WO2011108705A1

WO2011108705A1 - Photosensitive resin composition

Info

Publication number: WO2011108705A1
Application number: PCT/JP2011/055074
Authority: WO
Inventors: 憲司原
Original assignee: 株式会社Adeka
Priority date: 2010-03-05
Filing date: 2011-03-04
Publication date: 2011-09-09
Also published as: TW201140243A; CN102597879A; JP2011186069A; KR20110101073A

Abstract

Disclosed is a photosensitive resin composition—that can form a minute pattern by means of photolithography, can form a insulating film without heat treatment above 200°C, and has no problems of carrier being trapped and charge mobility decreasing when used as a gate insulating film of an organic thin-film transistor—containing a photo-radical generating agent and a polysiloxane compound having units represented by the belowmentioned general formulae (1-4). (In formula 1, R¹ represents a hydrogen atom or a methyl group, and R² represents an alkylene group having a carbon number of 1-5 that may have a substituent alkyl group. In formula 2, R³ represents a hydrogen atom or an alkyl group having a carbon number of 1-4. In formula 3, R⁴ represents an alkyl group having a carbon number of 1-6 or a cycloalkyl group having a carbon number of 5-6. In formula 4, R⁵ represents a hydrogen atom or an alkyl group having a carbon number of 1-4.)

Description

Photosensitive resin composition

The present invention relates to a photosensitive resin composition using a polysiloxane compound, and further relates to a negative photoresist (in particular, a permanent resist) using the photosensitive resin composition.

In recent years, researches on display devices such as liquid crystal display devices and EL display devices have been actively conducted, and electronic paper has attracted attention as one of display devices that can be driven with low power consumption. Electronic paper can be made as thin as paper, and has the advantage of being able to hold images even with low power consumption and with the power turned off, and is expected to be used for electronic books and posters It is done. If plastic film is used for the display substrate of electronic paper and organic thin film transistor is used for the drive part of the display device, it is flexible and it can be displayed without loss of quality even if it is bent. It is done.

The gate insulating film of the organic thin film transistor is generally manufactured by depositing a highly insulating inorganic material such as silicon carbide, silicon nitride, aluminum oxide, tantalum oxide, titanium oxide or the like by the CVD method. There is a problem in the manufacturing cost because a large vacuum system is required. Moreover, these inorganic materials are hard and rigid, and when applied to a flexible substrate such as a plastic film, there is a risk of breakage due to bending.

On the other hand, since many organic materials are soluble in organic solvents, they can be mass-produced inexpensively by coating and printing methods, and are excellent in flexibility and adhesion to plastic films. Therefore, studies on organic insulating materials for gate insulating films of organic thin film transistors are actively conducted.

In the case of electronic paper and the like, a fine display device is required, and in the gate insulating film of the organic thin film transistor used therein, the formation of a fine pattern is required. A method of forming a fine pattern is photolithography, and a photosensitive resin composition capable of forming a gate insulating film by photolithography contains a condensate of an alkoxysilane and a photoacid generator or a base generator. Photosensitive resin compositions (see, for example, Patent Documents 1 to 3) are known.
However, in such a photosensitive resin composition, current leakage may occur due to the remaining photoacid generator or base generator and their decomposition products. Further, in order to cure the photosensitive resin composition by crosslinking of the alkoxysilyl group, it is necessary to heat-treat about 200 to 500.degree. For this reason, plastic films, such as a polycarbonate and a polyethylene terephthalate, were not able to be used as a board | substrate. A photosensitive resin composition containing a polysiloxane compound having an epoxy group and a photoacid generator is known as a photosensitive resin composition capable of photolithography and obtaining an insulating film having high insulation properties. However, the insulating film obtained from such a photosensitive resin composition has a problem that carriers formed in the semiconductor layer are trapped by the hydroxyl groups generated by ring opening of epoxy and the charge mobility is lowered.

Unexamined-Japanese-Patent No. 6-148895 JP 2007-43055 A JP 2007-316531 A

Therefore, the object of the present invention is to form a fine pattern by photolithography, to form an insulating film without heat treatment exceeding 200 ° C., and to trap carriers when used as a gate insulating film of an organic thin film transistor. It is an object of the present invention to provide a photosensitive resin composition free from the problem of a decrease in charge mobility.

The present inventors arrived at the present invention as a result of earnest research in view of the above. That is, the present invention provides a photosensitive resin composition containing a polysiloxane compound having units represented by the following general formulas (1) to (4), and a photo radical generator.

(Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkylene group having 1 to 5 carbon atoms which may have a substituted alkyl group)

(Wherein, R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

(Wherein, R ⁴ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms)

(Wherein, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

The effects of the present invention are not only high transparency, but also photosensitivity that can provide an insulating layer excellent in heat resistance and solvent resistance that can withstand the temperature at the time of substrate manufacture, and further, resistance to aging change as a permanent resist. Resin composition (in particular, a negative photosensitive resin composition), and a negative photoresist (in particular, a permanent resist) using the photosensitive resin composition.

FIG. 1 is a schematic cross-sectional view of a bottom gate / top contact type organic thin film transistor in which a thin film obtained from the photosensitive resin composition of Examples 1 and 2 and Comparative Examples 1 and 2 is a gate insulating film.

Hereinafter, the present invention will be described in detail based on preferred embodiments.
First, a polysiloxane compound having units represented by the general formulas (1) to (4) (hereinafter sometimes referred to as the polysiloxane compound of the present invention) will be described.

In the above general formula (1), R ¹ represents a hydrogen atom or a methyl group, and a methyl group is preferable because of good storage stability. R ² represents an alkylene group having 1 to 5 carbon atoms which may have a substituted alkyl group. Examples of the alkylene group having 1 to 5 carbon atoms include methylene, ethylene, propylene, butylene and pentene. From the viewpoint of heat resistance, it is preferable that the number of carbon atoms is small. However, ethylene, propylene and Butylene is preferred, ethylene and propylene are more preferred, and propylene is most preferred. Examples of the substituted alkyl group which may be possessed in R ² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl and the like, but from the viewpoint of heat resistance, it does not have a substituted alkyl group. Is preferred.

In the above general formula (2), R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and as the alkyl group having 1 to 4 carbon atoms, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary Butyl, t-butyl and the like. As R ³ , a hydrogen atom is preferable because industrial availability is easy and heat resistance is good.

In the above general formula (3), R ⁴ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms. Examples of the alkyl having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, t-butyl, pentyl, isopentyl, neopentyl, 2-pentyl, t-pentyl, hexyl, 2-hexyl and the like And examples of the cycloalkyl group having 5 or 6 carbon atoms include cyclopentyl, cyclohexyl, methylcyclopentyl, cyclopentylmethyl and the like. From the viewpoint of good heat resistance, R ⁴ is preferably ethyl and methyl, more preferably methyl.

In the above general formula (4), R ⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl and t-butyl. As R ⁵ , a hydrogen atom is preferable because industrial availability is easy and heat resistance is good.

In the polysiloxane compound of the present invention, the content of the unit represented by the general formula (1) is preferably 0.1 to 5 mmol / g, more preferably 0.5 to 3 mmol / g, and 1 Most preferably, it is -2.5 mmol / g. The content of the unit represented by the general formula (2) is preferably 0.01 to 0.8 with respect to the total of the number of units represented by the general formulas (1) to (4). More preferably, it is 03 to 0.5, and most preferably 0.05 to 0.3. The content of the unit represented by the general formula (3) is preferably 0.03 to 0.8 with respect to the total of the number of units represented by the general formulas (1) to (4). More preferably, it is 07 to 0.7, and most preferably 0.15 to 0.6. The content of the unit represented by the general formula (4) is preferably 0.01 to 0.6 with respect to the total of the number of units represented by the general formulas (1) to (4). It is more preferably 03 to 0.4, and most preferably 0.05 to 0.25.

The ratio of the sum of the number of units represented by the general formula (2) to the number of units represented by the general formula (4) with respect to the number of units represented by the general formula (3) is Although it changes with uses for which a photosensitive resin composition is used, when using as a negative resist, 0.3-5.0 are preferable, 0.5-3 are more preferable, and 1.5-2.5. Is most preferred. Moreover, when using the photosensitive resin composition of this invention as transparent materials, such as a lens and an optical waveguide, 0.3-7.0 are preferable, 0.3-5 are still more preferable, 0.3-3 Is most preferred.

When the molecular weight of the polysiloxane compound of the present invention is too small, the coatability and film forming property of the photosensitive resin composition of the present invention become insufficient, and when the molecular weight is too large, the handling property decreases. The polysiloxane compound of the present invention preferably has a weight average molecular weight of 1,000 to 100,000, more preferably 2,000 to 50,000, and most preferably 3,000 to 20,000. In the present invention, the mass average molecular weight refers to a mass average molecular weight in terms of polystyrene when GPC analysis is performed using tetrahydrofuran (hereinafter referred to as THF) as a solvent.

The polysiloxane compound of the present invention may have a silanol group (SiOH group) remaining in the production process, but the presence of the silanol group reduces the storage stability of the photosensitive resin composition of the present invention. The content of silanol groups in the polysiloxane compound of the present invention is preferably 1.0 mmol / g or less, more preferably 0.1 mmol / g or less. In addition, the silanol group used the near-infrared spectrophotometer (refer Unexamined-Japanese-Patent 2001-208683, Unexamined-Japanese-Patent 2003-35667 etc.), and ²⁹ Si-NMR (refer Unexamined-Japanese-Patent 2007-217249 etc.). It can be quantified by instrumental analysis. The silanol group can be reduced by a halosilane compound or a hydrolyzable ester as described later.

The polysiloxane compound of the present invention preferably further has a unit represented by the following general formula (5) because adhesion is improved.

(Wherein, E represents a group having an epoxy group)

In the general formula (5), E represents a group having an epoxy group, and examples of the group having an epoxy group include groups represented by the following general formulas (6) to (8), and the adhesion is improved Groups having the following general formulas (7) and (8) are preferable, and groups having the following general formula (7) are more preferable, because the effect is large.

(Wherein, R ⁶ represents an alkylene group of 1 to 5 carbon atoms which may have a substituted alkyl group, and m represents a number of 0 or 1).

(Wherein, R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents an alkylene group having 1 to 5 carbon atoms which may have a substituted alkyl group, and n is 0 or 1).

(Wherein, R ⁹ represents an alkylene group of 1 to 5 carbon atoms which may have a substituted alkyl group)

In the above general formula (6), R ⁶ represents an alkylene group of 1 to 5 carbon atoms which may have a substituted alkyl group. Examples of the alkylene group having 1 to 5 carbon atoms include methylene, ethylene, propylene, butylene and pentene. From the viewpoint of heat resistance, it is preferable that the number of carbon atoms is small. However, ethylene, propylene and Butylene is preferred, ethylene and propylene are more preferred, and ethylene is most preferred. Examples of the substituted alkyl group which may be possessed in R ⁶ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl and the like, but from the viewpoint of heat resistance, it does not have a substituted alkyl group. Is preferred. m is preferably a number of 1 because m represents a number of 0 or 1 and the availability of raw materials is easy.

In the above general formula (7), R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents an alkylene group having 1 to 5 carbon atoms which may have a substituted alkyl group. Examples of the alkylene group having 1 to 5 carbon atoms include methylene, ethylene, propylene, butylene and pentene. From the viewpoint of heat resistance, it is preferable that the number of carbon atoms is small. However, ethylene, propylene and Butylene is preferred, ethylene and propylene are more preferred, and ethylene is most preferred. Examples of the substituted alkyl group which may be possessed in R ⁸ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl and the like, but from the viewpoint of heat resistance, it does not have a substituted alkyl group. Is preferred. n is preferably a number of 1 because n represents a number of 0 or 1 and the availability of raw materials is easy.

When the polysiloxane compound of the present invention further has a unit represented by the general formula (5), the effect of improving the adhesion is small when the content of the unit represented by the general formula (5) is too small, Moreover, since the tack may appear on the surface of a cured product obtained by curing the photosensitive resin composition of the present invention when the content is too large, the content of the unit represented by the general formula (5) is an epoxy equivalent It is preferably 2000 to 50000, and more preferably 3000 to 20000.

The polysiloxane compound of the present invention can be obtained by a hydrolysis condensation reaction of an alkoxysilane compound or a halosilane compound represented by the following general formulas (1a) to (4a), so-called sol-gel reaction.

(Wherein, R ¹ and R ² are as defined in the general formula (1), and X ¹ represents a halogen atom or an alkoxyl group having 1 to 4 carbon atoms).

(Wherein, R ³ has the same meaning as in the above general formula (2), and X ² represents a halogen atom or an alkoxyl group having 1 to 4 carbon atoms).

(Wherein, R ⁴ has the same meaning as in the above general formula (3), and X ³ represents a halogen atom or an alkoxyl group having 1 to 4 carbon atoms).

(Wherein, R ⁵ has the same meaning as in the above general formula (4), and X ⁴ represents a halogen atom or an alkoxyl group having 1 to 4 carbon atoms).

Examples of the alkoxysilane compound represented by the general formula (1a) include (acryloxymethyl) trimethoxysilane, (2-acryloxypropyl) trimethoxysilane, and (3-acryloxypropyl) trimethoxysilane. , (3-acryloxypropyl) triethoxysilane, (methacryloxymethyl) trimethoxysilane, (2-methacryloxypropyl) trimethoxysilane, (3-methacryloxypropyl) trimethoxysilane, (3- Methacryloxypropyl) triethoxysilane is mentioned, and as the halosilane compound represented by the above general formula (1a), for example, 3-acryloxypropyl) trichlorosilane, (3-methacryloxypropyl) trichlorosilane and the like can be mentioned . As the alkoxysilane compound or halosilane compound represented by the above general formula (1a), (3-methacryloxypropyl) trimethoxysilane, and (3-meth Roxypropyl) triethoxysilane is preferred, and (3-methacryloxypropyl) trimethoxysilane is more preferred.

Examples of the alkoxysilane compound represented by the above general formula (2a) include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, 4-methylphenyltrimethoxysilane, 4-methylphenyltriethoxysilane. Sisilane, 4-methylphenyltriisopropoxysilane and the like can be mentioned, and examples of the halosilane compound represented by the general formula (2a) include phenyltrichlorosilane, 4-methylphenyltrichlorosilane and the like. As the alkoxysilane compound or the halosilane compound represented by the above general formula (2a), phenyltrimethoxysilane and phenyltriethoxysilane are preferable because of their good reactivity and easy control of the reaction. More preferred is tosixisilane.

The alkoxysilane compound represented by the above general formula (3a) includes, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, diethylphenyldimethoxysilane, diethyldiethoxysilane, and diethyldiethoxysilane. Isopropoxysilane, dipropyldimethoxysilane, dipropyldietoxysilane, dipropyldiisopropoxysilane and the like can be mentioned, and as the halosilane compound represented by the general formula (3a), for example, dimethyldichlorosilane, diethyl Dichlorosilane, dipropyl dichlorosilane and the like can be mentioned. As the alkoxysilane compound or the halosilane compound represented by the above general formula (2a), dimethyldimethoxysilane and dimethyldietoxysilane are preferable because of their good reactivity and easy control of the reaction. More preferred is tosixisilane.

Examples of the alkoxysilane compound represented by the above general formula (4a) include diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, bis (4-methylphenyl) dimethoxysilane, bis (4) And the like. Examples of the halosilane compound represented by the general formula (4a) include diphenyldichlorosilane, bis (4-methylphenyl) dietoxysilane, bis (4-methylphenyl) diisopropoxysilane and the like. And phenyl) dichlorosilane and the like. As the alkoxysilane compound or the halosilane compound represented by the above general formula (4a), diphenyldimethoxysilane and diphenyldietoxysilane are preferable because of their good reactivity and easy control of the reaction. More preferred is tosixisilane.

When the alkoxysilane compounds or halosilane compounds represented by the general formulas (1a) to (4a) are hydrolyzed and condensed, it is preferable to react in a solvent using a catalyst such as an acid or a base. Examples of the solvent which can be used for the reaction include water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, toluene, xylene, cyclohexane and the like, and one of these is used It is also possible to use a mixture of two or more. In order to use a solvent other than water, it is preferable to carry out the reaction by adding an appropriate amount of water in order to accelerate the hydrolytic condensation reaction.

In the hydrolysis condensation reaction of an alkoxysilane compound or a halosilane compound, an alkoxysilyl group or a halosilyl group is hydrolyzed by water to form a silanol group, and the generated silanol groups are condensed, or the silanol group and an alkoxyl group or a chlorosilane group are condensed. As a result, a siloxane group (SiOSi group) is formed.

As the catalyst for the above-mentioned hydrolytic condensation reaction, inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid; formic acid, acetic acid, oxalic acid, citric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, monoisopropyl phosphate Organic acids such as; inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia etc .; amine compounds (organic bases) such as trimethylamine, triethylamine, monoethanolamine, diethanolamine etc .; Or two or more kinds in combination. The temperature of the hydrolytic condensation reaction varies depending on the type of solvent, type and amount of catalyst, etc., but it is preferably 0 to 80 ° C., more preferably 5 to 50 ° C., and most preferably 8 to 30 ° C.

When the alkoxysilane compounds or halosilane compounds represented by the general formulas (1a) to (4a) are hydrolyzed and condensed, the respective alkoxysilane compounds or halosilane compounds may be separately reacted or mixed and then reacted. The reaction may be carried out after mixing since reaction can be stably performed with little variation in the reaction products.

When the polysiloxane compound of the present invention further has a unit represented by the general formula (5), in addition to the alkoxysilane compound or the halosilane compound represented by the general formulas (1a) to (4a), the following general formula The alkoxysilane compound or the halosilane compound represented by (5a) may be hydrolyzed and condensed.

(Wherein, E is as defined in the above general formula (5), and X ⁵ represents a halogen atom or an alkoxyl group having 1 to 4 carbon atoms).

Examples of the alkoxysilane compound or halosilane compound represented by the general formula (5a) include 3,4-epoxybutyltrimethoxysilane, 2-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-glycidoxy-1-methylethyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxy Silane, 3,4-epoxycyclohexyltrimethoxysilane, 3,4-epoxycyclohexyltriethoxysilane, 2- (3,4-epoxy-4-methylcyclohexyl) propyltrimethoxysilane and the like can be mentioned.

In the case where the polysiloxane compound of the present invention is obtained by the hydrolysis condensation reaction of an alkoxysilane compound or a halosilane compound, the photosensitive resin composition of the present invention is obtained because the silanol group remains and the silanol group is present. It is preferable to seal the silanol group because the storage stability of When a silanol group is sealed, a method of trimethylsilylating with trimethylchlorosilane, hexamethyldisilazane, a method of alkoxylating with a hydrolysable ester compound such as ortho formate ester, ortho acetate ester, tetraalkoxymethane, carbonate ester, etc. It can be mentioned.

Next, the photoradical generator is described. In the present invention, a photo radical generator is a compound capable of initiating radical polymerization by energy beam irradiation, and examples of energy beam include ultraviolet light, electron beam, X-ray, radiation, high frequency and the like. Examples of photo radical generators include acetophenone photo radical generators, benzyl photo radical generators, benzophenone photo radical generators, thioxanthone photo radical generators, and acyl phosphine oxide photo radical generators. The photo radical generator may be used alone or in combination of two or more.

Examples of the acetophenone photoradical generator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, and the like. -Hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tert-butyl dichloroacetophenone, p-tert-butyl trichloroacetophenone, p-Azidobenzalacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1- (4 -Morpholino phenyl)-pig 1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, 2-hydroxy-2-methyl-1- [4-vinyl- (1-methylvinyl) phenyl Examples of propanone oligomers and the like can be mentioned.

Examples of the benzyl-based photoradical generator include diphenyl diketone (also referred to as benzyl), bis (4-methoxyphenyl) diketone (also referred to as anisyl), and the like.

Examples of the benzophenone-based photoradical generator include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide. Etc.

Examples of the thioxanthone photoradical generator include thioxanthone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chloro thioxanthone, 2-isopropyl thioxanthone, and 2,4-diethyl thioxanthone.

Examples of the acyl phosphine oxide photoradical generator include 2-methylbenzoyl diphenyl phosphine oxide, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2,4,6-trimethyl benzoyl phenyl phosphine acid methyl ester Monoacyl phosphine oxide based photo radical generators such as: bis (2,6-dimethoxybenzoyl) phenyl phosphine oxide, bis (2,4,6-trimethyl benzoyl) phenyl phosphine oxide, bis (2,6-dimethoxy) Examples include bisacylphosphine oxide photoradical generators such as benzoyl) -2,4,4-trimethylpentylphosphine oxide.

When the photosensitive resin composition of the present invention is cured and used as a gate insulating film for an organic thin film transistor, as the photo radical generator, a high charge mobility can be obtained, so an acylphosphine oxide type photo radical generator Monoacyl phosphine oxide photo radical generators are more preferred, and 2,4,6-trimethyl benzoyl diphenyl phosphine oxide is most preferred. When using 2 or more types of photo radical generating agent together, it is preferable that at least 1 type is an acyl phosphine oxide type photo radical generating agent.

In addition, when the photosensitive resin composition of the present invention is cured and used as a transparent material for lenses, waveguides, etc., a cured product having high transparency can be obtained as the photoradical generator, and thus an acetophenone-based material. Photoradical generators and acylphosphine oxide photoradical generators are preferred, acetophenone photoradical generators are more preferred, and 1-hydroxycyclohexyl phenyl ketone is most preferred. When two or more photoradical generators are used in combination, at least one is preferably an acetophenone photoradical generator.

The content of the photoradical generator in the photosensitive resin composition of the present invention is the kind of the photoradical generator, the content of the radically polymerizable group in the photosensitive resin composition of the present invention, and the type of active energy ray Although it changes with strength etc., it is preferable that it is 0.1-10 mass parts with respect to 100 mass parts of polysiloxane compounds of this invention, It is still more preferable that it is 0.2-7 mass parts, 0.3- Most preferably, it is 5 parts by mass. If the content of the photo radical generating agent is less than 0.1 parts by mass, curing may be insufficient, and if it exceeds 10 parts by mass, not only the increasing effect corresponding to the compounding amount can not be obtained, but rather Heat resistance, transparency, etc. may be adversely affected.

The photosensitive resin composition of the present invention may further contain an organic solvent. As such an organic solvent, for example, aromatic hydrocarbon compounds such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, diethylbenzene, tetrahydronaphthalene; pentane, isopentane, hexane, isohexane, heptane, isoheptane, octane, isooctane Saturated hydrocarbon compounds such as nonane, isononane, decane, isodecane, isododecane, cyclohexane, methylcyclohexane, mentane, decahydronaphthalene; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, Ether solvents such as 1,4-dioxane; acetone, methyl ethyl ketone, Ketone solvents such as isobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone and cyclohexanone; ester solvents such as ethyl acetate, methyl acetate, butyl acetate, propyl acetate and cyclohexyl acetate; propylene glycol monomethyl ether acetate, ethylene glycol Examples thereof include glycol ester solvents such as monoethyl ether acetate, dipropylene glycol methyl ether acetate, and diethylene glycol monoethyl ether acetate. These solvents can be used alone or in combination of two or more.

When the photosensitive resin composition of the present invention is used by a coating method or printing method, the content of the organic solvent is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the polysiloxane compound of the present invention And 10 to 100 parts by mass.

The photosensitive resin composition of the present invention may further contain, if necessary, a photosensitizer, a plasticizer, a thixotropy-imparting agent, a photoacid generator, a thermal acid generator, a dispersant, and an antifoamer, in addition to the organic solvent. And optional components such as pigments and dyes can be blended. The total content of these optional components is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the polysiloxane compound of the present invention.

The photosensitive resin composition of the present invention is cured by irradiating an active energy ray after forming a layer of the photosensitive resin composition of the present invention on an object such as a substrate. The method of forming the layer of the photosensitive resin composition of the present invention is not particularly limited, and, for example, dip coating, flow coating, brush coating, spray coating, extrusion coating, spin coating, roll coating Bar coating or the like can be used, and a patterned film can be formed by a method such as screen coating or roll transfer. It does not specifically limit as a target object in which the layer of the photosensitive resin composition of this invention is formed, A silicon substrate, a glass substrate, a metal plate, a plastics board etc. are used according to a use. The thickness of the layer of the photosensitive resin composition of the present invention formed on the object varies depending on the application, but 10 nm to 10 μm when used as an insulating film of a semiconductor element or a gate insulating film of an organic thin film transistor In the case of using as a core portion of 1 to 200 μm is a standard.

When the photosensitive resin composition of the present invention contains an organic solvent, heat treatment (pre-baking may be performed for the purpose of removing the organic solvent in the layer after forming the layer of the photosensitive resin composition of the present invention )I do. The conditions of the heat treatment are appropriately selected depending on the boiling point and vapor pressure of the used organic solvent, the thickness of the layer of the photosensitive resin composition of the present invention, and the heat resistant temperature of the object on which the layer is formed. A heat treatment of 30 seconds to 10 minutes at ̃140 ° C. is a standard.

As a light source which irradiates an active energy ray to the layer of the photosensitive resin composition, an ultra-high pressure mercury lamp, Deep UV lamp, high pressure mercury lamp, low pressure mercury lamp, metal halide lamp, excimer laser, etc. may be mentioned. It is suitably selected according to the photosensitive wavelength of the sensitizer. The irradiation energy of the active energy ray is appropriately selected according to the thickness of the layer of the photosensitive resin composition and the type and amount of use of the photoradical generator.

The layer of the photosensitive resin composition is cured by irradiation with an active energy ray, but heat treatment (sometimes referred to as post-baking) is performed to improve the adhesion between the layer of the cured product and an object such as a substrate. You may Such heat treatment is preferably performed at a temperature of 60 to 200 ° C. for 1 minute to 2 hours in an inert gas atmosphere such as nitrogen, helium, argon or the like.

The coating film obtained from the photosensitive resin composition of the present invention can be used for photolithography, and can be used as a negative photoresist (particularly, a permanent resist). When the photosensitive resin composition of the present invention is used as a negative photoresist, the photosensitive resin composition of the present invention is applied to a substrate or the like to form a coating film, which is exposed to active energy rays. The coating film of the base resin composition is coated with a photo mask and selectively irradiated with active energy rays, and then the light-shielded portion (uncured portion) is dissolved and dispersed in an organic solvent, developer, etc. By developing), a patterned cured film can be formed. Examples of the organic solvent which dissolves and disperses the light-shielded part are alkaline aqueous solution, acidic aqueous solution, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethanol, isopropanol, n-propanol, benzene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Ethyl acetate, butyl acetate, toluene, o-xylene, m-xylene, p-xylene, 1,3,5-trimethylbenzene, 1,3,4-trimethylbenzene and the like can be mentioned.

The cured film obtained by the photosensitive resin composition of the present invention is excellent in transparency, insulation, high refractive index, heat resistance, weather resistance, chemical resistance, etc. It is useful as an optical lens and an insulating film of a semiconductor device. In particular, when used as a gate insulating film of a transistor, there is little problem that carriers are trapped and charge mobility is reduced, and it is extremely useful as a gate insulating film of an organic thin film transistor.

EXAMPLES The present invention will be further described with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto.

Preparation Example A Preparation of Polysiloxane Compound A
In a reaction vessel having a stirrer, a thermometer and a refluxer, 124.2 g (0.5 mol) of 3-methacryloxypropyltrimethoxysilane, 39.7 g (0.2 mol) of phenyltrimethoxysilane, dimethyldimethoxysilane 132 2 g (1.1 mol), 75.3 g (0.2 mol) of diphenyldimethoxysilane and 300 g of 1-butanol as a solvent were charged. After stirring and heating to 70 ° C., 100 parts of a 0.12% aqueous phosphoric acid solution was dropped, and the reaction was further performed at 80 ° C. for 1 hour. Then, an aqueous solution of sodium hydroxide was added to neutralize the reaction liquid, and then reacted at 80 ° C. for 1 hour. After adding 300 g of toluene, the stirring was stopped and the separated water-containing layer was removed. The toluene layer was washed three times with 1000 g of water, and then the solvent was distilled off under reduced pressure at 40 ° C. in a nitrogen stream. To this, 300 g of triethyl orthoformate is added, and the mixture is treated at 130 ° C. for 1 hour, then the pressure is reduced at 80 ° C. under nitrogen stream to distill off volatile components such as unreacted triethyl orthoformate. Compound A was obtained. As a result of analysis by GPC, the mass average molecular weight was 7500, and as a result of analysis by ¹ H-NMR, no silanol group was detected.

Preparation Examples B to I: Preparation of Polysiloxane Compounds B to I
In Production Example A, except that the alkoxysilane compound shown in Table 1 was used, the same procedure as in Production Example A was performed, and polysiloxane compounds B to I shown in Table 1 were synthesized. The numerical values in the table represent the reaction molar ratio of the alkoxysilane compound. Among the polysiloxane compounds in Table 1, polysiloxane compounds A to E are the polysiloxane compounds of the present invention, and polysiloxane compounds F to I are comparative polysiloxane compounds. Table 2 shows the analysis results of mass average molecular weight and silanol group content.

[Examples 1 to 7 and Comparative Examples 1 to 5]
Polysiloxane compounds A to I, acrylates A and B described below, bis (2,6-dimethoxybenzoyl) phenyl phosphine oxide (hereinafter referred to as photo radical generator 1) as a photo radical generator, 1-hydroxycyclohexyl phenyl ketone (Hereinafter referred to as photo radical generator 2), [4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate] as a photoacid generator, platinum as a hydrosilylation catalyst Photosensitive resin compositions or thermosetting resin compositions of Examples 1 to 7 and Comparative Examples 1 to 5 were prepared with the composition of Table 3 using divinyl tetramethyldisiloxane complex and butyl acetate as a solvent .

<Evaluation of photosensitive resin composition as gate insulating film>
In order to evaluate the characteristics as a gate insulating film of the photosensitive resin composition or thermosetting resin composition obtained by the said Example and comparative example, the organic thin-film transistor as shown in FIG. 1 is produced as follows. did.
Chromium (Cr) was vapor-deposited on the glass substrate 6 to form a lead electrode having a width of 2 mm and a thickness of about 100 nm. The photosensitive resin compositions of Examples 1 and 2 and Comparative Example 1 and the thermosetting resin composition of Comparative Example 2 are spin-coated thereon to a film thickness of about 1 μm and air-dried. In Examples 1 and 2 and Comparative Example 1, the high-pressure mercury lamp was irradiated at 5000 mJ / cm ² , and in Comparative Example 2, the gate insulating film 5 was formed by curing by heating at 150 ° C. for 2 hours under a nitrogen atmosphere. A solution of poly- (3-hexyl) thiophene in xylene was spin-coated on the gate insulating film 5 so that the film thickness after drying was 30 nm, and air-dried to form an organic semiconductor film 1. Annealing treatment was performed at 150 ° C. for 30 minutes in a nitrogen atmosphere to activate poly- (3-hexyl) thiophene. Gold (Au) is vapor-deposited on the organic semiconductor film 1 to form a source electrode 2 and a drain electrode 3 with a channel width of 2 mm, a thickness of about 30 nm and a channel length of 100 μm. 12 bottom gate and top contact type organic thin film transistors were manufactured for each of and.

The transport characteristics of the organic thin film transistors of Examples 1 and 2 and Comparative Examples 1 and 2 were measured using a semiconductor parameter analyzer (manufactured by Keithley, product name SCS 4200) to calculate charge mobility μ. The charge mobility μ is defined by the following equation, and specifically, the graph in the saturation region when the square of the absolute value of the drain current I _D is plotted on the vertical axis and the gate voltage V _G is plotted on the horizontal axis. The charge mobility μ was determined based on the slope. The measurement was performed under a nitrogen gas atmosphere and in a light shielding state. The charge mobility μ was an average of the organic thin film transistors whose transport characteristics could be measured, and the number of the organic thin film transistors whose transport characteristics could not be measured due to current leakage was regarded as the number of defective products. The results are shown in Table 4.

<Heat colorability evaluation of photosensitive resin composition>
The photosensitive resin compositions of Examples 3 to 7 and Comparative Examples 1 and 3 are applied by spin coating on a 2.5 cm square glass substrate so that the film thickness after drying is about 500 μm. The solvent was allowed to evaporate. The test piece was heat treated at 120 ° C. for 30 minutes. A photomask with a line width of 1 mm was placed on the top of the heat-treated glass substrate, and ultraviolet light was applied at 100 mJ / cm ² with a high-pressure mercury lamp. Next, the test piece was immersed in a beaker containing ethyl acetate to dissolve and remove the uncured portion, and the air-dried one was used as a test piece for evaluation of heat colorability. The test pieces are all colorless and transparent, and the refractive index of the cured product at a wavelength of 837 nm is as shown in Table 6. The test piece was put in a thermostat at 150 ° C., taken out after 15 days, the coloration of the cured product was visually observed, and the heat colorability was evaluated according to the following evaluation criteria. The results are shown in Table 5.
<Evaluation criteria>
◎: No coloring is observed, and heat coloring is low.
○: Slightly colored and slightly heat-colored.
Δ: Clearly colored and heat coloring is high.
X: It is colored so that the line | wire of a character can not be distinguished through hardened | cured material, and heat | fever coloring property is very high.

As the results in Table 4 indicate, high charge mobility can be obtained in the gate insulating film obtained by curing the photosensitive resin composition of the present invention. On the other hand, a gate insulating film (comparative example 1) obtained by curing a photosensitive resin composition containing a polysiloxane compound having an epoxy group and a photoacid generator, a polysiloxane compound having a vinyl group, SiH In the gate insulating film (comparative example 2) obtained by curing a thermosetting resin composition containing a polysiloxane compound having a hydroxyl group and a hydrosilylation catalyst (platinum catalyst), only a low charge mobility can be obtained, especially the latter The problem is that the defective product rate is high.

In addition, as the results in Table 5 show, the photosensitive resin composition of the present invention can be used as a negative photoresist, and the cured product has a high refractive index and is thermally colored even at high temperatures. Is low (Examples 3 to 7). On the other hand, in the cured products (Comparative Examples 1 and 3 to 5) obtained by curing a photosensitive resin composition having a different composition from the photosensitive resin composition of the present invention, the heat colorability is high.
This shows that when the photosensitive resin composition of the present invention is used for a transparent high refractive index material such as a lens, an optical waveguide, etc., it can be used without losing transparency even at high temperatures. .

1 Organic semiconductor film (layer)
2 source electrode 3 drain electrode 4 gate electrode 5 insulating layer (gate insulating film)
6 Support (substrate)

Claims

A photosensitive resin composition comprising a polysiloxane compound having units represented by the following general formulas (1) to (4) and a photo radical generator.

(Wherein, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkylene group having 1 to 5 carbon atoms which may have a substituted alkyl group)

(Wherein, R 3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

(Wherein, R 4 represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms)

(Wherein, R 5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)
The photosensitive resin composition according to claim 1, wherein the polysiloxane compound having a unit represented by the general formulas (1) to (4) is a polysiloxane compound further having a unit represented by the following general formula (5). object.

(Wherein, E represents a group having an epoxy group)
Polysiloxanes obtained by hydrolytic condensation of alkoxysilane compounds or halosilane compounds represented by the following general formulas (1a) to (4a): polysiloxane compounds having units represented by the general formulas (1) to (4) The photosensitive resin composition according to claim 1, which is a siloxane compound.

(Wherein, R 1 and R 2 are as defined in the general formula (1), and X 1 represents a halogen atom or an alkoxyl group having 1 to 4 carbon atoms).

(Wherein, R 3 has the same meaning as in the above general formula (2), and X 2 represents a halogen atom or an alkoxyl group having 1 to 4 carbon atoms).

(Wherein, R 4 has the same meaning as in the above general formula (3), and X 3 represents a halogen atom or an alkoxyl group having 1 to 4 carbon atoms).

(Wherein, R 5 has the same meaning as in the above general formula (4), and X 4 represents a halogen atom or an alkoxyl group having 1 to 4 carbon atoms).
The photoradical generator is contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polysiloxane compound having a unit represented by the general formulas (1) to (4). The photosensitive resin composition according to item 1.