JP2006139083A - Photosensitive resin composition, method for forming thin film pattern and insulating film for electronic instrument - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polysilane-based photosensitive resin composition which has photosensitivity and can be developed by an alkali and from which a thin film having excellent electrical insulating property can be obtained; and to provide a method for forming a thin film pattern using the polysilane-based photosensitive resin composition. <P>SOLUTION: The photosensitive resin composition contains a polysilane expressed by general formula (1), a sensitizer, and an alkoxysilane polymer having a weight-average molecular weight of 300-50,000, which is blended in an amount of 25-3,000 parts by weight to 100 parts by weight of the polysilane. In the formula (1), R<SB>1</SB>, R<SB>2</SB>, R<SB>3</SB>and R<SB>4</SB>are each independently selected from the group comprising a substituted or unsubstituted aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a polar group, and hydrogen; and m and n are integers. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photosensitive resin composition having photosensitivity and capable of alkali development, a thin film pattern forming method using the same, and an insulating film for electronic equipment, and in particular, a photosensitive resin composition containing polysilane and an alkoxysilane polymer. About.

  In a manufacturing process of a semiconductor device, a liquid crystal display device, or a printed circuit board, various constituent materials including an element protective film and an interlayer insulating film are finely processed or patterned.

  Since polysilane has excellent heat resistance and transparency, it is expected to be used in heat resistant materials, insulating materials, optical devices, and the like. The silicon-silicon bond of polysilane has photodegradability. Therefore, if a thin film such as the above-described protective film or interlayer insulating film is formed of polysilane, various fine processing and pattern formation are possible by exposure and development.

  In recent years, in order to prevent air pollution, there is an increasing trend to suppress organic solvent emissions, particularly in Europe. In Japan, the Fire Service Act stipulates that equipment using organic solvents should be explosion-proof to prevent fires. From such a background, an alkaline aqueous solution such as an aqueous potassium hydroxide solution or an aqueous tetramethylammonium hydroxide solution is used as a developer for forming a pattern.

  When the silicon-silicon bond of the main chain of polysilane is cleaved by light irradiation, a silanol group (Si-OH group) is generated. This silanol group is soluble in an aqueous alkali solution. Therefore, polysilane has attracted attention as a material constituting a photosensitive resin composition capable of alkali development.

  However, since polysilane alone has low photosensitivity, the photosensitivity is improved by adding various sensitizers to polysilane.

  For example, Patent Document 1 below discloses a photosensitive resin composition obtained by adding a photoradical generator that generates a halogen radical by light to polysilane. It is said that the halogen radicals generated from the photoradical generator upon irradiation with light efficiently cut the silicon-silicon bond of the main chain of the polysilane, so that the photosensitivity of the polysilane is improved.

Patent Document 2 below discloses a photosensitive resin composition obtained by adding a photoradical generator and a photooxidant to polysilane. The photooxidant added together with the photoradical generator generates oxygen by photolysis. The generated oxygen is easily inserted into the silicon-silicon bond of the main chain of the polysilane, so that the photosensitivity of the polysilane is improved.
JP-A 61-189533 Japanese Patent No. 3274918

  However, when the photosensitive resin composition described in Patent Documents 1 and 2 is used to form a thin film pattern, the thin film remaining after exposure and development is made of polysilane. Since the thin film made of polysilane is gradually decomposed by light, the pattern shape may change with time. In particular, when used in a liquid crystal display device or the like, since the pattern is often exposed to light during actual use, suppression of the collapse of the pattern shape over time is strongly demanded. Further, the conventional thin film made of this type of polysilane has a problem that the electrical insulation is not sufficient.

  An object of the present invention is to obtain a thin film pattern that has photosensitivity, can be alkali-developed, is less susceptible to pattern deformation during pattern formation, and is excellent in electrical insulation, in view of the current state of the prior art described above. It is providing the insulating resin film for electronic devices formed by using the photosensitive resin composition which enables this, the formation method of the thin film pattern using this photosensitive resin composition, and this photosensitive resin composition.

  1st invention of this application contains the polysilane shown by following General formula (1), a sensitizer, and the alkoxysilane polymer whose weight average molecular weight is between 300-50000, and with respect to 100 weight part of polysilanes. An alkoxysilane polymer is blended in a proportion of 25 to 3000 parts by weight.

In the formula, R ₁ , R ₂ , R ₃ , and R ₄ are each substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, polar group, and hydrogen. Each independently selected from the group consisting of: m and n are integers.

  The second invention of the present application relates to a polysilane represented by the general formula (1), a sensitizer, an alkoxysilane polymer having a weight average molecular weight of 300 to 50,000, and a translucent particle having a particle diameter of 100 nm or less. The photosensitive resin composition is characterized in that the total of the alkoxysilane polymer and the translucent particles is 25 to 3000 parts by weight with respect to 100 parts by weight of the polysilane.

  3rd invention of this application contains the polysilane shown by the said General formula (1), a sensitizer, the alkoxysilane polymer whose weight average molecular weight is between 300-50000, and alkoxysilane, Polysilane 100 weight The photosensitive resin composition is characterized in that the total of the alkoxysilane polymer and the alkoxysilane is 25 to 3000 parts by weight with respect to parts.

  That is, in the first to third inventions (hereinafter collectively referred to as the present invention), the polysilane represented by the general formula (1), the sensitizer, and the weight average molecular weight are in the range of 300 to 50,000. And an alkoxysilane polymer. And since the said alkoxysilane polymer is contained in addition to the polysilane shown by the said General formula (1), and a sensitizer, it is possible to obtain the thin film pattern excellent in electrical insulation so that it may mention later. Is done.

  The thin film pattern forming method according to the present invention includes forming a photosensitive resin composition layer comprising the photosensitive resin composition of the first to third inventions on a substrate, and forming the photosensitive resin composition layer on the photosensitive resin composition layer. A step of selectively exposing according to a pattern to form a patterned latent image, a step of developing the photosensitive resin composition layer on which the latent image is formed with an alkaline aqueous solution to obtain a thin film pattern, and And a step of irradiating or heat-treating the thin film pattern after developing with an alkaline aqueous solution.

  The insulating film for electronic devices according to the present invention is formed using the photosensitive resin composition according to the present invention. In this case, the forming method is not particularly limited, and for example, the above-described thin film pattern forming method can be used.

  The liquid crystal display device according to the present invention is characterized by including, as a protective film, an insulating film for electronic equipment configured using a photosensitive resin composition configured according to the present invention. An insulating film for electronic equipment formed using a photosensitive resin composition configured using a photosensitive resin composition configured according to the invention is provided as an interlayer insulating film.

  Details of the present invention will be described below.

  As a result of intensive studies to achieve the above-described problems, the present inventors have used a photosensitive resin composition containing a sensitizer and an alkoxysilane polymer having a weight average molecular weight of 300 to 50,000 in a specific polysilane. For example, it has been found that the electrical conductivity of the thin film pattern obtained by using the alkoxysilane polymer having the specific weight average molecular weight can be enhanced by the photosensitivity sufficiently expressed by the specific polysilane. It came to an eggplant.

  The polysilane has a structure represented by the general formula (1).

In the general formula (1), R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different, and each is a substituted or unsubstituted aliphatic hydrocarbon group, fatty acid A group selected from the group consisting of a cyclic hydrocarbon group, an aromatic hydrocarbon group and a polar group, and m and n are integers.

  Examples of the substituted or unsubstituted aliphatic hydrocarbon group include methyl group, n-propyl group, n-butyl group, n-hexyl group, phenylmethyl group, trifluoropropyl group, and nonafluorohexyl group. Examples of the substituted or unsubstituted alicyclic hydrocarbon group include a cyclohexyl group and a methylcyclohexyl group, and examples of the substituted or unsubstituted aromatic hydrocarbon group include a p-tolyl group, o- Examples include a tolyl group, m-tolyl group, biphenyl group, and phenyl group. Examples of the substituted or unsubstituted polar group include a hydroxyl group-containing group, a carboxyl group-containing group, and a phenolic hydroxyl group-containing group. Can do.

  As described above, polysilane is used as a component for developing photosensitivity in the photosensitive resin composition according to the present invention. Among polysilanes, polyphenylalkylsilane is preferably used because it is particularly excellent in photosensitivity.

The number average molecular weight of the polysilane is preferably 2000 to 50000, and more preferably 5000 to 20000. The types of R ₁ , R ₂ , R ₃ , and R ₄ , and the values of m and n are not particularly important, and this polysilane is soluble in an organic solvent and applied to a uniform thin film having a thickness of 10 nm to 10 μm. If possible.

  The sensitizer used in the present invention is a compound that improves the photosensitivity of polysilane, and is not particularly limited as long as it is such a compound. For example, the photosensitivity of polysilane such as a photoradical generator and a photooxidant is used. Known sensitizers that can increase the sensitivities can be used.

  For example, as a photo radical generator, 2,4-bis (trihalomethyl) -6- (p-methoxyphenylvinyl) -1,3,5-triazine, 2,4,6-tris (trihalomethyl) -1 , 3,5-triazine, 2-alkyl-4,6-bis (trihalomethyl) -1,3,5-triazine, 2-aryl-4,6-bis (trihalomethyl) -1,3,5-triazine Triazine compounds such as 2-alkyl-4-aryl-6-trihalomethyl-1,3,5-triazine; tribromomethylphenyl sulfone; 1,4-di (trichloromethyl) benzene; 1,4-di (tri Fluoromethyl) benzene; acetophenones; benzophenones; benzoin ethers; sulfur compounds such as benzylmethyl ketal and thioxanthene; anthraquinones Thiol compounds; azobisisobutyronitrile; hydroperoxide, benzoyl peroxide, and an organic peroxide such as cumene peroxide.

  As photooxidants, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, t-butylperoxybenzoate, methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1, -bis (t-butylperoxy) -3,3 , 5-trimethylcyclohexane, di-t-butylperoxy-2-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2- Bis (t-butylperoxy) butane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, p-menthane hydro Peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α, α'-bis (t-butylperoxy) diisopropyl Benzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (T-Butylperoxy) hexyne-3-isobutyl Peroxide, 3,3,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoyl benzoyl peroxide, benzoyl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate Bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyacetate, t-butylperoxymaleic acid, t-butylperoxyisobutyrate, t-hexylperoxybenzoate, and the like. These compounds can be used alone or in combination of two or more. The sensitizer is preferably contained in an amount of 0.05 to 100 parts by weight, more preferably 1 to 75 parts by weight with respect to 100 parts by weight of polysilane. When the content of the sensitizer is less than 0.05 parts by weight, the decomposition reaction rate of polysilane may be extremely slow. Moreover, when there is more content of a sensitizer than 100 weight part, the precise | minute film | membrane derived from the photosensitive resin composition may not be obtained.

  The photosensitive resin composition of the present invention may further contain other compounds that can increase the ability of the sensitizer by using in combination with the above sensitizer.

  Examples of such other compounds include tertiary amines such as triethanolamine; sensitizing dyes such as coumarin, ketocoumarin and derivatives thereof, and thiopyrylium salts; palladium propionate, palladium acetate, acetylacetonate platinum, ethylacetate. Examples thereof include oxidants such as natoplatinum, palladium fine particles, and platinum fine particles.

  The said alkoxysilane polymer used in this invention is used in order to improve the electrical insulation of this thin film pattern when forming a thin film pattern using the photosensitive resin composition of this invention. The alkoxysilane used for obtaining the alkoxysilane polymer is not particularly limited, and examples thereof include phenyltrimethoxysilane, phenyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyldimethoxymethylsilane, and glycidoxypropyl. Triethoxysilane, glycidoxypropyldiethoxyethylsilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, tetramethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, tetra Mono-substituted trialkoxysilanes in addition to ethoxysilane, n-propyltriethoxysilane, isopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, etc. Condensates, condensates of mono-substituted trialkoxysilane and methyl silicate, or condensation products of disubstituted dialkoxy Kishikishi silane and monosubstituted trialkoxy silane and the like.

  Of these, polymers such as phenyltrimethoxysilane and phenyltriethoxysilane are preferably used because of their good compatibility with polysilane.

  The alkoxysilane polymer is obtained by polymerizing alkoxysilane by an appropriate method, and the polymerization method is not particularly limited. In the polymerization, an acid or an alkali can be used as a catalyst. Examples of the acid include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, and formic acid. Examples of the alkali include ammonia, potassium hydroxide, and sodium hydroxide. Further, the solvent for polymerization is not particularly limited.

  The weight average molecular weight of the alkoxysilane polymer used in the present invention needs to be in the range of 300 to 50000, and preferably in the range of 1000 to 5000 since the coating during film formation becomes a container. When the weight average molecular weight is less than 300, it is not a polymer but a monomer. On the other hand, if the weight average molecular weight exceeds 50,000, the compatibility of the alkoxysilane polymer with polysilane is lowered, and it becomes difficult to dissolve in a solvent, so that it is practically difficult to form a thin film pattern.

  In the first invention, the alkoxysilane polymer is blended in the range of 25 to 3000 parts by weight, preferably 50 to 300 parts by weight with respect to 100 parts by weight of the polysilane. If the amount is less than 25 parts by weight, the effect of enhancing the electrical insulation of the obtained thin film pattern cannot be sufficiently obtained, and if it exceeds 3000 parts by weight, it is difficult to impart photosensitivity.

  In the second and third inventions, the total blending ratio of translucent particles or alkoxysilane, which will be described later, and the alkoxysilane polymer is within a specific range with respect to polysilane.

  In the second invention, the translucent particles are blended in order to further enhance the light resistance and pattern stability of the obtained thin film pattern.

  The translucent particles are not particularly limited as long as they have better light resistance than polysilane.

  The translucent particles may be inorganic particles or organic particles as long as they are more light resistant than polysilane. Preferably, inorganic particles are preferably used compared to organic particles because of excellent heat resistance. Examples of the inorganic particles include silica particles, zinc oxide, titania, zirconia and the like, but are not particularly limited thereto. When inorganic particles are used, at least a part of the surface may be subjected to a hydrophobic treatment. Preferably, inorganic particles whose surface is partially hydrophobized are used, and silica particles whose surface is partially hydrophobized are suitably used as such inorganic particles. Moreover, it does not specifically limit as an organic particle, For example, polyethylene, a polypropylene, etc. can be mentioned.

  Both inorganic particles and organic particles are required to have translucency. When it does not have translucency, it becomes difficult to form a pattern by photolithography in the photosensitive resin composition according to the present invention.

  As described above, inorganic particles are preferably used as the translucent particles because the pattern stability can be effectively maintained, and silica particles are preferably used among them.

  In addition, the said translucent particle | grain may be added as an arbitrary component also in 1st invention and 3rd invention.

  In the second invention, the blending ratio of the translucent particles is in the range of 25 to 3000 parts by weight in total of the translucent particles and the alkoxysilane polymer described above, more preferably 100 parts by weight of polysilane. 40 to 2000 parts by weight. If the amount is less than 25 parts by weight, the stability of the shape of the obtained thin film pattern is impaired, and the electrical insulation is lowered. If the amount exceeds 3000 parts by weight, the solubility in an alkaline aqueous solution is lowered.

  The average particle diameter of the translucent particles is preferably in the range of 100 nm or less, and more preferably in the range of 30 nm or less. When the thickness exceeds 100 nm, the thin film becomes cloudy or a transparent film cannot be formed.

  In 3rd invention, in addition to the said polysilane, a sensitizer, and the said alkoxysilane polymer, alkoxysilane is contained. As an example of this alkoxysilane, the alkoxysilane used for obtaining the alkoxysilane polymer mentioned above can be illustrated. In 3rd invention, in addition to the said polysilane, a sensitizer, and the said alkoxysilane polymer, the electrical insulation of the thin film formed using the photosensitive resin composition is further comprised by containing alkoxysilane. Enhanced. In particular, when the heat treatment described below is performed, the electrical insulation is further enhanced because it acts to bridge the alkoxysilane polymer.

  The content rate of the said alkoxysilane shall be 25-3000 weight part as a total of an alkoxysilane polymer and an alkoxysilane with respect to 100 weight part of polysilanes, Preferably, it is the range of 50-300 weight part. If the amount is less than 25 parts by weight, the stability of the thin film pattern shape is impaired, and the electrical insulation is deteriorated. If the amount exceeds 3000 parts by weight, the solubility in an alkaline aqueous solution is lowered, and there is a possibility that alkali development cannot be performed.

  In the present invention, the polysilane is preferably used effectively because the polyphenylalkylsilane is excellent in photosensitivity as the polysilane. When polyphenylalkylsilane is used, among the alkoxysilanes, Phenylalkoxysilane is preferably used. That is, in the photosensitive resin composition using polyphenylalkylsilane and phenylalkoxysilane, each of the polyphenylalkylsilane and phenylalkoxysilane has a benzene ring, and the interaction between the benzene rings causes a phase difference. High solubility. Therefore, the solubility of the aqueous solution of the thin film obtained is excellent. That is, development with an alkaline aqueous solution can be performed easily and with high accuracy.

  The phenylalkoxysilane is not particularly limited, and examples thereof include phenyltrimethoxysilane and phenyltriethoxysilane.

  In the present invention, the translucent particles added in the second invention and the alkoxysilane added in the third invention may be used in combination.

  In preparing the photosensitive resin composition according to the present invention, the sensitizer and alkoxysilane polymer, and, if necessary, the translucent particles and / or alkoxysilane are added to the polysilane and mixed. Good. When mixing these components, it is preferable to mix them uniformly. Therefore, it is desirable to use an appropriate solvent, add these components to the solvent, dissolve and mix them. The method of adding each component, the mixing method and the temperature or pressure at the time of mixing are not particularly limited, but it is dark so as not to be exposed to light at the photosensitive wavelength of the sensitizer until the exposure process and development process described later. It is preferable to work in a place or under light shielding conditions.

  Although it does not specifically limit as said solvent, Aromatic hydrocarbon compounds, such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, diethylbenzene; Cyclohexane, cyclohexene, dipentene, n-pentane, isopentane, n-hexane, isohexane, Saturated or unsaturated hydrocarbon compounds such as 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, ethyl propyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibu 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, ethylcyclohexane, methylcyclohexane, p-menthane, o Menthane, m-menthane; ethers such as dipropyl ether and dibutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone and cycloheptanone; Examples include esters such as ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate, methyl cellosolve, ethyl acetate cellosolve, butyl cellosolve, ethyl lactate, propyl lactate, butyl lactate, isoamyl lactate, and butyl stearate. These solvents can be used alone or in combination of two or more.

  When the photosensitive resin composition is applied on the substrate to form the photosensitive resin composition layer, the mixing ratio of the solvent is such that the average molecular weight of polysilane, molecular weight distribution, It is appropriately selected according to the amount added. Therefore, the concentration of the photosensitive resin composition is preferably 0.1 to 50% by weight, more preferably 0.5 to 40% by weight.

  In the photosensitive resin composition according to the present invention, a filler, a pigment, a dye, a leveling agent, an antifoaming agent, an antistatic agent, an ultraviolet absorber, a pH adjusting agent, a dispersing agent, a dispersing aid, and a surface, as necessary. A modifier, a plasticizer, a drying accelerator, and an anti-sagging agent may be added.

  The method for forming 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. A step of selectively exposing the photosensitive resin composition layer 1 using a photomask 3 corresponding to the pattern to form a latent image 1A on the pattern (FIG. 1B), and a photosensitive layer on which the latent image is formed 1B is developed with an alkaline aqueous solution (FIG. 1C), and the thin film formation pattern 1C formed as described above is subjected to light irradiation or heat treatment. 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.

  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 a substrate to which the photosensitive resin composition is applied, a silicon substrate, a glass substrate, a metal plate, a plastics plate, various films, and the like are used depending on applications. 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.

As the light source, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer laser, or the like can be used. These light sources are appropriately selected according to the photosensitive wavelength of the sensitizer. The irradiation energy of light depends on the desired thickness of the thin film and the type of sensitizer, but generally 5 to 6000 mJ / cm ² is used. If it is less than 5 mJ / cm ² , the polysilane will not be sufficiently exposed. Further, if it is larger than 6000 mJ / cm ² , the exposure time may be prolonged,
There exists a possibility that the manufacturing efficiency per time of a thin film pattern may fall.

  In the exposed portion of the photosensitive resin composition layer irradiated with light in the pattern shape, the silicon-silicon bond of the main chain of polysilane is cleaved to generate silanol groups (Si—OH). In order to promote the generation of this silanol group, oxygen, ozone, water or moisture may be contacted. By developing the exposed photosensitive resin composition layer using a developer, the exposed portion of the photosensitive resin composition layer is dissolved and removed in the developer, and the unexposed portion remains on the substrate. As a result, a pattern is formed. This pattern is called a positive pattern because the exposed portion is removed. The photosensitive resin composition layer in the unexposed part is almost insoluble in the developer because silanol groups (Si—OH) are not generated. Therefore, in the thin film pattern forming method obtained by the present invention, good resolution can be obtained.

  An alkaline aqueous solution is used as the developer. 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 generally 10 seconds to 5 minutes. The thin film pattern used after development is preferably washed with distilled water to remove the aqueous alkali solution remaining on the thin film.

  When the thin film pattern obtained as described above contains translucent particles having light resistance superior to that of polysilane, the shape of the thin film pattern is less likely to change over time, and the shape stability and Light resistance is also improved. For example, when translucent particles such as silica particles are blended, the mechanical strength is enhanced by the portion where the translucent particles are present, and the light resistance and heat resistance are also enhanced. Even when it is used for exposure to light, the shape stability of the formed pattern is improved.

  In the thin film pattern forming method according to the present invention, light irradiation or heat treatment is performed after developing with an alkaline aqueous solution, that is, after forming a thin film pattern.

  By light irradiation, the polysilane forming the thin film pattern can be partially and forcibly decomposed to suppress further deterioration. That is, if the polysilane having an unstable shape is forcibly deteriorated in advance by irradiating light, it is possible to suppress the deterioration and fluctuation of the pattern shape over time during actual use.

  The light irradiation after forming the thin film pattern is performed using light of an appropriate wavelength as long as polysilane can be forcibly decomposed and deteriorated. Preferably, ultraviolet light or light having a longer wavelength than ultraviolet light is suitably used. Used. As for the irradiation amount and energy intensity at the time of this light irradiation, an appropriate irradiation amount and energy intensity capable of forcibly degrading polysilane may be selected.

  The heat treatment is generally performed at 50 to 1000 ° C, preferably 100 to 500 ° C. When an alkoxysilane or alkoxysilane polymer is contained, this heat treatment causes the alkoxysilane or alkoxysilane polymer to be thermally cross-linked, thereby further improving the shape stability and light resistance of the thin film pattern obtained. . The heating time and heating method for heating the alkoxysilane or alkoxysilane polymer are not particularly limited as long as the alkoxysilane or alkoxysilane polymer can be thermally crosslinked, and the heating time is usually about 10 minutes to 5 hours. As the heating device, a hot plate, an appropriate heater, or the like can be used.

  The heat treatment may be performed when no alkoxysilane or alkoxysilane polymer is contained. In that case, polysilane can be oxidized and decomposed into silicon dioxide.

  In the present invention, in addition to the heating step after the alkaline aqueous solution development, the light irradiation step may be used in combination, and either of them may be performed first.

  In addition, although the photosensitive resin composition which concerns on this invention is used suitably for forming a thin film pattern in various apparatuses, Preferably, the said thin film pattern is used effectively for the insulating film for electronic devices. By using the thin film pattern comprised using the photosensitive resin composition which concerns on this invention as an insulating film for electronic devices, the insulation of the obtained insulating film can be improved effectively. Examples of such an insulating film for electronic equipment include a TFT protective film for protecting a thin film transistor (TFT) in a liquid crystal display element, and an insulating protective film for protecting a filter in a color filter.

  FIG. 2 is a schematic front sectional view of a liquid crystal display element using the insulating film for electronic equipment of 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 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 film for electronic equipment 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 film for electronic equipment according to the present invention is used as the insulating protective film 34. Therefore, the electrical insulation of the protective film 34 is effectively enhanced. An ITO electrode 35 is formed on the protective film 34.

  In addition, since the insulating film for electronic devices according to the present invention is excellent in electrical insulation, it is not limited to the above-described liquid crystal display element and color filter, but includes, for example, a TFT protective film, a passivation film, and a semiconductor film of an organic EL element. Widely used as insulating films for various electronic devices such as interlayer insulating films and insulating partition walls of plasma displays.

  The photosensitive resin composition according to the first invention contains the polysilane represented by the general formula (1) described above, a sensitizer, and an alkoxysilane polymer having a weight average molecular weight in the range of 300 to 50,000, Since the alkoxysilane polymer is blended in an amount of 25 to 3000 parts by weight with respect to 100 parts by weight, sufficient photosensitivity is expressed by the polysilane and the sensitizer, and alkali development can be performed. Moreover, when the said alkoxysilane polymer is mix | blended in the said specific ratio, the electrical insulation of the formed thin film pattern is improved. Therefore, the thin film pattern formed using the photosensitive resin composition of the first invention is suitably used as an insulating film for electronic equipment, for example, as a protective film for liquid crystal display elements and an interlayer insulating film for semiconductor elements. Can be used.

  In the photosensitive resin composition which concerns on 2nd invention, the said polysilane, a sensitizer, the said alkoxysilane polymer, and the translucent particle | grains of the said specific particle diameter are contained, 100 weight part of polysilane, Since the total of alkoxysilane and translucent particle | grains is mix | blended in the ratio of 25-3000 weight part, sufficient photosensitivity is obtained with a polysilane and a sensitizer, and alkali image development can be performed. Moreover, electrical insulation is enhanced by the alkoxysilane polymer, and it becomes easy to form a uniform thin film by blending the translucent particles, and the mechanical strength of the obtained thin film can be increased. Therefore, the shape stability of the thin film pattern is also effectively improved.

  In the photosensitive resin composition which concerns on 3rd invention, the said polysilane, a sensitizer, the alkoxysilane polymer of the said specific weight average molecular weight, and an alkoxysilane are contained, The said alkoxy is contained with respect to 100 weight part of polysilane. Since the silane polymer and the alkoxysilane are blended in a proportion of 25 to 3000 parts by weight, sufficient photosensitivity can be obtained with the polysilane and the sensitizer, and alkali development can be performed. Thus, the electrical insulation of the thin film pattern obtained is improved. Furthermore, a crosslinked structure can be introduce | transduced by light irradiation or heat processing by containing alkoxysilane. Therefore, the electrical insulation of the formed thin film pattern can be further enhanced. In addition, it is possible to further suppress the deformation of the pattern shape, and it is possible to easily form a thin film having a stable pattern shape.

  In the method for forming a thin film pattern according to the present invention, a photosensitive resin composition layer composed of a photosensitive resin composition constituted according to the present invention is formed on a substrate and selectively exposed to form a latent image on the pattern. Thereafter, the photosensitive resin composition layer on which the latent image is formed is developed with an alkaline aqueous solution. Therefore, the Si-Si bond of polysilane is cleaved by light, and the exposed portion develops good solubility in an alkaline aqueous solution. By developing with the alkaline aqueous solution, a thin film pattern having a desired shape can be easily formed. can do.

  And since the said alkoxysilane polymer is contained in the photosensitive resin composition, the electrical insulation of the obtained thin film pattern is improved effectively.

  Further, when the thin film pattern is irradiated with light after development with an alkaline aqueous solution, the polysilane constituting the thin film pattern is forcibly deteriorated in advance by light irradiation. Therefore, even when exposed to light when using the finally obtained thin film pattern, it is difficult for polysilane to be decomposed by more light, and the collapse of the thin film pattern over time can be effectively suppressed. .

  In addition, when heat treatment is performed after developing with an alkaline aqueous solution to form a thin film pattern, alkoxysilane and the like are thermally cross-linked, thereby effectively improving the shape stability of the thin film pattern. Therefore, the collapse of the thin film pattern over time can be effectively suppressed.

  Since the insulating film for electronic devices according to the present invention is formed using the photosensitive resin composition configured according to the present invention, it is excellent in electrical insulation, and therefore the photosensitive resin composition according to the present invention. The above-mentioned insulating film for electronic devices formed by using, for example, is suitably used as a protective film for a liquid crystal display element or an interlayer insulating film for a semiconductor element, and effectively provides protection and interlayer insulation for a liquid crystal display element or a semiconductor element. Can be increased.

  Hereinafter, the present invention will be described in more detail by giving specific examples and comparative examples using the photosensitive resin composition according to the present invention.

(Preparation of polymethylphenylsilane)
A 500 mL separable cover and a separable flask attached with a cooling pipe were heated in a nitrogen stream to sufficiently remove moisture. 160 mL of anhydrous tetrahydrofuran was added to the separable flask from which moisture was removed, and 8.84 g of sodium was further added. Under a dry nitrogen stream, sodium was dispersed using a semicircular mechanical stirrer with a stainless steel net and heated to 80 ° C. in an oil bath. Next, 25 mL of methylphenyldichlorosilane was added to the separable flask and stirred at 80 ° C. for 2 hours. After completion of the reaction, the separable flask was cooled to room temperature. After cooling, 80 mL of anhydrous toluene was added to the separable flask, and the precipitated product was separated by filtration. Further, the obtained filtrate was concentrated using an evaporator, and 400 mL of isopropanol was added to obtain a precipitated product.

  The resulting precipitated product was separated by suction filtration and washed thoroughly with distilled water and methanol. After washing, it was dissolved in about 500 mL of toluene and washed with distilled water until neutral using a separatory funnel. After washing, the product was sufficiently dried with magnesium sulfate and then concentrated with an evaporator. After concentration, purification was performed by reprecipitation using 750 mL of a 2-to-1 solution of isopropanol and toluene to obtain crude polymethylphenylsilane. The obtained crude polymethylphenylsilane was dissolved in 100 mL of toluene. The dissolved toluene solution was reprecipitated and purified by putting it into 400 mL of a one-to-one solution of isopropanol and toluene. This purification by reprecipitation was performed three times in total. After purification, it was dried in a desiccator under reduced pressure for 15 hours to obtain polymethylphenylsilane (PMPS) having a number average molecular weight of 7000.

(Preparation of phenyltriethoxysilane polymer [hereinafter abbreviated as Ph-Si-O-polymer])
As an alkoxysilane polymer, a Ph-Si-O-polymer was prepared in the following manner.

  A 500 mL separable cover and a separable flask to which a cooling pipe was attached were heated under a nitrogen stream to sufficiently remove moisture. 10 g of phenyltriethoxysilane, 0.2 g of oxalic acid as a catalyst, 20 g of PGMEA (propylene glycol monomethyl ether acetate), and 2 g of water were put into a separable flask from which water had been removed, and 70 ° C. in an oil bath. Then, the mixture was reacted for 2 hours, then heated to 130 ° C. and further reacted for 2 hours to obtain a polymer solution. The polymer container thus obtained was vacuum degassed and dried to obtain a polymer (liquid). It was 1000 when the weight average molecular weight of the obtained Ph-Si-O-polymer was measured.

  A polymer solution was obtained and vacuum degassed and dried in the same manner as described above except that the reaction time at 130 ° C. was changed to 12 hours and 24 hours. As a result, solid Ph-SiO-polymers having weight average molecular weights of 50,000 and 100,000 were obtained.

  The polymethylphenylsilane (PMPS) and Ph-Si-O-polymer used in the following examples and comparative examples were obtained according to the above preparation methods.

Example 1
100 parts by weight of polymethylphenylsilane (PMPS), 10 parts by weight of 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, and 500 parts by weight of Ph-Si-O-polymer (Mw = 1000) Parts and 800 parts by weight of tetrahydrofuran were dissolved in a solvent of 800 parts by weight of propylene glycol monomethyl ether acetate to prepare a photosensitive resin composition. This photosensitive resin composition was spin-coated on a silicon wafer having a thickness of 0.75 mm at a rotational speed of 2000 rpm. After coating, it was dried in a hot air oven at 80 ° C. to form a coating film having a film thickness of 0.25 μm. Next, ultraviolet rays with a wavelength of 365 nm are applied to the coating film through a photomask having a predetermined pattern (USHIO Inc., Spot Cure SP-5), and the irradiation energy is 1000 mJ / cm ² . It was irradiated for 10 seconds with an ultraviolet illuminance of 100 mW / cm ² . After irradiation, the coating film was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide for 2 minutes.

As a result, the coating film was dissolved in the portion irradiated with ultraviolet rays, and an L / S 5 μm pattern derived from the photomask was formed. The thin film pattern thus formed was further irradiated with 1000 mJ / cm ² of ultraviolet rays by the ultraviolet irradiation device. Furthermore, the thin film pattern was heated for 1 hour on a hot plate heated to 300 ° C. to condense polymethylphenylsilane, thereby obtaining a thin film pattern.

(Example 2)
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the blending ratio of the Ph-Si-O-polymer with Mw = 1000 was 25 parts by weight, and a thin film pattern was formed.

(Example 3)
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the blending ratio of the Ph-Si-O-polymer with Mw = 1000 was 3000 parts by weight, and a thin film pattern was formed.

Example 4
Photosensitive in the same manner as in Example 1, except that 500 parts by weight of Ph-Si-O-polymer with Mw = 50000 was blended instead of the one with Mw = 1000 as the Ph-Si-O-polymer. A resin composition was prepared and a thin film pattern was obtained.

(Example 5)
No Ph-Si-O-polymer was added and instead Ph-Poss (heptacyclohexylsilsesquioxane, 1,3,5,7,9,11,14-Heptacyclic chlorophilic [7.3.1. ^5,11 ] Heptasiloxane-endo-3,7,14-triol) was prepared in the same manner as in Example 1 except that 500 parts by weight was blended, and a thin film pattern was formed. .

  The structure of the Ph-Poss is shown in the following formula (2).

(Example 6)
Except that, in preparing the photosensitive resin composition, 200 parts by weight of SiO ₂ particles (manufactured by Fuso Chemical Co., Ltd., trade name: PL-2L-PGMEA, primary particle diameter 15 nm) dispersed in PGMEA as light-transmitting particles were blended. In the same manner as in Example 1, a photosensitive resin composition was prepared and a thin film pattern was formed.

(Example 7)
A photosensitive resin composition was prepared in the same manner as in Example 1 except that 100 parts by weight of phenyltriethoxysilane (PTES) was further added as an alkoxysilane, and a thin film pattern was obtained.

(Example 8)
A photosensitive resin composition was prepared in the same manner as in Example 1 except that 200 parts by weight of the translucent particles used in Example 6 and 100 parts by weight of PTES used in Example 7 were further blended, and A thin film pattern was obtained.

(Comparative Example 1)
A photosensitive resin composition was prepared in the same manner as in Example 1 except that no Ph-SiO-polymer was used, and an attempt was made to form a thin film pattern.

(Comparative Example 2)
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the blending ratio of Ph-Si-O-polymer (Mw = 1000) was changed to 15 parts by weight, and an attempt was made to form a thin film pattern. It was.

(Comparative Example 3)
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the blending ratio of Ph-Si-O-polymer (Mw = 1000) was changed to 4000 parts by weight, and an attempt was made to form a thin film pattern. It was.

(Comparative Example 4)
A photosensitive resin composition was prepared in the same manner as in Example 1 except that a Ph-Si-O-polymer having Mw = 100000 was used as the Ph-Si-O-polymer used. The Si-O-polymer did not dissolve and a thin film pattern could not be formed.

(Comparative Example 5)
A photosensitive resin composition was prepared in the same manner as in Example 1 except that no alkoxysilane polymer was used and 500 parts by weight of PTES (phenyltriethoxysilane) was used, and a thin film pattern was obtained. .

(Evaluation)
The compositions of the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 5 are summarized in Table 1 below. Moreover, in Examples 1-8 and Comparative Examples 1-5, the result of having observed the shape of the thin film pattern finally obtained, and the volume resistance of the thin film pattern were evaluated with the following capacity | capacitance. The results are shown in Table 2 below.

  The meaning contents of the evaluation symbols in Table 2 are as follows.

    A: The pattern formation state is very good.

    A: The pattern formation state is good.

    Δ: Pattern collapse has occurred slightly.

    X: The pattern formation state is poor (the pattern collapses).

  Measurement of volume resistance: The volume resistance of a thin film pattern obtained by a method according to JIS K6911 was measured.

(A)-(c) is sectional drawing of each process for demonstrating the thin film pattern formation method which concerns on this invention. The front sectional view showing the liquid crystal display element in which the insulating protective film for electronic equipment concerning 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. 2. 1 is a partially cutaway front cross-sectional view showing a color filter in which an insulating protective film for electronic equipment according to the present invention is used.

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)
15 ... ITO
16 ... Alignment film 17 ... Alignment film 18 ... Sealing material 19 ... Liquid crystal 20 ... Spacer 21 ... Glass substrate 22 ... Color filter 23 ... ITO
31 ... Color filters 32a to 32c ... Pixels 33 ... Black matrix part 34 ... Protective film (insulating protective film for electronic equipment)
35 ... ITO electrode

Claims (7)

It contains a polysilane represented by the following general formula (1), a sensitizer, and an alkoxysilane polymer having a weight average molecular weight of 300 to 50,000, and the alkoxysilane polymer is 25 to 3000 weight with respect to 100 parts by weight of polysilane. A photosensitive resin composition characterized by being blended in a proportion of parts.

In the formula, R ₁ , R ₂ , R ₃ , and R ₄ are each substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, polar group, and hydrogen. Each independently selected from the group consisting of: m and n are integers. A polysilane represented by the following general formula (1), a sensitizer, an alkoxysilane polymer having a weight average molecular weight of 300 to 50,000, and translucent particles having a particle diameter of 100 nm or less, and 100 weight of polysilane The photosensitive resin composition characterized by the sum total of an alkoxysilane polymer and translucent particle | grains being the ratio of 25-3000 weight part with respect to a part.

In the formula, R ₁ , R ₂ , R ₃ , and R ₄ are each substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, polar group, and hydrogen. Each independently selected from the group consisting of: m and n are integers. A polysilane represented by the following general formula (1), a sensitizer, an alkoxysilane polymer having a weight average molecular weight of 300 to 50,000, and an alkoxysilane, and an alkoxysilane polymer and 100 parts by weight of the polysilane A photosensitive resin composition characterized in that the total amount of alkoxysilane is 25 to 3000 parts by weight.

In the formula, R ₁ , R ₂ , R ₃ , and R ₄ are each substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, polar group, and hydrogen. Each independently selected from the group consisting of: m and n are integers. Forming a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 3 on a substrate;
A step of selectively exposing according to a pattern to be formed on the photosensitive resin composition layer to form a patterned latent image;
Developing the photosensitive resin composition layer on which the latent image is formed with an alkaline aqueous solution to obtain a thin film pattern;
A method of forming a thin film pattern, comprising: developing the thin film pattern with light or heat treatment after developing with the alkaline aqueous solution.   The insulating film for electronic devices formed using the photosensitive resin composition of any one of Claims 1-3.   A liquid crystal display element comprising an insulating film for electronic equipment formed using the photosensitive resin composition according to claim 1 as a protective film. The semiconductor element provided with the insulating film for electronic devices formed using the photosensitive resin composition of any one of Claims 1-3 as an interlayer insulation film.

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