JP2008256974A - Positive photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition which retains a high transmittance and high sensitivity and has high storage stability at room temperature. <P>SOLUTION: The positive photosensitive resin composition comprises (A) an alkali-soluble acrylic polymer having a 3-16C side chain with an unsaturated bond at a terminal and having a number average molecular weight of 2,000-3,000, (B) a 1,2-quinonediazide compound and (C) a solvent. A cured film obtained using the composition is also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a positive photosensitive resin composition and a cured film obtained therefrom. More specifically, the present invention relates to a positive photosensitive resin composition suitable for use in display materials, a cured film thereof, and various materials using the cured film.

  In general, in a display element such as a thin film transistor (TFT) type liquid crystal display element or an organic EL (electroluminescent) element, a patterned electrode protective film, a planarizing film, an insulating film, and the like are provided. As a material for forming these films, among the photosensitive resin compositions, there are photosensitive resin compositions having a feature that the number of steps for obtaining a required pattern shape is small and sufficient flatness is provided. It is widely used than before.

  These films mentioned above have excellent process resistance such as heat resistance, solvent resistance, long-term baking resistance, metal sputtering resistance, good adhesion to the substrate, and the purpose of use. Further, various characteristics such as having a wide process margin capable of forming a pattern under various process conditions, high sensitivity and high transparency, and less film unevenness after development are required. Therefore, from the viewpoint of such required characteristics, conventionally, resins containing a naphthoquinonediazide compound have been widely used as the photosensitive resin composition.

In addition, these materials have been proposed to thermally crosslink and cure the formed pattern by adding an epoxy crosslinking agent or by adding a carboxyl group and an epoxy group in an acrylic resin (Patent Document 1). And 2).
JP 2000-103937 A JP-A-4-352101

However, a photosensitive resin composition containing an acrylic resin having an epoxy crosslinking system as described above has low storage stability at room temperature, and during use, the viscosity increases with the passage of time, making it difficult to control the film thickness over time. It may cause clogging of the piping of the coating device. In addition, the sensitivity may gradually decrease and development defects may occur.
In addition, a photosensitive resin composition containing an acrylic resin having a conventional epoxy crosslinking system requires freezing storage because of its high reactivity at room temperature, and will be thawed each time in use. Since the deterioration of performance rapidly with the passage of time, the remaining one after use of the composition once thawed can no longer be used again for producing a cured film, that is, it causes a large amount of product loss. .

  The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a positive photosensitive resin composition that maintains high transmittance and sensitivity and has high storage stability at room temperature.

As a result of intensive studies to solve the above problems, the present inventors have found the present invention.
That is, as a first aspect, the present invention relates to a positive photosensitive resin composition containing the following component (A), component (B) and solvent (C).
Component (A): an alkali-soluble acrylic polymer having 3 to 16 carbon atoms and having a side chain having an unsaturated bond at the terminal, and having a number average molecular weight of 2,000 to 30,000 in terms of polystyrene,
(B) component: 1,2-quinonediazide compound,
(C) Solvent.
As a second aspect, the present invention relates to the positive photosensitive resin composition according to the first aspect, in which the component (A) is an alkali-soluble acrylic polymer that sells an aliphatic side chain having an unsaturated bond at the terminal.
As a third aspect, the component (A) relates to a positive photosensitive resin composition according to the first aspect or the second aspect, which is an alkali-soluble acrylic polymer having a side chain having an acryloyl group or a methacryloyl group at the terminal. .
As a fourth aspect, the positive photosensitive resin according to any one of the first aspect to the third aspect, containing 5 to 100 parts by mass of the component (B) with respect to 100 parts by mass of the component (A). Relates to a conductive resin composition.
As a fifth aspect, as the component (D), the surfactant is further contained in an amount of 0.1% by mass or less in the positive photosensitive resin composition, according to any one of the first aspect to the fourth aspect. The present invention relates to a positive photosensitive resin composition.
As a sixth aspect, as the component (E), an adhesion promoter is further contained in an amount of 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A). The positive photosensitive resin composition as described in 1. above.
A seventh aspect relates to a cured film obtained using the positive photosensitive resin composition according to any one of the first aspect to the sixth aspect.
As an 8th viewpoint, it is related with the liquid crystal display element which has the cured film as described in a 7th viewpoint.
As a ninth aspect, the present invention relates to an array flattening film for a liquid crystal display comprising the cured film described in the seventh aspect.
As a tenth aspect, the present invention relates to an interlayer insulating film made of the cured film described in the seventh aspect.

The positive photosensitive resin composition of the present invention can provide a coating film in which the viscosity of the composition does not increase even after storage for 10 days at room temperature and the sensitivity does not change.
Therefore, a new positive type that eliminates the disadvantages of the epoxy-crosslinked photosensitive resin composition, which has been required to be stored in a frozen state, eliminates the loss of the remaining amount when thawed and used, and has been economically disadvantageous. A photosensitive resin composition and a coating film obtained therefrom can be provided.

The positive photosensitive resin composition of the present invention comprises an acrylic polymer as the following component (A), a quinonediazide compound as the component (B) and a solvent (C), and optionally a surfactant as the component (D). And (E) component adhesion promoter and further a composition containing other additives.
Hereinafter, details of each component will be described.

<(A) component>
The component (A) has a side chain having 3 to 16 carbon atoms and an unsaturated bond at the end (hereinafter referred to as a specific side chain) in the structure of the acrylic polymer, and the number in terms of polystyrene. An alkali-soluble acrylic polymer (hereinafter also simply referred to as an acrylic polymer) having an average molecular weight (hereinafter referred to as a number average molecular weight) of 2,000 to 30,000.

In the present invention, the acrylic polymer refers to a polymer obtained by homopolymerization or copolymerization using a monomer having an unsaturated double bond such as acrylic ester, methacrylic ester or styrene.
The acrylic polymer as the component (A) may be an acrylic polymer having such a structure, such as the main chain skeleton of the polymer constituting the acrylic polymer and the types of side chains that may be present other than the specific side chain. Is not particularly limited.

  However, when the number average molecular weight of the acrylic polymer of component (A) is excessively larger than 30,000, the flattening performance with respect to the step is lowered, while the number average molecular weight is less than 2,000 and too small. If it is, it may be insufficiently cured at the time of thermosetting and solvent resistance may be reduced. Accordingly, the acrylic polymer as the component (A) has a number average molecular weight in the range of 2,000 to 30,000.

  As described above, the specific side chain of the component (A) is not particularly limited as long as it has 3 to 16 carbon atoms and has an unsaturated bond at the terminal. Among these, a specific side chain represented by the following formula (1) is preferable.

In formula (1), R ₁ has 1 to 13 carbon atoms and is selected from an organic group selected from the group consisting of aliphatic groups, aliphatic groups containing cyclic structures, and aromatic groups, or a group thereof. An organic group comprising a combination of a plurality of organic groups. R ₁ may contain a bond such as an ester bond, an ether bond, an amide bond, or a urethane bond.

Specific examples of R ₁ include the following formula (A-1) to formula (A-10).

Among the specific side chains represented by the formula (1), a specific side chain that is an aliphatic side chain is particularly preferable.
More preferably, among the specific side chains represented by the formula (1), a specific side chain whose terminal is an acryloyl group or a methacryloyl group is particularly preferable.
More preferably, the unsaturated double bond contained in the specific side chain represented by the formula (1) is contained in an amount of 1 mol equivalent to 200 to 1,300 g equivalent of the acrylic polymer of the component (A). desirable.

  The method for obtaining the acrylic polymer having a specific side chain as described above is not particularly limited. For example, an acrylic polymer having a specific functional group is generated in advance by a polymerization method such as radical polymerization, and the specific functional group and A specific side chain can be generated by reacting a compound having an unsaturated bond at the terminal (hereinafter referred to as a specific compound) to obtain an acrylic polymer as the component (A).

Here, the specific functional group means one or more functional groups selected from the group consisting of a carboxyl group, a glycidyl group, a hydroxy group, an amino group having active hydrogen, a phenolic hydroxy group, an isocyanate group, and the like. .
Examples of the specific compound include glycidyl methacrylate, glycidyl acrylate, isocyanate ethyl methacrylate, isocyanate ethyl acrylate, methacrylic acid chloride, acrylic acid chloride, methacrylic acid, and acrylic acid.

  Among the acrylic polymers thus obtained, an acrylic polymer having a preferred specific side chain is an acrylic polymer having a side chain represented by formula (1), that is, in the following formula (2): An acrylic polymer having the structure represented.

(In Formula (2), R ₁ has 1 to 13 carbon atoms as defined in Formula (1) above, and is composed of an aliphatic group, an aliphatic group containing a cyclic structure, and an aromatic group. An organic group selected from the group or a combination of a plurality of organic groups selected from these groups, and R ₁ includes a bond such as an ester bond, an ether bond, an amide bond, or a urethane bond. R ₂ represents a hydrogen atom or a methyl group.)

  In the reaction for generating the specific side chain, preferred combinations of the specific functional group and the specific compound include a carboxyl group and an epoxy group, a hydroxy group and an isocyanate group, a phenolic hydroxy group and an epoxy group, a carboxyl group and an isocyanate group, amino A combination of a group and an isocyanate group, a hydroxy group and an acid chloride, and the like. More specifically, a carboxyl group and glycidyl methacrylate, and a hydroxy group and isocyanate ethyl methacrylate are preferable.

The acrylic polymer having the above specific functional group is a monomer having a functional group (specific functional group) for reacting with a specific compound, that is, a carboxyl group, a glycidyl group, a hydroxy group, an amino group having active hydrogen, a phenolic group. A (co) polymer obtained by polymerizing a monomer selected from the group consisting of monomers having a hydroxy group or an isocyanate group as an essential constituent, and having a number average molecular weight of 2,000 to 25,000 It is. In that case, the monomer which has a specific functional group may be individual, and if it is a combination which does not react during superposition | polymerization, multiple types may be used together.
Specific examples of the monomer having the specific functional group necessary for obtaining the acrylic polymer having the specific functional group are shown below, but the invention is not limited thereto.

  Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl). ) Maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.

  Examples of the monomer having a glycidyl group include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene, 1,7. -Octadiene monoepoxide etc. are mentioned.

  Examples of the monomer having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3- Dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, poly (Ethylene glycol) ethyl ether methacrylate, 5-acryloyl Shi-6-hydroxy-norbornene-2-carboxylic-6-lactone, 5-methacryloyloxy-6-hydroxy-norbornene-2-carboxylic-6-lactone and the like.

  Examples of the monomer having an amino group having active hydrogen include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.

  Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide and the like.

  Furthermore, as a monomer which has an isocyanate group, acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, m-tetramethyl xylene isocyanate, etc. are mentioned, for example.

Moreover, in this invention, when obtaining the acrylic polymer which has a specific functional group, the monomer which has a non-reactive functional group which can be copolymerized with the monomer which has the above-mentioned specific functional group can be used together.
Specific examples of the monomer having a non-reactive functional group include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.
Hereinafter, although the specific example of the monomer which has a non-reactive functional group is given, it is not limited to these.

Examples of the acrylic ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert- Butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2 -Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate And, like 8-ethyl-8-tricyclodecyl acrylate.

  Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert- Butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ -Butyrolactone methacrylate, 2-propyl-2 Adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and, 8-ethyl-8-tricyclodecyl methacrylate.

  Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

  Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The method for obtaining an acrylic polymer having a specific functional group used in the present invention is not particularly limited. For example, a monomer having a specific functional group, another monomer having a non-reactive functional group capable of copolymerization, and initiation of polymerization if desired. It can be obtained by carrying out a polymerization reaction at a temperature of 50 to 110 ° C. in a solvent in which an agent or the like is present. In that case, the solvent used will not be specifically limited if it dissolves the monomer which comprises the acrylic polymer which has a specific functional group, and the acrylic polymer which has a specific functional group. As a specific example, the solvent described in the (C) solvent mentioned later is mentioned.
The acrylic polymer having a specific functional group thus obtained is usually in a solution state dissolved in a solvent.

Next, a specific compound is reacted with the obtained acrylic polymer having a specific functional group to obtain an acrylic polymer (hereinafter also referred to as a specific copolymer) as the component (A). At that time, usually, a solution of an acrylic polymer having a specific functional group is subjected to the reaction.
Specifically, for example, a specific copolymer is obtained by reacting a solution of an acrylic polymer having a carboxyl group with glycidyl methacrylate at a temperature of 80 ° C. to 150 ° C. in the presence of a catalyst such as benzyltriethylammonium chloride. be able to. In that case, the solvent used will not be specifically limited if the monomer which comprises a specific copolymer, and a specific copolymer are melt | dissolved. As a specific example, the solvent described in the (C) solvent mentioned later is mentioned.
The specific copolymer which is the component (A) thus obtained is usually in the state of a solution in which the specific copolymer is dissolved in a solvent.

In addition, after the solution of the specific copolymer which is the component (A) obtained as described above is added under stirring such as diethyl ether or water to cause reprecipitation, the generated precipitate is filtered and washed. The powder of the specific copolymer can be obtained by drying at normal temperature or under reduced pressure at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer remaining in the solution of the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be redissolved in a solvent (C) described later and used as a solution.
In the present invention, the acrylic polymer of component (A) may be a mixture of a plurality of types of specific copolymers.

<B component>
As the 1,2-quinonediazide compound as component (B), in a compound having either a hydroxy group or an amino group, or a compound having both a hydroxy group and an amino group, these hydroxy group or amino group ( In the case of having both a hydroxy group and an amino group, preferably 10 to 100 mol%, particularly preferably 20 to 95 mol% of the total molar amount) is esterified with a 1,2-quinonediazidesulfonic acid compound, Alternatively, amidated compounds can be mentioned.

Examples of the compound having a hydroxy group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, ethyl gallate, 1,3,3-tris (4-hydroxyphenyl). ) Butane, 4,4-isopropylidene diphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxyphenylsulfone, 4,4 -Hexafluoroisopropylidenediphenol, 4,4 ', 4 "-trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4,4'-[1- [4- [1- (4- Hydroxyphenyl) -1-methylethyl]
Phenyl] ethylidene] bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 3,4,4′-pentahydroxybenzophenone, phenol compounds such as 2,5-bis (2-hydroxy-5-methylbenzyl) methyl, ethanol, 2-propanol, 4-butanol, cyclohexanol, Examples include aliphatic alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, and butyl lactate. .

  Examples of the compound containing an amino group include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine. Anilines such as 4,4′-diaminophenylmethane and 4,4′-diaminodiphenyl ether, and aminocyclohexane.

Furthermore, examples of the compound containing both a hydroxy group and an amino group include o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, and 2,4-diaminophenol. 4,4′-diamino-4 ″ -hydroxytriphenylmethane, 4-amino-4 ′, 4 ″ -dihydroxytriphenylmethane, bis (4-amino-3-carboxy-5-hydroxyphenyl) ether, Bis (4-amino-3-carboxy-5-hydroxyphenyl) methane, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) propane, 2,2-bis (4-amino-3-) Aminophenols such as carboxy-5-hydroxyphenyl) hexafluoropropane, 2-aminoethanol , Mention may be made of 3-aminopropanol, the alkanol amines such as 4-amino-cyclohexanol.

  These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

  The content of the component (B) in the positive photosensitive resin composition of the present invention is preferably 5 to 100 parts by weight, more preferably 8 to 50 parts by weight, more preferably 100 parts by weight of the component (A). The amount is preferably 10 to 40 parts by mass. When the amount is less than 5 parts by mass, the difference in dissolution rate between the exposed portion and the unexposed portion of the positive photosensitive resin composition in the developer is reduced, and patterning by development may be difficult. On the other hand, when the amount exceeds 100 parts by mass, the 1,2-quinonediazide compound is not sufficiently decomposed by exposure in a short time and the sensitivity is lowered, or the component (B) absorbs light to improve the transparency of the cured film. It may be reduced.

<(C) Solvent>
The (C) solvent used in the present invention dissolves the (A) component and the (B) component, and dissolves the (D) component to the (E) component, which will be described later, if desired. The solvent is not particularly limited in its type and structure as long as it has a good solubility.
Examples of such a solvent (C) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol. Monomethyl ether acetate, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone , Ethyl 2-hydroxypropionate, 2-hydroxy-2 Ethyl methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate , Methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

These solvents can be used singly or in combination of two or more.
Among these (C) solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, etc. have good coating properties and safety Is preferable from the viewpoint of high. These solvents are generally used as solvents for photoresist materials.

<D component>
Component (D) is a surfactant. The positive photosensitive resin composition of the present invention can further contain a surfactant for the purpose of improving the coating properties as long as the effects of the present invention are not impaired.

(D) Although it does not restrict | limit especially as surfactant of a component, For example, a fluorine-type surfactant, a silicone type surfactant, a nonionic surfactant etc. are mentioned. As this type of surfactant, for example, commercially available products such as those manufactured by Sumitomo 3M Co., Ltd., Dainippon Ink Chemical Co., Ltd., or Asahi Glass Co., Ltd. can be used. These commercial products are convenient because they can be easily obtained. Specific examples thereof include F-top EF301, EF303, EF352 (manufactured by Gemco Co., Ltd.), MegaFac R30, R08, R90, BL20, R61, F171, F173, F471, F475, F479, F474, F477, F480. F482, F483, F484 (Dainippon Ink Chemical Co., Ltd.), Florard FC430, FC431 (Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, Fluorosurfactants such as SC106 (Asahi Glass Co., Ltd.) can be used.
(D) The surfactant of a component can be used individually by 1 type or in combination of 2 or more types.
When the surfactant is used, the content thereof is preferably 0.1% by mass or less in 100% by mass of the positive photosensitive resin composition. Even if the amount of the surfactant used as the component (D) is set to an amount exceeding 0.1% by mass, the effect of improving the coating property becomes dull and not economical.

<E component>
Component (E) is an adhesion promoter. In the positive photosensitive resin composition of the present invention, an adhesion promoter may be added for the purpose of improving the adhesion to the substrate after development. Specific examples of such adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, Alkoxysilanes such as diphenyldimethoxysilane and phenyltriethoxysilane, hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, silazanes such as dimethyltrimethylsilylamine, trimethylsilylimidazole, vinyltrichlorosilane, γ-aminopropyltri Ethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (N-piperidini ) Silanes such as propyltriethoxysilane, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptoimidazole, etc. Examples thereof include cyclic compounds, urea such as 1,1-dimethylurea and 1,3-dimethylurea, and thiourea compounds.

The above adhesion promoter is, for example, a commercial product manufactured by Shin-Etsu Chemical Co., Ltd., Momentive Performance Materials Japan GK (former GE Toshiba Silicone Co., Ltd.) or Toray Dow Corning Co., Ltd. These compounds can also be used, and these commercial products are readily available.
As the component (E), one or two or more of the adhesion promoters can be used.
The addition amount of these adhesion promoters is usually preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A). If it is used in excess of 10 parts by mass, the heat resistance of the coating film may be reduced, and if it is less than 0.5 part by mass, sufficient effects of the adhesion promoter may not be obtained.

<Other additives>
Furthermore, as long as the positive photosensitive resin composition of the present invention does not impair the effects of the present invention, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, or a polyhydric phenol, A dissolution accelerator such as a polyvalent carboxylic acid can be contained.

<Positive photosensitive resin composition>
The positive photosensitive resin composition of the present invention comprises an alkali-soluble acrylic polymer as component (A), (
B) Component 1,2-quinonediazide compound and (C) solvent, and optionally 1 (D) surfactant, (E) adhesion promoter, and other additives It is a composition which can further contain seeds or more.

Among these, preferred examples of the positive photosensitive resin composition of the present invention are as follows.
[1]: A positive photosensitive resin composition containing 5 to 100 parts by mass of the component (B) based on 100 parts by mass of the component (A) and dissolving these components in the solvent (C).
[2]: A positive photosensitive resin composition further containing 0.1% by mass or less of component (D) in the composition of [1] above.
[3]: A positive photosensitive resin composition further containing 0.5 to 10 parts by mass of the component (E) based on 100 parts by mass of the component (A) in the composition of the above [1] or [2]. .

  The ratio of the solid content in the positive photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, and is, for example, 1 to 80% by mass. It is 5 to 60% by mass, or 10 to 50% by mass. Here, solid content means what remove | excluded the (C) solvent from all the components of the positive photosensitive resin composition.

  The method for preparing the positive photosensitive resin composition of the present invention is not particularly limited. For example, the component (A) (alkali-soluble acrylic polymer) is dissolved in the solvent (C) and this solution is used. (B) component (1,2-quinonediazide compound) is mixed in a predetermined ratio to make a uniform solution, or at an appropriate stage of this preparation method, component (D) (surfactant) Agent), (E) component (adhesion promoter) and other additives are further added and mixed.

  In the preparation of the positive photosensitive resin composition of the present invention, the solution of the specific copolymer (A) obtained by the polymerization reaction in the solvent (C) can be used as it is. When the component (B) is added to the solution of the component (A) in the same manner as described above to make a uniform solution, a solvent (C) may be further added for the purpose of adjusting the concentration. At this time, the (C) solvent used in the process of forming the specific copolymer and the (C) solvent used for concentration adjustment when preparing the positive photosensitive resin composition are the same or different. May be.

Thus, the prepared positive photosensitive resin composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

<Coating film and cured film>
The positive photosensitive resin composition of the present invention is applied to a semiconductor substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, or an ITO substrate. Etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following slit, ink jet coating, etc., and then pre-dried in a hot plate or oven to form a coating film can do. Then, a positive photosensitive resin film is formed by heat-treating this coating film.

  As conditions for this heat treatment, for example, a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C. to 160 ° C. and a time of 0.3 to 60 minutes are employed. The heating temperature and heating time are preferably 80 to 140 ° C. and 0.5 to 10 minutes.

  The film thickness of the positive photosensitive resin film formed from the positive photosensitive resin composition is, for example, 0.1 to 30 μm, is, for example, 0.2 to 10 μm, and is further, for example, 0.2 to 5 μm. It is.

  On the coating film obtained above, a mask having a predetermined pattern is attached, irradiated with light such as ultraviolet rays, and then developed with an alkaline developer, so that the exposed portion is washed out and the edge has a sharp relief. A pattern is obtained.

  Examples of the alkaline developer that can be used include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline. Alkaline aqueous solutions such as amine aqueous solutions such as ethanolamine, propylamine, and ethylenediamine. Further, a surfactant or the like can be added to these developers.

  Among the above, a tetraethylammonium hydroxide 0.1 to 2.38 mass% aqueous solution is generally used as a photoresist developer, and the alkaline developer is also used in the photosensitive resin composition of the present invention. It can be developed satisfactorily without causing problems such as swelling.

  Further, as a developing method, any of a liquid piling method, a dipping method, a rocking dipping method, and the like can be used. The development time at that time is usually 15 to 180 seconds.

  After the development, the positive photosensitive resin film is washed with running water, for example, for 20 to 90 seconds, and then air-dried with compressed air or compressed nitrogen or by spinning to remove moisture on the substrate, and A patterned film is obtained.

  Subsequently, the pattern forming film is subjected to post-baking for thermosetting, specifically by heating using a hot plate, an oven, etc., thereby providing heat resistance, transparency, and flatness. In addition, a film having a good relief pattern with excellent water absorption and chemical resistance can be obtained.

  The post-bake is generally processed at a heating temperature selected from the range of 140 ° C. to 250 ° C. for 5 to 30 minutes when on a hot plate and 30 to 90 minutes when in an oven. The method is taken.

  Thus, such a post-bake can provide a target cured film having a good pattern shape.

As described above, the positive photosensitive resin composition of the present invention has a high storage stability, a sufficiently high sensitivity, a very small film loss at an unexposed portion during development, and a coating having a fine pattern. A film can be formed.
Moreover, the cured film obtained from this coating film has the characteristics that it is excellent in heat resistance and solvent resistance, and is highly transparent. For this reason, it can be suitably used in applications such as an array flattening film of a TFT type liquid crystal element together with various films in a liquid crystal display and an organic EL display such as an interlayer insulating film, a protective film, and an insulating film.

  In particular, due to poor storage stability so far, the disadvantages of the epoxy-crosslinked photosensitive resin composition, which has been disadvantageous economically in addition to performance deterioration, are eliminated, and after storage for 10 days, it is almost the same as immediately after production. A new positive-type photosensitive resin composition capable of maintaining a high quality can be obtained, and a coating film and a cured film obtained from the composition can be suitably used for the various materials described above.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these Examples.

[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
MAA: methacrylic acid MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate CHMI: N-cyclohexylmaleimide GMA: glycidyl methacrylate DCM: dicyclopentyl methacrylate BTEAC: benzyltriethylammonium THPA: 1,2,3,6-tetrahydrophthalic anhydride AIBN: Azobisisobutyronitrile PGMEA: Propylene glycol monomethyl ether acetate QD: 1 mol of 1,3,3-tris (4-hydroxyphenyl) butane and 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride A compound synthesized by a condensation reaction.
CL1: Epolide GT-401 (alicyclic epoxy resin) manufactured by Daicel Chemical Industries, Ltd.
MPTS: γ-methacryloxypropyltrimethoxysilane R30: manufactured by Dainippon Ink & Chemicals, Inc. Megafax R-30 (trade name)

[Measurement of number average molecular weight and weight average molecular weight]
The number average molecular weight and weight average molecular weight of the (specific) copolymer obtained in accordance with the following synthesis example were determined using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation and the elution solvent tetrahydrofuran was determined. The measurement was performed under the condition of flowing through a column at a flow rate of 1 ml / min (column temperature: 40 ° C.) for elution. The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

<Synthesis Example 1>
MAA (40.0 g) and DCM (40.0 g) are used as monomer components constituting the copolymer, AIBN (2 g) is used as a radical polymerization initiator, and these are polymerized in a solvent PGMEA (120 g). By making it react, the copolymer solution (copolymer density | concentration: 40 mass%) which is Mn6,300 and Mw10,600 was obtained (P1). The polymerization temperature was adjusted to 60 to 100 ° C.

<Synthesis Example 2>
By adding GMA (26.0 g), BTEAC (1.1 g), and PGMEA (39 g) to 200 g of the copolymer (P1) and reacting them, the component (A) of Mn7,200 and Mw13,200 (specific copolymer weight) A solution (specific copolymer concentration: 40% by mass) was obtained (P2). The reaction temperature was adjusted to 90 to 120 ° C.

<Synthesis Example 3>
GMA (66.1 g), BTEAC (2.8 g), and PGMEA (99.2 g) were added to 200 g of the copolymer (P1) and reacted. The reaction temperature at this time was adjusted to 90 to 120 ° C.
By adding THPA (23.2 g) and PGMEA (34.8 g) to 200 g of the obtained reaction liquid and adjusting the temperature to 80 to 100 ° C., the reaction was conducted to obtain Mn 9,300, Mw 20,500 (A) A solution (specific copolymer concentration: 40% by mass) of a component (specific copolymer) was obtained (P3).

<Synthesis Example 4>
As monomer components constituting the copolymer, MAA 15.5 g, CHMI 35.3 g, HEMA 25.5 g, MMA 23.7 g were used, and AIBN 5 g was used as a radical polymerization initiator, and these were used in a solvent PGMEA 200 g. Then, a copolymer solution (copolymer concentration: 27.5% by mass) having Mn 4,100 and Mw 7,600 was obtained by performing a polymerization reaction at a temperature of 60 ° C. to 100 ° C. in FIG. (P4)

<Synthesis Example 5>
As monomer components constituting the copolymer, MAA 23.0 g, GMA 40.0 g,
By using 37.0 g of DCM, 5 g of AIBN as a radical polymerization initiator, and carrying out a polymerization reaction at a temperature of 60 ° C. to 100 ° C. in 200 g of a solvent PGMEA, a copolymer having Mn 4,300 and Mw 9,600 is obtained. A combined solution (copolymer concentration: 27.5% by mass) was obtained. (P5)

<Examples 1 to 4 and Comparative Examples 1 to 4>
In accordance with the composition shown in the following Table 1, (B) component and (C) solvent, (D) component, (E) component and other components (epoxy resin) ) Were mixed at a predetermined ratio, and stirred at room temperature for 3 hours to obtain a uniform solution, thereby preparing positive photosensitive resin compositions of Examples and Comparative Examples.

  With respect to the obtained positive photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4, respectively, from the viewpoint of storage stability of the composition, the sensitivity of the coating film and the film reduction (in the unexposed part) In addition, the solvent resistance of the cured film was measured and evaluated.

[Solution stability evaluation]
For the positive photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4 described above, the sensitivity and film loss were measured by the following methods immediately after preparation of the compositions and after storage for 10 days at room temperature. ,evaluated.

[Evaluation of sensitivity]
The positive photosensitive resin composition was applied on a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5.5 mW / cm ² for a predetermined time by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. Thereafter, development was performed by immersing in a 0.4% by mass tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution for 60 seconds, followed by washing with running ultrapure water for 20 seconds. The lowest exposure amount (mJ / cm ² ) at which no undissolved portion remained in the exposed area was evaluated as sensitivity.
Table 2 shows the sensitivity of the composition immediately after preparation and the amount of change in sensitivity of the composition after storage for 10 days for each composition.

[Evaluation of film reduction]
The positive photosensitive resin composition was applied on a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. This membrane was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds and then washed with running ultrapure water for 20 seconds. Next, by measuring the thickness of this film, the degree of film reduction in the unexposed area due to development was evaluated. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.
Table 2 shows the degree of film thickness reduction of the composition immediately after preparation and the amount of change in the film thickness reduction degree of the composition after storage for 10 days.

[Evaluation of solvent resistance]
The positive photosensitive resin composition just prepared was applied on a silicon wafer using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. This coating film was post-baked by heating at 230 ° C. for 30 minutes to form a cured film having a thickness of 2.1 μm. This coating film was immersed in NMP for 1 minute at room temperature. A film having no change in film thickness before and after immersion was marked with ◯, and a film with a decrease in film thickness was marked with x.

[Evaluation results]
The results of the above evaluation are shown in Table 2 below.

  As can be seen from the results shown in Table 2, all of the positive photosensitive resin compositions of Examples 1 to 4 have high sensitivity, no film loss in unexposed areas, and high after storage of the solution at room temperature for 10 days. The sensitivity was maintained. Furthermore, there was no problem with solvent resistance after curing.

  On the other hand, in Comparative Examples 1 and 3, although the positive photosensitive resin composition had high solution stability, thermosetting did not occur due to post-baking, and sufficient solvent resistance was not obtained. In Comparative Examples 2 and 4, although sufficient solvent resistance was obtained after post-baking, a decrease in sensitivity and an increase in film loss were observed after the solution was stored at room temperature for 10 days.

  The positive photosensitive resin composition according to the present invention is suitable as a material for forming a cured film such as a protective film, a planarizing film, and an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element. In particular, it is also suitable as a material for forming an interlayer insulating film of a TFT type liquid crystal element, a protective film for a color filter, an array flattening film, an uneven film under a reflective film of a reflective display, an insulating film of an organic EL element, etc. Furthermore, it is also suitable as various electronic materials such as a microlens material.

Claims (10)

A positive photosensitive resin composition comprising the following component (A), component (B) and solvent (C).
Component (A): an alkali-soluble acrylic polymer having 3 to 16 carbon atoms and having a side chain having an unsaturated bond at the terminal, and having a number average molecular weight of 2,000 to 30,000 in terms of polystyrene,
(B) component: 1,2-quinonediazide compound,
(C) Solvent.   The positive photosensitive resin composition according to claim 1, wherein the component (A) is an alkali-soluble acrylic polymer having an aliphatic side chain having an unsaturated bond at the terminal.   The positive photosensitive resin composition according to claim 1 or 2, wherein the component (A) is an alkali-soluble acrylic polymer having a side chain having an acryloyl group or a methacryloyl group at the terminal.   The positive photosensitive resin composition as described in any one of Claims 1 thru | or 3 containing 5-100 mass parts (B) component with respect to 100 mass parts of (A) component.   The positive photosensitive resin according to any one of claims 1 to 4, further comprising 0.1% by mass or less of a surfactant as a component (D) in the positive photosensitive resin composition. Composition.   The positive type according to any one of claims 1 to 5, further comprising 0.5 to 10 parts by mass of an adhesion promoter as component (E) with respect to 100 parts by mass of component (A). Photosensitive resin composition.   The cured film obtained using the positive photosensitive resin composition as described in any one of Claims 1 thru | or 6.   A liquid crystal display element having the cured film according to claim 7.   An array planarizing film for a liquid crystal display comprising the cured film according to claim 7.   An interlayer insulating film comprising the cured film according to claim 7.