtain a thin film pattern comprising the cured photosensitive resin composition layer after forming a patterned latent image. Therefore, the crosslinking reaction of the alkoxysilane condensate proceeds, and a patterned latent image can be formed. In addition, the photosensitive resin composition layer on which the latent image is formed can be easily developed using a developer such as acid or alkali.

  Furthermore, in the present invention, after the step of forming a patterned latent image, the cured photosensitive resin composition layer is irradiated with a light beam having a wavelength B different from the wavelength A, and the second photoacid or base generator is used. Since it further includes a step of generating an acid or a base, even if an uncrosslinked component of the alkoxysilane condensate remains in the photosensitive resin composition layer, The crosslinking reaction can be allowed to proceed. Therefore, in the obtained thin film pattern, the crosslinking efficiency of the alkoxysilane condensate is increased, and the residual ratio of the uncrosslinked component of the alkoxysilane condensate is reduced. Therefore, the thin film pattern excellent in insulation performance can be provided by the thin film pattern manufacturing method of the present invention.

  Further, in order to advance the crosslinking reaction of the uncrosslinked component of the alkoxysilane condensate, it is only necessary to irradiate the light beam having the wavelength B before or after development. It is possible to suppress deterioration of the substrate, the thin film pattern, and portions other than the thin film pattern on the substrate due to heat treatment.

  When the step of generating an acid or base from the second photoacid or base generator is performed after the step of obtaining the thin film pattern, the photosensitive resin composition layer that is an unexposed portion is removed, Since only the cured photosensitive resin composition layer, which is an exposed portion, can be irradiated with light having a wavelength B, the uncrosslinked component of the alkoxysilane condensate can be more effectively cross-linked, and the thin film has an excellent pattern shape A pattern can be obtained.

  Details of the present invention will be described below.

  In order to achieve the above-mentioned problems, the inventors of the present invention have made extensive studies on a photosensitive resin composition containing a condensate of alkoxysilane used for pattern formation. As a result, the acid or base activated by irradiation with light of wavelength A is obtained. In addition to the first photoacid or base generator that generates acid, a second photoacid or base generator that is activated by irradiation with light having a wavelength B different from wavelength A to generate an acid or base is further included. After irradiating the photosensitive resin composition layer with light having a wavelength A, and exposing the photosensitive resin composition layer to light having a wavelength B different from the wavelength A, the crosslinking efficiency of the alkoxysilane condensate is effective. It has been found that a thin film pattern that can be improved in terms of electrical insulation performance and thereby has a very excellent electrical insulation performance, and has led to the present invention.

  The photosensitive resin composition according to the present invention includes an alkoxysilane condensate, a first photoacid or base generator that generates an acid or a base by being irradiated with light having a wavelength A, and a wavelength different from the wavelength A. And a second photoacid or base generator which is activated by irradiation with the B light to generate an acid or a base.

  The alkoxysilane condensate comprises a condensate obtained by condensing alkoxysilane. The condensate of alkoxysilane is contained at least one, and therefore, a condensate of two or more alkoxysilanes may be contained.

  In this invention, it is preferable to contain the condensate of the alkoxysilane obtained by condensing the alkoxysilane represented by following formula (1).

Si (X) _p (Y) _q (Z) _4-pq Formula (1)
In the above formula (1), X represents hydrogen or a non-hydrolyzable organic group having 1 to 30 carbon atoms, Y represents an alkoxy group, Z represents a hydrolyzable group other than an alkoxy group, p represents an integer of 0 to 3, q represents an integer of 1 to 4, and p + q ≦ 4. When p is 2 or 3, the plurality of X may be the same or different. When q is 2 to 4, a plurality of Y may be the same or different. When p + q ≦ 2, the plurality of Z may be the same or different.

  The alkoxy group Y and the hydrolyzable group Z other than the alkoxy group are usually hydrolyzed by heating in the temperature range of room temperature (25 ° C.) to 100 ° C. without catalyst in the presence of excess water. A group capable of forming a silanol group, or a group capable of further condensation to form a siloxane bond.

  Although it does not specifically limit as said alkoxy group Y, Specifically, C1-C6 alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned.

  Although it does not specifically limit as hydrolyzable group Z other than the said alkoxy group, Specifically, halogeno groups, such as chlorine and a bromine, an amino group, a hydroxyl group, or a carboxyl group etc. are mentioned.

  The non-hydrolyzable organic group X is not particularly limited, and examples thereof include an organic group having 1 to 30 carbon atoms that hardly causes hydrolysis and is a stable hydrophobic group. As the organic group having 1 to 30 carbon atoms which is a stable hydrophobic group, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, octyl group, pentyl group, decyl group, dodecyl group, tetradecyl group, Alkyl groups having 1 to 30 carbon atoms such as hexadecyl group, octadecyl group and eicosyl group, and alkyl halide groups such as fluorinated, chlorinated and brominated alkyl groups (for example, 3-chloropropyl group, 6-chloropropyl group) , 6-chlorohexyl group, 6,6,6-trifluorohexyl group, etc.), aromatic substituted alkyl groups such as halogen-substituted benzyl groups (for example, benzyl group, 4-chlorobenzyl group, 4-bromobenzyl group, etc.) ), Aryl groups (eg phenyl group, tolyl group, mesityl group, naphthyl group, etc.), vinyl groups and epoxy groups Group, an organic group containing an amino group, and the like organic group containing a thiol group.

  Specific examples of the alkoxysilane include, for example, triphenylethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triethylmethoxysilane, ethyldimethylmethoxysilane, methyldiethylmethoxysilane, ethyldimethylethoxysilane, methyldiethyl. Ethoxysilane, phenyldimethylmethoxysilane, phenyldiethylmethoxysilane, phenyldimethylethoxysilane, phenyldiethylethoxysilane, methyldiphenylmethoxysilane, ethyldiphenylmethoxysilane, methyldiphenylethoxysilane, ethyldiphenylethoxysilane, tert-butoxytrimethylsilane, butoxy Trimethylsilane, dimethylethoxysilane, methoxydimethylvinylsilane , Ethoxydimethylvinylsilane, diphenyldiethoxysilane, phenyldiethoxysilane, dimethyldimethoxysilane, diacetoxymethylsilane, diethoxymethylsilane, 3-chloropropyldimethoxymethylsilane, chloromethyldiethoxymethylsilane, diethoxydimethylsilane Diacetoxymethylvinylsilane, diethoxymethylvinylsilane, diethoxydiethylsilane, dimethyldipropoxysilane, dimethoxymethylphenylsilane, methyltrimethoxysilane, methyltriethoxysilane, methyl-tri-n-propoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, ethyl-tri-n-propoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyl-tri-n Propoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isobutyltripropoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyl Tripropoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltripropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, octyltripropoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, dodecyltripropoxysilane, tetra Decyltrimethoxysilane, tetradecyltriethoxysilane, tetradecyltripropoxysilane, hex Sadecyltrimethoxysilane, hexadecyltriethoxysilane, hexadecyltripropoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, octadecyltripropoxysilane, eicosyldecyltrimethoxysilane, eicosyltriethoxysilane, eicosyltripropoxy Silane, 6-chlorohexyltrimethoxysilane, 6,6,6-trifluorohexyltrimethoxysilane, benzyltrimethoxysilane, 4-chlorobenzyltrimethoxysilane, 4-bromobenzyltri-n-propoxysilane, phenyltrimethoxy Silane, phenyltriethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-amino Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, N-β-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltri Methoxysilane, triethoxysilane, trimethoxysilane, triisopropoxysilane, tri-n-propoxysilane, triacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraiso Examples include propoxysilane and tetraacetoxysilane. An alkoxysilane condensate obtained by condensing these alkoxysilanes is more preferably used. In constituting the alkoxysilane condensate, it is sufficient that at least one alkoxysilane is used, and therefore two or more alkoxysilanes may be used.

  The photosensitive resin composition according to the present invention comprises a first photoacid generator or photobase generator that is activated by irradiation with light having a wavelength A to generate an acid or a base, and a light having a wavelength B different from the wavelength A. A second photoacid generator or a photobase generator that is activated by irradiation to generate an acid or a base is contained.

  The feature of the present invention is that it is activated by irradiation with light of a wavelength B different from the wavelength A, in addition to the first photoacid generator or photobase generator that is activated by irradiation with light of wavelength A to generate an acid or base. And a second photoacid generator or photobase generator that generates an acid or a base. As will be described in detail later by including the first and second photoacid or base generator, the photosensitive resin composition layer is irradiated with light having a wavelength A, and the acid or base is generated from the first photoacid or base generator. After the base is generated and exposed, the photosensitive resin composition layer is further irradiated with a light beam having a wavelength B different from the wavelength A, whereby the crosslinking efficiency of the alkoxysilane condensate can be greatly enhanced.

  The first photoacid or base generator causes the crosslinking reaction of the alkoxysilane condensate by irradiation with light of wavelength A to cure the photosensitive resin composition to obtain a cured photosensitive resin. The second photoacid or base generator, which is a generator, causes the crosslinking reaction of a non-crosslinked alkoxysilane condensate contained in the cured photosensitive resin to proceed by irradiation with light having a wavelength B different from the wavelength A. A photoacid or base generator is preferred. In this case, the non-crosslinked component of the alkoxysilane condensate in the cured photosensitive resin can be further reduced.

  Further, by irradiating the light beam having the wavelength B, a new acid or base can be reliably generated from the second photoacid or base generator, and therefore the second photoacid or base generator has the wavelength A It is more preferable that the photoacid or base generator is not activated when irradiated with the light.

  More preferably, the wavelength λmax of the light beam that most activates the first photoacid or base generator is different from the wavelength λmax of the light beam that most activates the second photoacid or base generator. When the wavelength λmax at which the first and second acid or base generators are most activated is different, an acid or a base can be effectively generated from the first and second acid or base generators, respectively. In the present invention, the wavelength λmax at which the photoacid or base generator is most activated means a wavelength that shows the maximum peak of the absorption wavelength that appears when the photoacid or base generator is irradiated with light beams having different wavelengths. Shall.

  The wavelength difference between the wavelength λmax of the light beam most activating the first photoacid or base generator and the wavelength λmax of the light beam most activating the second photoacid or base generator is 50 nm or more. preferable. When the wavelength difference is 50 nm or more, when the photosensitive resin composition layer is exposed to light having a wavelength A which is the wavelength λmax of the light that most activates the first photoacid or base generator, the second photoacid or base generator is exposed. It becomes difficult to generate an acid or a base from the photoacid or base generator.

  After the photosensitive resin composition layer was irradiated with light having a wavelength A and exposed, the uncrosslinked component of the alkoxysilane condensate tended to remain in the photosensitive resin composition layer. When the uncrosslinked component remained in the photosensitive resin composition layer, the insulating performance of the obtained thin film pattern tended to be inferior. Since the uncrosslinked component of the alkoxysilane condensate has an OH structure, it is considered that the insulation performance deteriorates due to the OH structure remaining in the thin film pattern. In the present invention, after the exposure, the photosensitive resin composition layer is further irradiated with a light beam having a wavelength B different from the wavelength A, so that the crosslinking reaction of the uncrosslinked component proceeds and the proportion of the OH structure in the thin film pattern is reduced. Therefore, it is possible to provide a thin film pattern having excellent insulation performance.

Although it does not specifically limit as said 1st, 2nd photo-acid generator, For example, onium salt etc. are mentioned. More specifically, diazonium, phosphonium, and iodonium salts such as BF ₄ ⁻ , PF ₆ ⁻ , SBF ₆ ⁻ , and ClO ₄ ^— , and other organic halogen compounds, organic metals, and organic halides can be used. .

  The first and second photoacid generators are not particularly limited, but include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethaneantimonate, triphenylsulfonium benzosulfonate, cyclohexylmethyl (2-oxocyclohexyl). Sulfonium salt compounds such as sulfonium trifluoromethanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexylsulfonylcyclohexanone, dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, iodonium such as diphenyliodonium trifluoromethanesulfonate Salt, N-hydroxysuccinimide trifluoromethanesulfo Over doors and the like. A 1st photo-acid generator may be used independently and 2 or more types may be used together. A 2nd photo-acid generator may be used independently and 2 or more types may be used together.

  The first and second photoacid generators are not particularly limited, but preferably at least one compound selected from the group consisting of a more reactive onium salt, diazonium salt, and sulfonate ester is used. It is done.

  The content ratio of the first photoacid generator is preferably in the range of 0.05 to 50 parts by weight with respect to 100 parts by weight of the alkoxysilane condensate. When the first photoacid generator is less than 0.05 parts by weight, the sensitivity may not be sufficient and it may be difficult to form a thin film pattern. When the first photoacid generator exceeds 50 parts by weight, it is difficult to uniformly apply the photosensitive resin composition, and a residue may be generated after development.

  The content ratio of the second photoacid generator is preferably in the range of 0.05 to 50 parts by weight with respect to 100 parts by weight of the alkoxysilane condensate. More preferably, it is the range of 0.1-20 weight part. When the second photobase generator is less than 0.05 parts by weight, the crosslinking efficiency of the alkoxysilane condensate may not be sufficiently increased by irradiation with light of wavelength B, and the insulation performance of the thin film pattern may be reduced. May be inferior. When the amount of the second photobase generator exceeds 50 parts by weight, it may be excessive to increase the crosslinking efficiency of the condensate of alkoxysilane. In addition, residues resulting from the excess second photoacid generator May occur and the insulation performance may deteriorate.

  In addition to these photosensitizers, the first and second photoacids or base generators, a sensitizer may be further added in order to increase sensitivity.

  The sensitizer is not particularly limited. Specifically, benzophenone, p, p′-tetramethyldiaminobenzophenone, p, p′-tetraethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, Anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2- Chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-t rt-butylanthraquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis ( 5,7-dimethoxycarbonylcoumarin) and coronene, and the like are preferable.

  Although it does not specifically limit as said 1st, 2nd photobase generator, For example, a cobalt amine complex, o-acyl oxime, a carbamic acid derivative, a formamide derivative, a quaternary ammonium salt, a tosylamine, a carbamate, an amine imide compound etc. Can be mentioned. Specific examples include 2-nitrobenzyl carbamate, 2,5-dinitrobenzyl cyclohexyl carbamate, N-cyclohexyl-4-methylphenylsulfonamide, 1,1-dimethyl-2-phenylethyl-N-isopropylcarbamate, and the like. . A 1st photobase generator may be used independently and 2 or more types may be used together. A 2nd photobase generator may be used independently and 2 or more types may be used together.

  As the first and second photobase generators, amine imide compounds that generate a base upon irradiation with light are preferably used. Such an amineimide compound is not particularly limited as long as it generates a base when irradiated with light. Examples of such amine imide compounds include compounds represented by the following general formula (2) or (3).

In the above formulas (2) and (3), R ¹ , R ² and R ³ are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkylidene having 1 to 8 carbon atoms. Group, a cycloalkyl group having 4 to 8 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, a phenoxyalkyl group having 1 to 6 carbon atoms, a phenyl group, an electron donating group and / or an electron withdrawing group And a benzyl group substituted with a group, a benzyl group, an electron donating group and / or an electron withdrawing group. As a C1-C8 alkyl group, the alkyl group which has a substituent other than a linear alkyl group, for example, an isopropyl group, an isobutyl group, t-butyl group etc. are included. Among these substituents, from the viewpoint of ease of synthesis, solubility of amine imide, etc., an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 8 carbon atoms, and a phenoxyalkyl group having 1 to 6 carbon atoms. Is preferred. R ⁴ independently represents an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, a cycloalkyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenyl group. Ar ¹ in the general formula (2) is an aromatic group, and such an amine imide compound is known prior to the filing of the present application as disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-35949. Are available. In the general formula (3), Ar ² is an aromatic group.

  The amine imide compound has higher base generation efficiency than a compound that generates a primary or secondary amine when irradiated with light. Therefore, it is desirable to include an amine imide compound because the exposure time can be shortened and the manufacturing process can be shortened.

  The content ratio of the first photobase generator is preferably in the range of 0.05 to 50 parts by weight with respect to 100 parts by weight of the alkoxysilane condensate. If the first photobase generator is less than 0.05 parts by weight, the sensitivity may not be sufficient and it may be difficult to form a thin film pattern. When the first base generator exceeds 50 parts by weight, it is difficult to uniformly apply the photosensitive resin composition, and a residue may be generated after development.

  The content ratio of the second photobase generator is desirably in the range of 0.05 to 50 parts by weight with respect to 100 parts by weight of the alkoxysilane condensate. More preferably, it is the range of 0.1-20 weight part. When the second photobase generator is less than 0.05 parts by weight, the crosslinking efficiency of the alkoxysilane condensate may not be sufficiently increased by irradiation with light of wavelength B, and the insulation performance of the thin film pattern may be reduced. May be inferior. When the amount of the second photobase generator exceeds 50 parts by weight, it may be excessive to increase the crosslinking efficiency of the condensate of alkoxysilane. In addition, residues resulting from the excess second photobase generator may be present. May occur and the insulation performance may deteriorate.

  In the present invention, an appropriate solvent may be added in addition to the alkoxysilane condensate and the first and second photoacid or base generators. By adding a solvent, a photosensitive resin composition that can be easily applied can be provided.

  The solvent is not particularly limited as long as it can dissolve the alkoxysilane condensate, but is an aromatic hydrocarbon compound such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, diethylbenzene; cyclohexane, cyclohexene, dipentene, n Saturated or unsaturated hydrocarbon compounds such as pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, isodecane, tetrahydronaphthalene, squalane; diethyl Ether, di-n-propyl ether, di-isopropyl ether, dibutyl ether, ethylpropyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol Ethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether , Ethylene glycol methyl ethyl ether, tetrahydrofuran, 1,4-dioxane, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl cyclohexa , Methylcyclohexane, p-menthane, o-menthane, m-menthane; ethers such as dipropyl ether and dibutyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, cyclopentanone, Ketones such as cyclohexanone and cycloheptanone; ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl lactate, propyl lactate, butyl lactate, isoamyl lactate, stearic acid Examples include esters such as butyl. These solvents may be used independently and 2 or more types may be used together.

  What is necessary is just to select the mixing | blending ratio of the said solvent suitably so that it may apply uniformly, for example when apply | coating the photosensitive resin composition on a board | substrate and forming the photosensitive resin composition layer. Preferably, the concentration of the photosensitive resin composition is 0.5 to 60% by weight, more preferably about 2 to 40% by weight in terms of solid content.

  If necessary, other additives may be further added to the photosensitive resin composition according to the present invention. Such additives include fillers, pigments, dyes, leveling agents, antifoaming agents, antistatic agents, UV absorbers, pH adjusters, dispersants, dispersion aids, surface modifiers, plasticizers, plasticizers. Examples include accelerators and sagging inhibitors.

  The method for producing a thin film pattern according to the present invention includes a step of forming a photosensitive resin composition layer 1 made of the photosensitive resin composition according to the present invention, as shown in FIG. The photosensitive resin composition layer 1 is selectively exposed with a light beam having a wavelength A using a photomask 3 according to the above, and an acid or a base is generated from the first photoacid or base generator. A step of curing the composition layer to form a patterned latent image 1A (FIG. 1B), a step of developing the photosensitive layer 1B on which the latent image has been formed with an alkaline aqueous solution (FIG. 1C), and Is provided.

  Here, development means an operation of immersing the photosensitive layer 1B on which a latent image is formed in an alkaline aqueous solution, an operation of washing the surface of the photosensitive layer 1B with an alkaline aqueous solution, or an alkaline aqueous solution on the surface of the photosensitive layer 1B. It includes various operations for treating the photosensitive layer 1B with an alkaline aqueous solution, such as a spraying operation. The developing solution is not limited to an alkaline aqueous solution, and an acidic aqueous solution or various solvents may be used. Examples of the solvent include the various solvents described above. Examples of the acidic aqueous solution include oxalic acid, formic acid, acetic acid and the like.

  Although the process of forming the said photosensitive resin composition layer is not specifically limited, For example, the photosensitive resin composition which concerns on this invention is provided on the board | substrate 2 shown in FIG. 1, and the photosensitive resin composition layer 1 is formed. A method is mentioned. As a specific method in this case, a general coating method can be used, for example, dip coating, roll coating, bar coating, brush coating, spray coating, spin coating, extrusion coating. Work, gravure coating, etc. can be used. As the substrate on which the photosensitive resin composition is applied, a silicon substrate, a glass substrate, a metal plate, a plastics plate, or the like is used depending on the application. The thickness of the photosensitive resin composition layer varies depending on the use, but 10 nm to 10 μm is a standard. When a solvent is used to dissolve the photosensitive resin, the photosensitive resin composition layer coated on the substrate is preferably heat-treated to dry the solvent. The heat treatment temperature is generally 40 ° C. to 200 ° C., and is appropriately selected according to the boiling point and vapor pressure of the solvent.

  A photosensitive resin composition layer is formed on a substrate, heat-treated as necessary, and then the photosensitive resin composition layer is covered with a photomask and irradiated with light in a pattern. Thereby, a latent image having a necessary pattern shape can be formed. What is necessary is just to use the common thing marketed as a photomask.

  In the exposed portion of the photosensitive resin composition layer irradiated with light in the pattern shape, the crosslinking of the alkoxysilane condensate proceeds by the action of the acid or base generated from the first acid generator upon exposure. Therefore, as a result of the progress of crosslinking in the exposed portion, the photosensitive resin composition layer is cured and becomes insoluble in the developer.

  By developing the exposed photosensitive resin composition layer using a developer, the unexposed portion of the photosensitive resin composition layer is dissolved and removed in the developer, and the exposed portion remains on the substrate. As a result, a thin film pattern 1C composed of a cured photosensitive resin composition layer is formed. This thin film pattern is called a negative pattern because the unexposed portion is removed.

  As the developer, an explosion-proof facility is unnecessary, and the burden on the facility due to corrosion or the like is small, so an alkaline aqueous solution is preferably used. For example, alkaline aqueous solutions, such as tetramethylammonium hydroxide aqueous solution, sodium silicate aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, are mentioned. The time required for development depends on the thickness of the photosensitive resin composition layer and the type of solvent, but is preferably in the range of 10 seconds to 5 minutes because development can be efficiently performed and production efficiency is increased. The thin film pattern used after development is preferably washed with distilled water to remove the alkaline aqueous solution remaining on the thin film.

  In the method for producing a thin film pattern according to the present invention, after the step of forming a patterned latent image, the cured photosensitive resin composition layer is irradiated with a light beam having a wavelength B different from the wavelength A, and the second photoacid is produced. Alternatively, the method further includes a step of generating an acid or a base from the base generator. Since the photosensitive resin composition according to the present invention contains a second photoacid or base generator that generates an acid or a base by irradiation with a light beam having a wavelength B different from the wavelength A, when the light beam having a wavelength B is irradiated, An acid or base is generated from the photoacid or base generator of No. 2.

  By the way, after exposure to form a patterned latent image, most of the alkoxysilane condensate is crosslinked in the exposed portion, but the exposed portion of the photosensitive resin composition layer is usually slightly alkoxy. The uncrosslinked component of the silane condensate remains. However, in the method for producing a thin film pattern of the present invention, crosslinking of the uncrosslinked component of the alkoxysilane condensate proceeds by the acid or base generated from the second photoacid or base generator upon irradiation with light of wavelength B. The residual amount of the uncrosslinked component can be reduced. In particular, by containing a second photoacid or base generator that is not activated by irradiation with light of wavelength A that is irradiated when forming a pattern, second photoacid or base is generated by irradiation with light of wavelength B. Since a new acid can be generated from the agent, the crosslinking reaction of the alkoxysilane condensate can proceed efficiently and reliably.

  When irradiating the cured photosensitive resin composition layer with the light beam having the wavelength B before the step of obtaining the thin film pattern, the uncured photosensitive resin composition layer that is an unexposed portion is irradiated with the light beam having the wavelength B. It is necessary not to be done. That is, only the cured photosensitive resin composition layer, which is the exposed portion, is irradiated with a light beam having a wavelength B different from the wavelength A so that the uncured photosensitive resin composition layer is not cured by irradiation with the light beam with the wavelength B. It is necessary not to irradiate the uncured photosensitive resin composition layer which is an unexposed portion.

  The step of generating an acid or base from the second photoacid or base generator is preferably performed after the step of obtaining a thin film pattern. In this case, the photosensitive resin composition layer that is an unexposed portion is removed, and only the cured photosensitive resin composition layer that is an exposed portion can be irradiated with light having a wavelength B. The cross-linking component can be effectively cross-linked, and a thin film pattern having an excellent pattern shape can be obtained.

  Although it does not specifically limit as a light source for irradiating the light of wavelength A or wavelength B, such as an ultraviolet-ray and visible light, A superhigh pressure mercury lamp, a Deep UV lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer laser, etc. are used. be able to. These light sources are appropriately selected according to the photosensitive wavelength of the first and second photoacids or base generators or sensitizers.

The irradiation energy of light for irradiating the photosensitive resin composition layer with light of wavelength A and generating an acid or base from the first photoacid or photobase generator is the desired film thickness, the first photoacid or Although depending on the type of base generator or sensitizer, it is generally in the range of 10 to 1000 mJ / cm ² . When it is less than 10 mJ / cm ² , the alkoxysilane condensate is not sufficiently exposed. Moreover, when larger than 1000 mJ / cm < ² >, there exists a possibility that exposure time may become long and there exists a possibility that the manufacturing efficiency per time of a thin film pattern may fall.

After the exposure, the cured photosensitive resin composition layer is irradiated with light having a wavelength B, and the irradiation energy of light for generating an acid or a base from the second photoacid or photobase generator is 10 to 200,000 mJ / A range of cm ² is preferred. If it is less than 10 mJ / cm ^2, acid or base may not be sufficiently generated from the second photoacid or photobase generator. Moreover, when larger than 200,000 mJ / cm < ² >, there exists a possibility that irradiation time may become long and there exists a possibility that the manufacturing efficiency per time of a thin film pattern may fall.

  When the photosensitive resin composition does not contain the second photoacid or base generator as in the prior art, in order to reduce the uncrosslinked component of the alkoxysilane condensate and increase the crosslinking efficiency, for example, It is necessary to heat-treat the thin film pattern at a very high temperature of 500 ° C. or higher. In order to perform heat treatment at such a very high temperature of 500 ° C. or higher, it is necessary to use special heating equipment. Furthermore, when heat treatment is performed at 500 ° C. or higher, not only the substrate and the thin film pattern but also other portions on the substrate tend to deteriorate.

  However, in the present invention, since the second photoacid or base generator is further contained in addition to the first photoacid or base generator, the photosensitive resin composition layer cured after exposure is cured. By further irradiating with light of wavelength B, the crosslinking efficiency of the alkoxysilane condensate can be effectively increased.

  In addition, in the manufacturing method of the thin film pattern which concerns on this invention, it irradiates when exposing the light ray of the wavelength which generate | occur | produces an acid or a base from a 2nd photoacid or a base generator, From a 1st photoacid or a base generator In the case of irradiation after exposure to light having a wavelength that generates an acid or base, the second photoacid or base generator becomes the first photoacid or base generator, and the first photoacid or base generator becomes It becomes the second photoacid or base generator. That is, the first photoacid or base generator and the second photoacid or base generator can be used interchangeably by appropriately selecting the wavelength of the light beam to be irradiated upon exposure and after exposure. However, in the present invention, a photoacid or base generator that generates an acid or a base by light having a wavelength irradiated upon exposure is referred to as a first photoacid or base generator.

  The photosensitive resin composition according to the present invention is suitably used for forming a thin film pattern in various apparatuses, but preferably, the thin film pattern is effectively used for a protective film of an electronic device. By using a thin film pattern formed using the photosensitive resin composition according to the present invention as an insulating protective film of an electronic device, the shape stability of the obtained insulating protective film can be effectively increased. Examples of the insulating protective film of such an electronic device include, for example, a TFT protective film for protecting a thin film transistor (TFT), that is, a passivation film, a protective film for protecting a filter in a color filter, that is, an overcoat film, and an organic EL element. And a protective film, that is, a passivation film.

  FIG. 2 is a schematic front sectional view of a liquid crystal display element using the insulating protective film for electronic equipment according to the present invention, and FIG. 3 is a partially cutaway front sectional view showing an enlarged main part thereof.

  As shown in FIG. 2, the liquid crystal display element 11 has a structure in which a TFT 13 is formed on a glass substrate 12. A TFT protective film 14 is formed so as to cover the TFT 13. In the liquid crystal display element 11, the TFT protective film 14 is composed of the insulating protective film for electronic equipment of the present invention.

  The TFT protective film 14 is patterned to have a desired planar shape in the liquid crystal display element 11 so as to cover the TFT 13, and the stability of the pattern shape is excellent.

  In FIG. 2, an ITO electrode 15 is formed on the TFT protective film 14. An alignment film 16 is formed so as to cover the ITO electrode 15, and the alignment film 16 is opposed to the other alignment film 17 located above. The space between the alignment films 16 and 17 is sealed with a sealing material 18 and filled with a liquid crystal 19. Further, a spacer 20 is disposed between the alignment films 16 and 17 in order to ensure the thickness of the space.

  The alignment film 17 is supported by the upper glass substrate 21. That is, the color filter 22 and the ITO electrode 23 are formed on the lower surface of the glass substrate 21, and the alignment film 17 is formed so as to cover the ITO electrode 23.

  Further, as shown in an enlarged view in FIG. 3, more specifically, the portion where the TFT 13 is formed has a gate electrode 13a formed on the glass substrate 12 so as to cover the gate electrode 13a. A gate insulating film 13b is formed. A semiconductor layer 13c is formed on the gate insulating film 13b so as to face the gate electrode 13a. A source electrode 13d and a drain electrode 13e are connected to the semiconductor layer 13c.

  The above-described TFT protective film 14 is laminated so as to cover the TFT 13 configured as described above.

  FIG. 4 is a partially cutaway sectional view showing an example of a configuration in which the insulating protective film according to the present invention is used as a protective film in a liquid crystal display element or a color filter. Here, the color filter 31 includes a red pixel 32a, a green pixel 32b, a blue pixel 32c, and a black matrix unit 33. An insulating protective film 34 is formed so as to cover them, and the insulating protective film 34 for electronic equipment according to the present invention is used as the insulating protective film 34. Therefore, the shape stability of the planar shape of the protective film 34 is effectively enhanced. An ITO electrode 35 is formed on the protective film 34.

  The insulating protective film for electronic equipment according to the present invention is not limited to the above-described liquid crystal display element and color filter, but includes, for example, a TFT protective film for organic EL elements, an interlayer insulating film for IC chips, an interlayer protective film for IC chips, Widely used as insulating protective films for various electronic devices such as sensor insulating layers. Therefore, according to the present invention, it is possible to provide a display device such as the organic EL element or liquid crystal display element provided with the thin film as a protective film for electronic equipment, a color filter, or a thin film transistor provided with the thin film as a passivation film.

  Among these, a thin film obtained by introducing a crosslinked structure by irradiating the photosensitive resin composition according to the present invention with light is suitably used as a gate insulating film of a field effect thin film transistor. That is, in the thin film transistor provided by the present invention, the gate insulating film is formed by the thin film pattern formed as described above. In this case, as described above, a large-scale vacuum apparatus is not required for forming the gate insulating film. Therefore, the gate insulating film can be formed inexpensively and efficiently.

  In addition, since the gate insulating film is formed of the crosslinked film of the photosensitive resin composition, the mobility can be increased and the on / off current value can be increased.

  In addition, the thin film transistor according to the present invention preferably further includes a passivation film, and this passivation film is also constituted by a crosslinked film of the photosensitive resin composition. Even in this case, the protection performance under high temperature and high humidity can be improved as compared with the case where a passivation film made of a conventional PVA film is used.

  In the thin film transistor according to the present invention, as described above, the gate insulating film is constituted by the crosslinked film of the specific photosensitive resin composition, and thus other structures are not particularly limited. That is, a field effect thin film transistor including a semiconductor layer, a source electrode, a drain electrode, and a gate electrode provided in contact with the semiconductor layer, and the gate insulating film disposed between the gate electrode and the semiconductor layer. As long as there is a physical structure, it is not particularly limited. Specific examples of the structure of such a field effect thin film transistor are illustrated in FIGS.

  In the thin film transistor 41 shown in FIG. 5, the gate electrode 43 is formed on the substrate 42. A gate insulating film 44 is formed so as to cover the gate electrode 43. The gate insulating film 44 is composed of a crosslinked film of the specific photosensitive resin composition. A semiconductor layer 45 is stacked on the gate insulating film 44. A source electrode 46 and a drain 47 electrode are formed in contact with the semiconductor layer 45. Further, a passivation film 48 is formed so as to cover the semiconductor layer 45, the source electrode 46 and the drain electrode 47. An ITO electrode 49 connected to the drain electrode 47 is formed thereon.

  On the other hand, in the thin film transistor 51 shown in FIG. 6, the semiconductor layer 53 is formed on the substrate 52. A gate insulating film 54 is formed on the semiconductor layer 53. The gate insulating film 54 is formed of a crosslinked film of the photosensitive resin composition. A gate electrode 55 is formed on the gate insulating film 54. On the other hand, the source electrode 56 and the drain electrode 57 penetrate the gate insulating film 54 and are bonded to the semiconductor layer 53.

  A passivation film 58 is formed on the gate insulating film 54 and the gate electrode 55. Further, a passivation film 59 is laminated to flatten the upper surface, and an ITO electrode 70 connected to the drain electrode 57 is formed on the passivation film 59.

  As shown in the thin film transistors 41 and 51, the structure of the thin film transistor to which the present invention is applied is not particularly limited. Further, there is no particular limitation on the material forming the semiconductor layer in the thin film transistor according to the present invention, and various semiconductors such as amorphous silicon, polysilicon, and organic semiconductor can be used. The source electrode, the drain electrode, and the gate electrode can also be made of an electrode material made of an appropriate metal.

  Further, the passivation films 48, 58 and 59 are not essential, but are preferably formed of a crosslinked film of the photosensitive resin composition. However, the passivation films 48, 58 and 59 may be made of an inorganic material such as SiN or may be made of an organic material such as PVA. Further, the passivation films 48, 58, and 59 may be configured using a combination of a crosslinked film of the photosensitive resin composition and an inorganic material such as SiN or an organic material such as PVA.

  Hereinafter, the present invention will be clarified by giving examples and comparative examples of the present invention. In addition, this invention is not limited to a following example.

(Materials used)
[Condensate of alkoxysilane]
To a 100 ml flask equipped with a condenser, 5 g of phenyltriethoxysilane, 10 g of triethoxysilane, 0.5 g of oxalic acid, 5 ml of water and 50 ml of propylene glycol monomethyl ether acetate were added. The solution was stirred using a semicircular type mechanical stirrer and reacted at 70 ° C. for 6 hours with a mantle heater. Subsequently, ethanol and residual water produced by the condensation reaction with water were removed using an evaporator. After completion of the reaction, the flask was left to reach room temperature to prepare an alkoxysilane condensate.

[Photoacid generator or photobase generator]
(A1) Sulfonate (Photo acid generator, CAS No. 83697-53-4, manufactured by Midori Chemical Co., Ltd., trade name: NAI-100, λmax: 336 nm)
(A2) Triazine compound (photo acid generator, CAS No. 71255-78-42, manufactured by Midori Chemical Co., Ltd., trade name: TAZ-107, λmax: 356 nm)
(A3) Sulfonate (Photoacid generator, CAS No. 34684-40-7, Midori Chemical, trade name: SI-105, λmax: 234 nm)
(A4) Sulfonium salt (photoacid generator, CAS No. 578355-99-1, Midori Chemical, trade name: TPS-102, λmax: 233 nm)
(B1) Carbamate compound (photobase generator, CAS No. 119137-03-0, manufactured by Midori Chemical Co., Ltd., trade name: NBC-101, λmax: 254 nm)
(Example 1)
After mixing 100 g of the alkoxysilane condensate, 3 g of the photoacid generator (A1), and 3 g of the photoacid generator (A3), the mixture is dissolved in 500 g of tetrahydrofuran as a solvent to obtain a photosensitive resin composition. Prepared.

(Examples 2 to 10 and Comparative Example 1)
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the type and blending amount of the photoacid generator or photobase generator used were changed as shown in Table 1 below.

(Evaluation of photosensitive resin composition)
(1) State of patterning As a base material, the glass substrate by which aluminum was vapor-deposited on the surface layer was used, and each photosensitive resin composition of an Example and a comparative example was spin-coated at the rotation speed of 1500 rpm on this glass substrate. After coating, it was dried in a hot air oven at 80 ° C. to form a coating film.

Next, when irradiating 365 nm ultraviolet rays through a photomask having a predetermined pattern, an ultraviolet irradiation device (manufactured by USHIO INC., Multilight ii type ML-501C / B, super high pressure mercury lamp) is used, and 254 nm. When irradiating the ultraviolet rays, a low-pressure mercury lamp is used, and the ultraviolet rays having the wavelength A shown in Table 1 below are applied to the coating film through a bandpass filter having the wavelength A shown in Table 1 below so that the irradiation energy is 500 mJ / cm ^2. Irradiation with ultraviolet illuminance of 100 mW / cm ² for 5 seconds. After irradiating with ultraviolet rays, the coating film was heated in a hot air oven at 100 ° C. for 5 minutes. Thereafter, the coating film was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide and developed to form a thin film pattern.

Furthermore, when irradiating 365 nm ultraviolet rays, an ultraviolet irradiating device (manufactured by USHIO INC., Multilight ii type ML-501C / B, ultra-high pressure mercury lamp) is used. Through the bandpass filter of wavelength B shown in Table 1 below, the thin film pattern was irradiated with UV light of wavelength B shown in Table 1 below for 30 seconds at an ultraviolet illumination of 100 mW / cm ² so that the irradiation energy was 3000 mJ / cm ² . . Next, the thin film pattern was heat-treated in a hot air oven at 150 ° C. for 30 minutes and further in a hot air oven at 200 ° C. for 1 hour.

The state of patterning of the thin film pattern thus obtained was evaluated according to the following evaluation criteria.
[Criteria for patterning status]
○: A good pattern is formed. Δ: A pattern is formed only partially. ×: A pattern is not formed. (2) Volume resistance Further, regarding the thin film pattern obtained as described above, R8252 (electrometer), The volume resistance was determined according to JIS K 6911 using R12704 (module) (manufactured by Advantest).

  The results are shown in Table 1 below.

1A to 1C are cross-sectional views of each step for explaining a method for manufacturing a thin film pattern according to the present invention. FIG. 2 is a front sectional view showing a liquid crystal display element in which the insulating protective film for electronic equipment according to the present invention is used. FIG. 3 is a partially cutaway front cross-sectional view for explaining a main part of the liquid crystal display element shown in FIG. FIG. 4 is a partially cutaway front sectional view showing a color filter in which the insulating protective film for electronic equipment of the present invention is used. FIG. 5 is a schematic front sectional view showing a structural example of the thin film transistor of the present invention. FIG. 6 is a schematic front sectional view showing another structural example of the thin film transistor of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Photosensitive resin composition layer 1A ... Latent image 1B ... Photosensitive layer 1C ... Thin film pattern 2 ... Substrate 3 ... Photomask 11 ... Liquid crystal display element 12 ... Glass substrate 13 ... TFT
DESCRIPTION OF SYMBOLS 13a ... Gate electrode 13b ... Gate insulating film 13c ... Semiconductor layer 13d ... Source electrode 13e ... Drain electrode 14 ... TFT protective film (insulating protective film for electronic devices)
DESCRIPTION OF SYMBOLS 15 ... ITO electrode 16 ... Orientation film 17 ... Orientation film 18 ... Sealing material 19 ... Liquid crystal 20 ... Spacer 21 ... Glass substrate 22 ... Color filter 23 ... ITO electrode 31 ... Color filter 32a-32c ... Pixel 33 ... Black matrix part 34 ... Insulating protective film (Insulating protective film for electronic equipment)
35 ... ITO electrode 41 ... Thin film transistor 42 ... Substrate 43 ... Gate electrode 44 ... Gate insulating film 45 ... Semiconductor layer 46, 47 ... Source or drain electrode 48 ... Passivation film 49 ... ITO electrode 51 ... Thin film transistor 52 ... Substrate 53 ... Semiconductor layer 54 ... Gate insulating film 55 ... Gate electrode 56, 57 ... Source or drain electrode 58,59 ... Passivation film 70 ... ITO electrode

Claims (15)

  An alkoxysilane condensate, a first photoacid or base generator that generates an acid or base upon activation by irradiation with light of wavelength A, and an acid or acid that is activated by irradiation with light of wavelength B different from wavelength A; A photosensitive resin composition comprising a second photoacid or base generator for generating a base. The first photoacid or base generator causes the crosslinking reaction of the alkoxysilane condensate by irradiation with light of wavelength A to cure the photosensitive resin composition to obtain a cured photosensitive resin. Or a base generator,
The photoacid which makes the said 2nd photoacid or base generator advance the crosslinking reaction of the condensate of the said alkoxysilane which is not bridge | crosslinked contained in the said photosensitive resin hardened | cured material by irradiation of the light of the wavelength B different from the wavelength A The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is a base generator.   The photosensitive resin composition according to claim 1 or 2, wherein the second photoacid or base generator is a photoacid or base generator that is not activated when irradiated with light having a wavelength of A.   The wavelength λmax of the light beam that most activates the first photoacid or base generator is different from the wavelength λmax of the light beam that most activates the second photoacid or base generator. Item 4. The photosensitive resin composition according to any one of Items 1 to 3.   The wavelength difference between the wavelength λmax of the light beam most activating the first photoacid or base generator and the wavelength λmax of the light beam most activating the second photoacid or base generator is 50 nm or more, The photosensitive resin composition of any one of Claims 1-4.   0.05 to 50 parts by weight of the first photoacid or base generator and 0.05 to 50 parts by weight of the second photoacid or base generator with respect to 100 parts by weight of the alkoxysilane condensate. The photosensitive resin composition of any one of Claims 1-5 each contained in the ratio of a part. Forming a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 6 on a substrate;
Depending on the pattern to be formed, the photosensitive resin composition layer is selectively exposed with a light beam having a wavelength A to generate an acid or a base from the first photoacid or base generator. Curing the layer to form a patterned latent image;
After forming the patterned latent image, developing the photosensitive resin composition layer on which the latent image is formed with a developer to obtain a thin film pattern comprising the cured photosensitive resin composition layer;
After the step of forming the patterned latent image, the cured photosensitive resin composition layer is irradiated with a light beam having a wavelength B different from the wavelength A, and an acid or a base is applied from the second photoacid or base generator. And a step of generating the thin film pattern.   The method for producing a thin film pattern according to claim 7, wherein a step of generating an acid or a base from the second photoacid or base generator is performed after the step of obtaining the thin film pattern.   The protective film for electronic devices formed using the photosensitive resin composition of any one of Claims 1-6.   A transistor comprising a thin film formed using the photosensitive resin composition according to claim 1 as a protective film.   A color filter comprising a thin film formed using the photosensitive resin composition according to claim 1 as a protective film.   An organic EL device comprising a thin film formed using the photosensitive resin composition according to claim 1 as a protective film.   It is a gate insulating film of a field effect type transistor, Comprising: It consists of a thin film formed using the photosensitive resin composition of any one of Claims 1-6, The gate insulating film characterized by the above-mentioned.   A field-effect thin film transistor comprising a semiconductor layer, a source electrode and a drain electrode provided in contact with the semiconductor layer, a gate electrode, and a gate insulating film disposed between the gate electrode and the semiconductor layer. A thin film transistor, wherein the gate insulating film is composed of a thin film formed using the photosensitive resin composition according to any one of claims 1 to 6.   Field effect type comprising a semiconductor layer, a source electrode and a drain electrode provided in contact with the semiconductor layer, a gate electrode, a gate insulating film disposed between the gate electrode and the semiconductor layer, and a passivation film It is a thin-film transistor, Comprising: The said passivation film is a thin film formed using the photosensitive resin composition of any one of Claims 1-6, The thin-film transistor characterized by the above-mentioned.

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