KR20130106280A - Photosensitive resin composition and display device - Google Patents

Abstract

 [Problem] A positive photosensitive resin composition which satisfies the basic performance requirements for the electrode protective film, the planarization film, and the insulating film by curing, and at the same time obtains a film having a high hardness, which is required for the materials of various display devices, is obtained. to provide. In addition, a display device having excellent mechanical strength is provided. [Solution] A display having an alkali-soluble acrylic polymer having a side chain having an unsaturated bond at its terminal, a quinone diazide compound, a silsesquioxane, a photosensitive resin composition containing a solvent, and a film formed by curing the resin composition. An apparatus is provided.

Description

Photosensitive resin composition and display apparatus {PHOTOSENSITIVE RESIN COMPOSITION AND DISPLAY DEVICE}

The present invention relates to a photosensitive resin composition and a display device.

Displays such as an active matrix drive type liquid crystal display device having a thin film transistor (TFT) or an active matrix drive type organic EL display device having an organic electroluminescence (EL) element and a thin film transistor connected thereto. The apparatus is provided with a patterned electrode protective film, planarization film, insulating film and the like. Generally as a material which forms these films, the photosensitive resin composition is used, and the number of processes for obtaining a predetermined | prescribed pattern shape is especially small, and the thing excellent in transparency is used widely.

In addition, the electrode protective film, the planarization film, and the insulating film require various characteristics required for the display device. Specifically, the process resistance such as heat resistance, solvent resistance, reflow-resistant property, and metal sputter resistance should be excellent, adhesiveness with the lower extremity should be good, and the pattern may be changed under various process conditions according to the purpose of use. It has a wide process margin which can be formed, it has high sensitivity with respect to light, has high transparency, and there is little film thickness nonuniformity after image development. Therefore, conventionally, the photosensitive resin composition containing a naphthoquinone diazide compound has been used universally.

On the other hand, with the recent spread of the touch panel, the display apparatus provided with the touch panel in the liquid crystal display element or organic electroluminescent element is increasing. As a touch panel method, there are a resistive film method, a capacitive method, an ultrasonic method, an optical method, an electromagnetic induction method, and the like. In view of performance, many manufacturers adopting the capacitive method are increasing. In the capacitive method, wirings made of a transparent conductive film are formed on the substrate, and an interlayer insulating film is provided to prevent conduction between the wirings. High hardness is required for this interlayer insulating film. There is also an in-cell touch panel in which a touch panel mechanism is incorporated in the liquid crystal display element. In this case, higher hardness is required for the electrode protective film.

Moreover, although the glass substrate is used for the conventional display apparatus, in recent years, in addition to weight reduction, thinning, large size, curved display, etc. with respect to a display apparatus, the demand of high durability etc. in a portable device is increasing. Therefore, the practical use of the resin substrate which consists of plastics, such as a polyethylene terephthalate, a polybutylene terephthalate, a polyether sulfone, a polycarbonate, and a polyimide, is considered instead of a glass substrate. When the flexible display is enabled by the application of the resin substrate, high hardness is further required for the electrode protective film, the planarization film and the insulating film in terms of increasing the mechanical strength.

By the way, in the photosensitive resin composition, there are a negative type which hardens by exposure and the solubility to a developing solution becomes low, and a positive type which increases solubility to a developing solution by exposure. Most of the negative type uses an organic solvent as a developer, which causes problems in handling and environment. Moreover, since a solvent swells a film | membrane at the time of image development, there also exists a problem that it is difficult to form a fine wiring. On the other hand, the positive type is advantageous over the negative type in the above-described point, but there is a problem that it is difficult to realize high hardness as compared with the negative type where the curing proceeds by exposure.

Patent Document 1 includes at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and at least one selected from the group consisting of oxiranyl group-containing unsaturated compounds and oxetanyl group-containing unsaturated compounds. A positive radiation sensitive resin composition containing a copolymer of an unsaturated mixture containing, a 1,2-quinonediazide compound and a silsesquioxane having an aryl group having 6 to 15 carbon atoms is described. According to this composition, although it seems that the pattern shape thin film suitable for an interlayer insulation film etc. can be formed, there exists a problem that a crosslinking reaction is slow and it is difficult to acquire reflow property.

Patent Document 2, an acryl-based copolymer obtained by copolymerizing at least one of a silsesquioxane polyhedral oligomer-containing unsaturated compound, unsaturated carboxylic acid and unsaturated carboxylic anhydride, an epoxy group-containing unsaturated compound and an olefinically unsaturated compound, and 1,2-quinonedia A photosensitive resin composition comprising a zide compound is disclosed. This composition is excellent in the flatness, sensitivity, resolution, heat resistance and transparency after development, and appears to be suitable as an insulating film of a display device. By the way, in this case, since monofunctional silsesquioxane is used, the silsesquioxane part does not crosslink in the polymer after copolymerization, and it is concerned that the hardness of the film obtained is lacking.

In patent document 3, the photosensitive resin composition suitable as an insulating film of a display apparatus is disclosed. The composition is selected from ethylenically unsaturated group-containing compounds, cationic polymerizable compounds such as photopolymerization initiators and glycidyl ether compounds, and photocationic polymerization initiators and at least one compound among quinonediazide compounds, diazonium compounds and azide compounds. At least one photosensitive organic component, inorganic particles, and silsesquioxanes in cage form. However, this configuration has a problem that the resolution is lowered due to the added inorganic particles in order to maintain shape retention during firing. In fact, in the Example of patent document 3, the via-hole diameter retention after baking of the via pattern which has a hole diameter of 20 micrometers is 65%.

Japanese Patent Publication No. 2009-229892 Japanese Patent Publication No. 2007-119777 Japanese Patent Publication No. 2007-47247

This invention is made | formed in view of the said problem. That is, the object of the present invention is to satisfy the basic performance requirements for the electrode protective film, the planarization film, and the insulating film by curing, and to obtain a film having a high hardness recently required for various display materials. It is providing a type photosensitive resin composition. Moreover, the objective of this invention is providing the display apparatus excellent in mechanical strength.

The photosensitive resin composition of this invention,

(A): alkali-soluble acrylic polymer which has a side chain which has an unsaturated bond at the terminal,

(B): quinonediazide compound,

(C): silsesquioxane,

(D): solvent

It contains.

It is preferable that the number average molecular weights of the alkali-soluble acrylic polymer of (A) are 2,000-50,000 in polystyrene conversion.

In the alkali-soluble acrylic polymer of (A), it is preferable that the terminal of a side chain is acryloyl group, methacryloyl group, vinylphenyl group, or isopropenyl phenyl group.

It is preferable that the quinonediazide compound of (B) is contained in the quantity used as 5-100 mass parts with respect to 100 mass parts of alkali-soluble acrylic polymers of (A).

It is preferable to contain the silsesquioxane of (C) in the quantity used as 5-100 mass parts with respect to 100 mass parts of alkali-soluble acrylic polymers of (A).

It is preferable that the photosensitive resin composition of this invention contains (E) thermal acid generator in the quantity which becomes 0.1-30 mass parts further with respect to 100 mass parts of alkali-soluble acrylic polymers of (A).

The photosensitive resin composition of this invention contains the compound which has 2 or more vinyl groups directly couple | bonded with (F) benzene ring in the amount which becomes 1-40 mass parts with respect to 100 mass parts of alkali-soluble acrylic polymers of (A) further. It is desirable to.

It is preferable that the photosensitive resin composition of this invention contains the acrylic polymer which has an epoxy group (G) epoxy group in a side chain further with respect to 100 mass parts of alkali-soluble acrylic polymers of (A) in the quantity used as 0.5-40 mass parts.

It is preferable that the photosensitive resin composition of this invention contains (H) adhesion promoter further in quantity of 20 mass parts or less with respect to 100 mass parts of alkali-soluble acrylic polymers of (A).

It is preferable that the photosensitive resin composition of this invention contains (I) surfactant further in 1.0 mass part or less with respect to 100 mass parts of photosensitive resin compositions.

The display apparatus of this invention has a film | membrane which hardens the photosensitive resin composition of this invention, It is characterized by the above-mentioned.

According to the present invention, it is possible to provide a positive photosensitive resin composition which, by curing, satisfies the basic performance requirements for the electrode protective film, the flattening film and the insulating film, and becomes a film having a high hardness.

Moreover, the high quality display apparatus excellent in mechanical strength is provided by providing the cured film obtained from this photosensitive resin composition.

The positive photosensitive resin composition of this invention contains the following (A) component, (B) component, (C) component, and (D) solvent.

(A) component: Alkali-soluble acrylic polymer which has a side chain which has an unsaturated bond at the terminal

(B) Component: Quinone diazide compound

(C) component: silsesquioxane

(D) solvent

Moreover, the photosensitive resin composition of this invention is a compound which has two or more vinyl groups directly bonded to the (E) component: thermal-acid generator, (F) component: benzene ring mentioned later as another component as needed, (G ) Component: It is also possible to contain the acrylic polymer which has an epoxy group in a side chain, (H) component: adhesion promoter, and (I) component: surfactant, and the other component mentioned later.

Hereinafter, each component is demonstrated in detail.

≪ Component (A) >

(A) component is an alkali-soluble acrylic polymer which has a side chain which has an unsaturated bond in the terminal. Preferably, the alkali-soluble acrylic polymer is an acrylic polymer having a polystyrene reduced number average molecular weight (hereinafter referred to as a number average molecular weight) of 2,000 to 50,000.

In the present invention, the acrylic polymer refers to a polymer obtained by homopolymerizing or copolymerizing a monomer having an unsaturated double bond such as acrylic acid ester, methacrylic acid ester and styrene. Although the acrylic polymer of (A) component should just be an acrylic polymer which has such a structure, the kind of frame | skeleton of the principal chain, side chain, etc. of the polymer which comprise an acrylic polymer are not specifically limited.

However, when the number average molecular weight of the acrylic polymer of (A) component exceeds too much 50,000, the planarization performance with respect to a level | step difference may fall. On the other hand, when the number average molecular weight is too small, less than 2,000, solvent resistance may decrease due to insufficient curing at the time of thermosetting. Therefore, it is more preferable that a number average molecular weight exists in the range of 2,000-50,000.

The acrylic polymer of the component (A) preferably has 3 to 16 carbon atoms, and preferably has a side chain (hereinafter, referred to as a specific side chain) having an unsaturated bond at its terminal. On the other hand, per 1 mol equivalent of the unsaturated bond of the terminal contained in the said specific side chain, it is the quantity which the acrylic polymer of (A) component is 200-1,300 g equivalent, and it is preferable to have an unsaturated bond of the terminal.

As said specific side chain, it is especially preferable that it is a structure represented by following formula (1). The specific side chain represented by Formula (1) is bonded to the ester bond part of an acrylic polymer as shown in Formula (1-1).

[Formula 1]

In formula (1), R <_1> is 1-14 organic carbon atoms, The organic group chosen from the group which consists of an aliphatic group containing an aliphatic group, a cyclic structure, and an aromatic group, or the some organic group chosen from the said group. Organic group consisting of a combination of. In addition, R ₁ may contain an ester bond, an ether bond, an amide bond, or a urethane bond.

As a specific example of R <_1> , following formula (A-1)-a formula (A-11) etc. are mentioned.

On the other hand, in the formula, the ** side is bonded to the ester bond moiety of the acrylic polymer, and the * side is bonded to the carbon atom (carbon atom to which R ₂ is bonded) having a double bond of formula (1).

(2)

In formula (1), R <_2> represents a hydrogen atom or a methyl group, and it is more preferable that R <_2> is a hydrogen atom.

It is preferable that the specific side chain represented by Formula (1) is an acryloyl group, a methacryloyl group, a vinylphenyl group, or an isopropenyl phenyl group, for example, R <_1> is a formula (A-1)-a formula ( It is preferable that it is a specific side chain represented by A-3) and Formula (A-7)-Formula (A-11).

The method of obtaining the acrylic polymer which has such a specific side chain is not specifically limited. For example, the acrylic polymer which has a specific functional group mentioned later is produced by polymerization methods, such as radical polymerization previously. Subsequently, this specific functional group can be made into the acrylic polymer which is (A) component by making a specific side chain react with the compound (henceforth a specific compound) which has an unsaturated bond at the terminal.

Here, a specific functional group means functional groups, such as a carboxyl group, a glycidyl group, a hydroxyl group, an amino group which has an active hydrogen, a phenolic hydroxyl group, or an isocyanate group, or several types of functional group selected from these.

Moreover, as a specific compound, glycidyl acrylate, glycidyl methacrylate, isocyanate ethyl acrylate, isocyanate ethyl methacrylate, acrylic acid chloride, methacrylic acid chloride, acrylic acid, methacrylic acid, m -Tetramethyl xylene diisocyanate, chloro styrene, bromostyrene, allyl glycidyl ether, vinyl ethylene oxide, vinyl cyclohexene oxide, (alpha), (alpha)-dimethyl-m- isopropenyl benzyl isocyanate, etc. are mentioned.

In the acrylic polymer obtained by such a method, an example of a preferable structure is an acrylic polymer which has a structural unit represented by Formula (2).

(3)

In formula (2), R <_1> is the same as what was defined by Formula (1) mentioned above, ie, it is C1-C14, It is selected from the group which consists of an aliphatic group containing an aliphatic group, a cyclic structure, and an aromatic group. It is an organic group which consists of an organic group or the combination of several organic group chosen from this group. In addition, R ₁ may include a bond such as an ester bond, an ether bond, an amide bond, or a urethane bond.

In formula (2), R <_3> represents a hydrogen atom or a methyl group.

In the reaction for producing the specific side chain described above, a preferable combination of a specific functional group and a group involved in the reaction as a functional group of the specific compound is a carboxyl group, a glycidyl group (epoxy group), a hydroxyl group, an isocyanate group, or a phenolic hydroxy. Group, glycidyl group (epoxy group), carboxyl group and isocyanate group, amino group and isocyanate group, or hydroxyl group and acid chloride. And a more preferable combination is a carboxyl group and glycidyl methacrylate, or a hydroxyl group and isocyanate ethyl methacrylate.

In addition, in the reaction which produces the specific side chain mentioned above, the acrylic polymer which has a specific functional group is a monomer which has a functional group (specific functional group) for reacting with a specific compound, ie, a carboxyl group, glycidyl group, a hydroxyl group, active hydrogen As a copolymer obtained by making the monomer which has an amino group, a phenolic hydroxyl group, an isocyanate group, etc. which have an essential component into an essential component, the thing of the number average molecular weights 2,000-25,000 is mentioned. Here, the monomer which has a specific functional group used for superposition | polymerization may be used individually by 1 type, and multiple types of monomer may be used together if it is a combination in which specific functional groups do not react during superposition | polymerization.

Although the specific example of the monomer suitable for obtaining the acrylic polymer which has a specific functional group, ie, the monomer which has a specific functional group, is given to the following, it is not limited to these.

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

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

As a monomer which has a hydroxyl group, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxy, for example. Butyl 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 Acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone Can be.

As a monomer which has an amino group which has active hydrogen, 2-aminoethyl acrylate, 2-aminomethyl methacrylate, etc. are mentioned, for example.

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

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

In this invention, when obtaining the acrylic polymer which has a specific functional group, the monomer which has a non-reactive functional group copolymerizable with the monomer which has a specific functional group can be used together.

As a monomer which has a non-reactive functional group, an acrylic acid ester compound, a methacrylic acid ester compound, a maleimide compound, an acrylonitrile, a maleic anhydride, a styrene compound, a vinyl compound, etc. are mentioned, for example. Hereinafter, although the specific example of the monomer which has a non-reactive functional group is mentioned, It is not limited to these.

As an acrylate ester compound, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2, for example , 2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxy ethyl acrylate, methoxy triethylene glycol acrylate, 2- ethoxy ethyl acrylate, Tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, γ-butyrolactone acrylate, dicyclopentanyl Acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, and the like.

As a methacrylic acid ester compound, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, for example. Latex, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, meth Oxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl 2-adamantyl methacrylate, γ-butyrolactone methacrylate, dicyclopentanyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate and 8-ethyl-8-tricyclodecyl methacrylate Rate And the like.

As a vinyl compound, methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether, etc. are mentioned, for example. have.

As a styrene compound, styrene, methyl styrene, chloro styrene, bromostyrene, etc. are mentioned, for example.

As a maleimide compound, maleimide, N-methyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, etc. are mentioned, for example.

In this invention, the method of obtaining the acrylic polymer which has a specific functional group is not specifically limited. For example, the polymerization reaction is carried out at a temperature of 50 to 110 ° C. in a solvent in which a monomer having the specific functional group, a monomer having another copolymerizable non-reactive functional group, and a polymerization initiator or the like coexist if necessary. Obtained. The solvent used at this time will not be specifically limited if it melt | dissolves the monomer and polymerization initiator which participate in reaction. As a specific example, what is described in the (D) solvent mentioned later is mentioned.

The acrylic polymer which has a specific functional group obtained by said method is a solution state melt | dissolved in the solvent normally.

By making a specific compound react with the obtained acrylic polymer which has a specific functional group, the acrylic polymer (henceforth a specific copolymer) which is (A) component is obtained. On the other hand, after obtaining the acrylic polymer which has a specific functional group normally, this polymer in a solution state is made to react with a specific compound as it is, and a specific copolymer is obtained.

Specifically, for example, by adding glycidyl methacrylate to a solution of an acrylic polymer having a carboxyl group and reacting at a temperature of 80 ° C to 150 ° C in the presence of a catalyst such as benzyltriethylammonium chloride, Copolymers can be obtained. The solvent used at this time will not be specifically limited if it melt | dissolves the monomer and specific copolymer which comprise a specific copolymer. As a specific example, what was described in the (D) solvent mentioned later is mentioned.

The specific copolymer obtained by said method is a solution state melt | dissolved in the solvent normally.

Moreover, in reaction of the acrylic polymer which has a specific functional group, and a specific compound, when the combination of a specific functional group and the functional group which a specific compound has is a carboxyl group and a glycidyl group, you may react dicarboxylic anhydride to the hydroxyl group produced | generated. . Since the hydrophilicity of the specific copolymer finally obtained by this improves, the applicability | paintability and solubility at the time of using for the photosensitive resin composition become favorable.

As such dicarboxylic anhydride, a phthalic anhydride, trimellitic anhydride, naphthalenedicarboxylic anhydride, a 1, 2- cyclohexane dicarboxylic anhydride, 4-methyl- 1, 2- cyclohexane dicarboxylic acid, for example Main acid anhydride, 4-phenyl-1,2-cyclohexanedicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, bicyclo [2.2. 2.] octene-2,3-dicarboxylic anhydride etc. are mentioned.

The solution of the specific copolymer is added under stirring such as diethyl ether, water, and the like to reprecipitate, and the resulting precipitate is filtered and washed, followed by normal temperature or heat drying under normal pressure or reduced pressure to obtain a powder of the specific copolymer. Can be. By such an operation, the polymerization initiator and unreacted monomer which coexist with a specific copolymer can be removed, As a result, the powder of the refined specific copolymer is obtained. On the other hand, when it cannot fully refine | purify by operation once, what is necessary is to dissolve again the obtained powder to a solvent, and to perform the said operation repeatedly. In this invention, the powder of a specific copolymer may be used as it is, or the powder of a specific copolymer may be redissolved in the solvent (D) mentioned later, and it may be used as a solution state. In the present invention, the acrylic polymer of the component (A) may be a mixture of plural kinds of specific copolymers.

&Lt; Component (B) >

The quinonediazide compound of the component (B) is preferably a quinonediazide compound having either a hydroxy group or an amino group, or both a hydroxy group and an amino group. Such a quinonediazide compound is obtained by, for example, reacting a 1,2-quinonediazide compound with a compound having a hydroxy group and / or a compound having an amino group.

As said 1, 2- quinone diazide compound, Preferably, 1, 2- naphthoquinone- 2- diazide- 5-sulfonyl chloride, 1, 2- naphthoquinone- 2- diazide- 4-sulfonate 1,2-quinonediazidesulfonic acid compounds, such as a polyyl chloride, etc. are used suitably.

More preferably, in a hydroxyl group or an amino group (when it has both a hydroxyl group and an amino group, the total amount), Preferably it is 10-100 mol%, Especially preferably, 20-95 mol% is 1, 2- quinone A quinone diazide compound obtained by esterification or amidation with a diazide sulfonic acid compound is used.

In this invention, the said quinonediazide compound can be used individually or in combination of 2 or more types.

Examples of the compound having a hydroxy group reacted with the 1,2-quinonediazide (sulfonic acid) compound include, for example, phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, and catechol. , Methyl gallate, ethyl gallate, 1,3,3-tris (4-hydroxyphenyl) butane, 4,4-isopropylidenediphenol, 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 (α, α , α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene), 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ' , 4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 3,4,4'4 pentahydroxybenzo Phenolic compounds such as phenone and 2,5-bis (2-hydroxy-5-methylbenzyl) methyl, ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene And aliphatic alcohols such as glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol or ethyl lactate and butyl lactate.

Moreover, as a compound containing the amino group made to react with a 1, 2- quinonediazide (sulfonic acid) compound, for example, aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4 Anilines or aminos such as -aminobiphenyl, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenylether Cyclohexane etc. are mentioned.

Moreover, as a compound containing both the hydroxyl group and amino group made to react with a 1, 2- quinonediazide (sulfonic acid) compound, for example, o-aminophenol, m-aminophenol, p-aminophenol, 4-amino Resorcinol, 2,3-diaminophenol, 2,4-diaminophenol, 4,4'-diamino-4 ''-hydroxytriphenylmethane, 4-amino-4 ', 4''-di Hydroxytriphenylmethane, bis (4-amino-3-carboxy-5-hydroxyphenyl) ether, bis (4-amino-3-carboxy-5-hydroxyphenyl) methane, 2,2-bis (4- Aminophenols such as amino-3-carboxy-5-hydroxyphenyl) propane and 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) hexafluoropropane or 2-aminoethanol, 3- Alkanolamines, such as an amino propanol and 4-amino cyclohexanol, etc. are mentioned.

In the positive photosensitive resin composition of this invention, content of (B) component becomes like this. Preferably it is 5-100 mass parts, More preferably, it is 8-50 mass parts, More preferably, with respect to 100 mass parts of (A) component. 10-40 mass parts. When it is less than 5 mass parts, the dissolution rate difference with respect to the developing solution of the exposure part and unexposed part of positive type photosensitive resin composition may become small, and patterning by image development may become difficult. Moreover, when it exceeds 100 mass parts, since a 1, 2- quinonediazide compound will not fully decompose | disassemble by short time exposure, a sensitivity may fall, and (B) component may absorb light and may reduce transparency of a cured film. have.

&Lt; Component (C) >

(C) component is a silsesquioxane, and specifically is a polysiloxane represented by _{[(RSiO 3/2) n} ] ( wherein, R represents a monovalent organic group.). Although the structure of (C) component may be any of a random structure, a ladder structure, a fully cage structure, an incomplete cage structure, etc., it is not specifically limited. In addition, the silsesquioxane which consists of single or 2 types or more combination can be used for (C) component.

Silsesquioxane is normally manufactured by the sol-gel method which hydrolyzes a trialkoxysilane. By changing the kind of trialkoxysilane used as a raw material, the silsesquioxane from which a property differs is obtained. Specific examples of trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane. , 3- (2-aminoethyl) trimethoxysilane, 3-ureidepropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxy Silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, trifluoropropyltrimethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxy Silane, n-hexyltriethoxysilane, and the like. These trialkoxysilanes may be used independently and may use 2 or more types together. Among them, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimeth Silsesquioxane obtained using at least one trialkoxysilane selected from the group consisting of oxysilane and 3-acryloxypropyltrimethoxysilane is preferable from the point of reacting with (A) component at the time of thermosetting. .

Content of (C) component in the positive photosensitive resin composition of this invention becomes like this. Preferably it is 5-100 mass parts, More preferably, it is 10-80 mass parts, More preferably, with respect to 100 mass parts of (A) component. It is 15-60 mass parts. When it is less than 5 mass parts, the hardness of the cured film formed using positive type photosensitive resin composition may become low, and when it becomes larger than 100 mass parts, tack may generate | occur | produce in the coating film after prebaking.

<(D) solvent>

(D) A solvent melt | dissolves the said (A) component, (B) component, and (C) component, and also melt | dissolves the below-mentioned (E) component-(I) component, other components, etc. which are added as needed. As long as it is a solvent which has the solubility to make, the kind, structure, etc. are not specifically limited.

As a preferable (D) solvent in the positive photosensitive resin composition of this invention, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol mono Methyl 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, 2-hydroxypropionate ethyl, 2-hydroxy-2-methylpropionic acid To ethyl, ethyl ethoxy acetate, ethyl hydroxy acetate, methyl 2-hydroxy-3-methyl butyrate, methyl 3-methoxypropionate, and 3-methoxypropionic acid Methyl, 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone, etc. are mentioned.

These solvents may be used alone or in combination of two or more thereof. As the solvent (D), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate and butyl lactate have good coating properties and safety. This is preferable from the viewpoint of high. These are generally used as a solvent for photoresist materials.

<(E) component-[I] component>

As described above, the positive photosensitive resin composition of the present invention is constituted by dissolving the (A) component, the (B) component and the (C) component in the (D) solvent. It is also possible to contain each component of (I)-(I).

<(E) component>

The component (E) is a thermal acid generator, which is not particularly limited as long as it is a compound that thermally decomposes during postbaking to generate an acid, specifically, a compound that thermally decomposes at 150 ° C to 250 ° C to generate an acid. Such compounds include, for example, bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyltosylate, o-nitrobenzyltosylate, 1,2,3- Phenylene tris (methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morpholinium salt, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid Butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p -Tosylate, N-ethyl-4-toluenesulfonamide, diphenyl iodonium chloride, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium mesylate, diphenyl iodonium tosylate, diphenyl iodonium bromide , Diphenyl iodonium tetra Fluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroacenate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) Iodonium mesylate, bis (p-tert-butylphenyl) iodonium tosylate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium tetrafluor Roborate, Bis (p-tert-butylphenyl) iodium chloride, Bis (p-chlorophenyl) iodium chloride, Bis (p-chlorophenyl) iodium tetrafluoroborate, Triphenylsulfonium chloride, Triphenylsul Ponium bromide, tri (p-methoxyphenyl) sulfoniumtetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphonate, tri (p-ethoxyphenyl) sulfoniumtetrafluoroborate, Triphenylphosphonium chloride, tripe Phosphonium bromide, triphenylsulfonium trifluoromethanesulfonate, tri (p-methoxyphenyl) phosphoniumtetrafluoroborate, tri (p-methoxyphenyl) phosphonium hexafluorophosphonate and tri (p -Ethoxyphenyl) phosphonium tetrafluoroborate, etc. are mentioned.

Moreover, the compound shown by following formula (3)-formula (70) is mentioned as a thermal acid generator of (E) component.

[Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

[Formula 7]

[Formula 8]

[Chemical Formula 9]

[Formula 10]

[Formula 11]

[Chemical Formula 12]

The thermal acid generator of a triphenyl sulfonium salt system is preferable at the point which is high in transparency among the said thermal acid generators.

In the positive photosensitive resin composition of this invention, content of (E) component becomes like this. Preferably it is 0.1-30 mass parts, More preferably, it is 0.5-20 mass parts, More preferably, with respect to 100 mass parts of (A) component. It is 1-10 mass parts. When it is less than 0.1 mass part, the thermosetting speed may be slow and pencil hardness may fall. Moreover, when it exceeds 30 mass parts, some hardening may begin at the time of prebaking, a residual film may arise in an exposure part, or the storage stability of a solution may fall.

<(F) component>

The component (F) is a compound having two or more vinyl groups directly bonded to a benzene ring, wherein the compound may be a compound having two or more vinyl groups in the same benzene ring, or includes two or more benzene rings. In the case of the compound to be mentioned, one of the compounds in which the sum total of the vinyl groups couple | bonded with the different benzene rings may be 2 or more. By adding the compound of (F) component to the positive photosensitive resin composition of this invention, thermosetting with (A) component can improve and hardness can be improved.

Specific examples of the compound having two or more vinyl groups directly bonded to the benzene ring include o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, 4,4'-divinylbiphenyl, and Tris- (4 -Vinylphenyl) methane and 4,4'-oxybis (vinylbenzene). As (F) component, the compound which has 2 or more of vinyl groups directly bonded to the benzene ring can be used individually or in combination of 2 or more types.

In the positive photosensitive resin composition of this invention, content of (F) component becomes like this. Preferably it is 1-40 mass parts, More preferably, it is 3-30 mass parts, More preferably, with respect to 100 mass parts of (A) component. It is 5-20 mass parts. When it is less than 1 mass part, pencil hardness may fall. Moreover, when it exceeds 40 mass parts, a tack may generate | occur | produce in the coating film after prebaking.

<(G) component>

(G) A component is an acrylic polymer which has an epoxy group in a side chain. By adding the acrylic polymer which has an epoxy group in a side chain in the photosensitive resin composition of this invention, the film reduction of an unexposed part can be suppressed at the time of image development. In addition, the mixture of the acrylic copolymer which has a some kind of epoxy group in a side chain can be used for the acrylic copolymer of (G) component.

The acrylic polymer as (G) component is the same as (A) component using epoxy-group containing monomers, such as glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and epoxy cyclohexylmethyl methacrylate. It can be obtained by a polymerization method. Its number average molecular weight is 2,000-25,000.

The acrylic polymer as (G) component can be obtained using the monomer which has an epoxy group individually or in multiple types, and can also use together the monomer copolymerizable with the monomer which has these epoxy groups. The copolymerizable monomer is not particularly limited as long as it does not react with the epoxy group during the polymerization. However, the monomer capable of copolymerizing preferably has no carboxyl group or amino group. When copolymerizing with the copolymerizable monomer, it is preferable that the ratio of the monomer which has an epoxy group is 20 mol% or more. As such a copolymerizable monomer, an acrylic acid ester compound, a methacrylic acid ester compound, a maleimide compound, an acrylonitrile, a maleic anhydride, a styrene compound, a vinyl compound, etc. are mentioned, for example. Hereinafter, although the specific example of the said monomer is given, it is not limited to these.

As an acrylate ester compound, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2, for example , 2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxy ethyl acrylate, methoxy triethylene glycol acrylate, 2- ethoxy ethyl acrylate, Tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, γ-butyrolactone acrylate, 8-methyl -8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2,3-dihydroxyprop Fill acrylate, diethylene glycol monoacrylate, 4-hydroxybutyl acrylate, caprolactone 2- (acryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate and 5-acryloyloxy-6 -Hydroxy norbornene-2-carboxylic-6-lactone, etc. are mentioned.

As a methacrylic acid ester compound, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, for example. Latex, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, meth Methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 3-methacryloyloxypropyltrimethoxysilane, 2-methyl -2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8 Tricyclodecylmethac Latex, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monomethacrylate, capro Lactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether methacrylate and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone Can be mentioned.

As a vinyl compound, methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether, etc. are mentioned, for example. have.

As a styrene compound, styrene, methyl styrene, chloro styrene, bromostyrene, etc. are mentioned, for example.

As a maleimide compound, maleimide, N-methyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, etc. are mentioned, for example.

The method of obtaining the acrylic polymer which has an epoxy group of the said (G) component is not specifically limited. For example, it is obtained by making it polymerize-react at 50-110 degreeC in the monomer which has an epoxy group, the monomer which can be copolymerized as needed, and the polymerization initiator etc. coexist as needed. The solvent used at this time will not be specifically limited if it melt | dissolves the monomer and polymerization initiator which participate in reaction. As a specific example, the solvent described in the above-mentioned (D) solvent is mentioned. The acrylic polymer which has an epoxy group obtained by such a method is the solution state melt | dissolved in the solvent normally.

The solution of the acrylic copolymer of the (G) component obtained by the above-mentioned method is thrown in again under stirring, such as diethyl ether or water, and reprecipitated, and the produced precipitate is filtered and washed, and it is normal temperature or pressure_reduction | reduced_pressure. By heating and drying, it can be set as the powder of the acrylic copolymer of (G) component. Through such operation, the polymerization initiator and unreacted monomer which coexist with the acrylic copolymer of (G) component can be removed, As a result, the powder of the acrylic copolymer of refined (G) component is obtained. What is necessary is just to dissolve again the obtained powder to a solvent and just to perform repeatedly said operation, when it cannot fully refine | purify by operation once. In this invention, the powder of the acrylic copolymer of the said (G) component may be used as it is, or the powder of the acrylic copolymer of the (G) component may be redissolved in the (D) solvent, and may be used in a solution state.

In the positive photosensitive resin composition of this invention, content of (G) component becomes like this. Preferably it is 0.5-40 mass parts, More preferably, it is 1-30 mass parts, More preferably, with respect to 100 mass parts of (A) component. It is 3-20 mass parts. When it is less than 0.5 mass part, the unexposed part may film | membrane decrease at the time of image development. Moreover, when it exceeds 40 mass parts, the image development of an exposure part may become bad or a sensitivity may fall large.

<(H) component>

(H) A component is an adhesion promoter. By using an adhesion promoter, the adhesiveness of the cured film of positive type photosensitive resin composition and the board | substrate after image development can be improved.

Specific examples of the adhesion promoter include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, and vinyltrichlorosilane; Trimethylmethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrie Alkoxysilanes such as oxysilane, γ-glycidoxypropyltriethoxysilane, γ- (N-piperidinyl) propyltriethoxysilane, and γ-ureidepropyltriethoxysilane; Silazanes such as hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine and trimethylsilylimidazole; Benzotriazoles, benzimidazoles, indazoles, imidazoles, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, urazoles, thiuracils, mercaptoimidazoles and Heterocyclic compounds such as mercaptopyrimidine; And urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea. One type or two types or more of these can be combined and used as a (H) component.

As the adhesion promoter, commercially available compounds can be used, and these are, for example, Shin-Etsu Chemical Co., Ltd., Momentive, or Dow Corning Toray Co., Ltd. It can be obtained easily from the back. For example, it is also called a silane coupling agent and can also obtain and use a commercially available thing. As a specific example of such a product, Z-6011, 6020, 6023, 6026, 6050, 6094, 6610, 6883, 6675, 6676, 6040, 6041, 6042, 6043, 6044 by Dow Corning Toray Silicone Co., Ltd. , 6920, 6940, 6075, 6172, 6300, 6519, 6550, 6825, 6030, 6033, 6530, 6062, 6911 or 6860, Shin-Etsu Silicone, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE- 9103, KBM-573, KBM-575, KBM-6123 or KBE-585, Momentive A-151, A-171, A-172, A-2171, Y-9936, A-174, A-186, A- 187, A-1871, A-189, A-1891, A-1100, A-1110, A-1120, A-2120, Y-9669 or A-1160.

In the positive photosensitive resin composition of this embodiment, the addition amount of (H) component is 20 mass parts or less with respect to 100 mass parts of (A) component, Preferably it is 0.01-10 mass parts, More preferably, it is 0.5-10 mass It is wealth. When 20 mass parts or more are used, the heat resistance of a coating film may fall, and when it is less than 0.1 mass part, sufficient effect of an adhesion promoter may not be acquired.

<(I) component>

(I) A component is surfactant. By using surfactant, the applicability | paintability of a positive photosensitive resin composition can be improved. (I) A component can be used individually or in combination of 2 or more types.

Surfactant which is (I) component of this embodiment will not be restrict | limited especially if it is a range which does not impair the effect of this invention. For example, a fluorine-type surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned. Surfactants of this kind are, for example, Sumitomo 3M Ltd., DIC Corporation or Asahi Glass Co., Ltd. It can be obtained easily from the back. As specific examples thereof, EFTOP EF301, EF303, EF352 (above, manufactured by Tohkem Products Corp. (currently, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFAC R30, R08, R90, BL20, R61, F171, F173, F471, F475, F479, F474, F477, F480, F482, F483, F484 (more than DIC corporation), FLUORAD FC430, FC431 (more than Sumitomo 3M Ltd.), ASAHI GUARD AG710, SURFLON S-382, SC101, And fluorine-based surfactants such as SC102, SC103, SC104, SC105, and SC106 (above, manufactured by Asahi Glass Co., Ltd.).

When surfactant is used as (I) component of the positive photosensitive resin composition of this embodiment, the content is 1.0 mass part or less normally in 100 mass parts of positive photosensitive resin compositions, Preferably it is 0.5 mass part. It is as follows. When the usage-amount of surfactant which is (I) component is set to the quantity exceeding 1.0 mass part, the improvement effect of applicability anticipated corresponding to increase of content will not be acquired. That is, it becomes an inefficient use method.

<Other ingredients>

Positive type photosensitive resin composition of this invention can contain (E) component-(I) component as mentioned above, However, if it does not impair the effect of this invention further, it contains other components as needed. It is also possible. As other components, additives, such as a rheology modifier, a pigment, dye, a storage stabilizer, an antifoamer, or a dissolution promoter, such as a polyhydric phenol and a polycarboxylic acid, are mentioned.

<Positive Photosensitive Resin Composition>

Positive type photosensitive resin composition of this invention,

(A) an alkali-soluble acrylic polymer which has a side chain which has a unsaturated bond at the terminal as a component,

(B) a quinone diazide compound as a component,

As the (C) component silsesquioxane,

(D) It is melt | dissolved in a solvent, and is comprised.

This positive photosensitive resin composition is further, if necessary, respectively,

Thermal acid generator as (E) component,

A compound having two or more vinyl groups directly bonded to a benzene ring as a component (F),

Acrylic polymer which has an epoxy group in a side chain as (G) component,

(H) adhesion promoter,

Surfactant as (I) component

And one or more of the above-described additives as other components.

Preferable examples of the positive photosensitive resin composition of the present invention are as follows.

[1] Positive type photosensitive resin composition containing 5-100 mass parts (B) component and 5-100 mass parts (C) component based on 100 mass parts of (A) component, and these melt | dissolved in the (D) solvent. .

[2] In the composition of [1], the positive photosensitive resin composition further contains 0.1 to 30 parts by mass based on 100 parts by mass of the component (E).

[3] The positive photosensitive resin composition, wherein the composition of [1] or [2] further contains 1 to 40 parts by mass based on 100 parts by mass of the component (F).

[4] The positive photosensitive resin composition, wherein the composition of [1], [2] or [3] further contains 0.5 to 40 parts by mass based on 100 parts by mass of the component (G).

[5] In the composition of the above [1], [2], [3] or [4], the composition further contains (H) component in an amount of 20 parts by mass or less based on 100 parts by mass of the component (A). Type photosensitive resin composition.

[6] In the composition of the above [1], [2], [3], [4] or [5], the amount of (I) component is 1.0 parts by mass or less with respect to 100 parts by mass of the positive photosensitive resin composition. Positive photosensitive resin composition to contain.

The ratio of solid content in the positive photosensitive resin composition of this invention is not specifically limited as long as each component is melt | dissolving uniformly in a solvent. For example, it is 1-80 mass%, For example, it is 5-60 mass%, or 10-50 mass%. Here, solid content means what remove | excluding the (D) solvent from the whole component of positive type photosensitive resin composition.

The preparation method of the positive photosensitive resin composition of this invention is not specifically limited. As an example, (A) component (acrylic polymer) is melt | dissolved in the (D) solvent and (B) component (quinonediazide compound) and (C) component (silsesquioxane) are melt | dissolved in this solution in a predetermined ratio. The method of mixing and setting it as a uniform solution is mentioned. In addition, in the appropriate step of this preparation method, (E) component (thermal acid generator), (F) component (compound having two or more vinyl groups directly bonded to the benzene ring), and (G) component (epoxy group are The preparation method which adds and mixes the acrylic polymer which has in a side chain), (H) component (adhesion promoter), (I) component (surfactant), and another component further is mentioned.

In preparing the positive photosensitive resin composition of the present invention, the solution of the specific copolymer obtained by the polymerization reaction in the solvent (D) can be used as it is, in which case, as described above for the solution of this component (A) When (B) component, (C) component, etc. are put and it is set as a uniform solution, (D) solvent can also be further added for the purpose of concentration adjustment. At this time, the (D) solvent used for the formation process of a specific copolymer and the (D) solvent used for density | concentration adjustment at the time of preparation of a positive photosensitive resin composition may be the same, and may differ.

Thus, it is preferable to use the positive photosensitive resin composition of the prepared solution state after filtering using the filter etc. which have a pore diameter of about 0.2 micrometer.

<Film and Cured Film>

Next, the method of forming a coating film using the positive photosensitive resin composition of this invention, after that, light irradiation and thermosetting, and obtaining a cured film is demonstrated.

First, a semiconductor substrate such as a silicon substrate or a silicon nitride substrate is prepared. In addition, a glass substrate, a quartz substrate, etc. can also be used instead of a semiconductor substrate. Further, a silicon dioxide film, an indium tin oxide (ITO) film, or a metal film such as aluminum, molybdenum or chromium may be formed on the substrate.

On the prepared semiconductor substrate, the positive photosensitive resin composition of this invention is apply | coated by spin coating, flow coating, roll coating, slit coating, spin coating following ink, or inkjet coating. Subsequently, the coating film can be formed by preliminary drying in a hot plate or an oven. Then, heat treatment is performed on the coating film. As heat processing conditions, the heating temperature and heating time suitably selected within the range of the temperature of 70 degreeC thru | or 160 degreeC and time 0.3 to 60 minutes are employ | adopted, for example. Heating temperature and a heat time become like this. Preferably they are 80 degreeC-140 degreeC, and 0.5 to 10 minutes, respectively.

The film obtained above is irradiated with light, such as an ultraviolet-ray, through the mask which has a predetermined pattern. Subsequently, by developing with alkaline developing solution, an exposed part is washed and a relief pattern with a sharp cross section is obtained.

Examples of the alkaline developer include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and ethanolamine, propylamine and ethylene. Amine aqueous solution, such as diamine, etc. are mentioned. Surfactant etc. may be added to these developing solutions.

In said alkaline developing solution, the 0.1-2.38 mass% aqueous solution of tetraethylammonium hydroxide is generally used as a developing solution of a photoresist. Also in the case of the film | membrane obtained from the positive photosensitive resin composition of this invention, a favorable image development process can be performed using this alkaline developing solution, without causing a problem, such as swelling.

As the developing method, any of a puddle (liquid) method, a dipping method, a rocking dipping method, and the like can be used. The developing time is usually 15 to 180 seconds.

On the film | membrane which completed the image development process, washing | cleaning is performed with running water, for example for 20 to 90 second. Subsequently, moisture on the substrate is removed by using air or compressed nitrogen or air drying by spinning to obtain a patterned film.

The patterned film is post-baked for thermosetting. Specifically, it heats using a hotplate or oven. As a post-baking, generally, the method of processing for 5 to 30 minutes on a hotplate and 30 to 90 minutes in an oven is employ | adopted at the heating temperature selected in the range of temperature 140 degreeC-250 degreeC.

By post-baking, the cured film which has a favorable relief pattern excellent in heat resistance, transparency, planarization property, low water absorption, chemical-resistance, etc. is obtained. This cured film has high hardness, is excellent in heat resistance and solvent resistance, and has high transparency. Thereby, it can use suitably for various films, such as an interlayer insulation film, a protective film, an insulation film, etc. in a liquid crystal display or an organic electroluminescent display. Moreover, it is used suitably also for the use of the array planarization film | membrane of a TFT type liquid crystal element. And this invention also makes the display apparatus which has the said cured film object.

(Example)

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

[Simple Symbol Used in Example]

The meanings of the brief symbols used in the following examples are as follows.

AA: Acrylic acid

MAA: methacrylic acid

MMA: methyl methacrylate

GMA: glycidyl methacrylate

DCPM: Dicyclopentanyl methacrylate

THPA: 1,2,3,6-tetrahydrophthalic anhydride

PA: phthalic anhydride

ACSQ: acryloyl group modified silsesquioxane

MACSQ: methacryloyl group modified silsesquioxane

DVB: divinylbenzene (isomer mixture)

AIBN: azobisisobutyronitrile

BTEAC: benzyltriethylammonium chloride

TAG1: triphenylsulfonium trifluoromethanesulfonate

TAG2: diphenyl iodonium trifluoromethanesulfonate

TAG3: 2-methyl-α- [5-[(propylsulfonyl) oxy] imino]-(5H) -2-thienylidene] benzeneacetonitrile (compound represented by formula (6) above)

PGMEA: Propylene glycol monomethyl ether acetate

NMP: n-methyl-2-pyrrolidone

QD: condensation of 1 mol of α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene with 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonylchloride Compound synthesized by reaction

MPTS: 3-methacryloyloxypropyltrimethoxysilane

UPS: γ-Auraidpropyltriethoxysilane

R30: MEGAFAC R-30 (brand name) made in DIC Corporation

[Measurement of number average molecular weight and weight average molecular weight]

The number average molecular weight and the weight average molecular weight of the specific copolymer and the specific crosslinked product obtained according to the following synthesis examples were obtained by using the GPC apparatus (Shodex® Columns KF803L and KF804L) manufactured by JASCO Corporation, to elute the solvent tetrahydrofuran. It measured on the conditions which flowed into the column (column temperature 40 degreeC), and eluted at a flow volume of 1 ml / min. In addition, the following number average molecular weight (henceforth Mn) and a weight average molecular weight (henceforth Mw) were shown by polystyrene conversion value.

&Lt; Synthesis Example 1 &

As the monomer component constituting the copolymer, GMA (40.0 g) and DCPM (40.0 g) were used, and AIBN (2 g) was used as the radical polymerization initiator, and these were polymerized in solvent PGMEA (120 g). The copolymer solution (copolymer concentration: 40 mass%) which is Mw 10,600 was obtained (P1). In addition, polymerization temperature was adjusted to the temperature of 60 degreeC-100 degreeC.

&Lt; Synthesis Example 2 &

A solution of (A) component (specific copolymer) which is Mn 7,300 or Mw 13,600 by adding and reacting AA (20.0 g), BTEAC (1.1 g) and PGMEA (31.7 g) to 200 g of the copolymer (P1) ( Specific copolymer concentration: 40 mass%) was obtained (P2). In addition, reaction temperature was adjusted to 90-120 degreeC.

&Lt; Synthesis Example 3 &

A solution (specific copolymer concentration) of (A) component (specific copolymer) which is Mn 7,900 and Mw 13,600 by adding THPA (42.8 g) and PGMEA (107 g) to 252.8 g of the specific copolymer solution (P2) for reaction. : 40 mass%) was obtained (P3). In addition, reaction temperature was adjusted to 80-100 degreeC.

&Lt; Synthesis Example 4 &

As the monomer component constituting the copolymer, GMA (20.0 g) and MMA (20.0 g) were used, and AIBN (1 g) was used as the radical polymerization initiator, and these were polymerized in solvent PGMEA (95.7 g), thereby obtaining Mn 4,300. And Mw 8,400 (copolymer concentration: 30 mass%) were obtained (P4). In addition, polymerization temperature was adjusted to 60 to 100 degreeC.

&Lt; Synthesis Example 5 &

A solution (specific copolymer concentration) of (A) component (specific copolymer) of Mn 7,800 and Mw 13,900 by adding and reacting 252.8 g of the specific copolymer solution (P2) with PA (43.9 g) and PGMEA (110 g). : 40 mass%) was obtained (P5). In addition, reaction temperature was adjusted to 80-100 degreeC.

&Lt; Synthesis Example 6 &

As a monomer component constituting the copolymer, MAA (40.0 g) and DCPM (40.0 g) were used, and AIBN (2 g) was used as a radical polymerization initiator, and these were polymerized in a solvent PGMEA (120 g), whereby Mn 5,100, The copolymer solution (copolymer concentration: 40 mass%) which is Mw 9,800 was obtained (P6). In addition, polymerization temperature was adjusted to 60 to 100 degreeC.

&Lt; Synthesis Example 7 &

A solution of (A) component (specific copolymer) which is Mn 6,500, Mw 12,900 by adding and reacting 200 g of the copolymer (P6) with GMA (33.0 g), BTEAC (1.1 g) and PGMEA (49.5 g) ( Specific copolymer concentration: 40 mass%) was obtained (P7). In addition, reaction temperature was adjusted to 90-120 degreeC.

&Lt; Synthesis Example 8 &

As the monomer component constituting the copolymer, GMA (20.0 g) and MPTS (20.0 g) were used, and AIBN (1 g) was used as the radical polymerization initiator, and these were polymerized in solvent PGMEA (120 g) to give Mn 3,700, The copolymer solution (copolymer concentration: 30 mass%) which is Mw 7,300 was obtained (P8). In addition, polymerization temperature was adjusted to 60 to 100 degreeC.

<Examples 1 to 7 and Comparative Examples 1 to 3>

According to the composition shown in following Table 1, (B) component and (C) component, the (D) solvent, and (E)-(I) component are mixed by the predetermined ratio in the solution of (A) component, The positive photosensitive resin composition of each Example and each comparative example was prepared by stirring at room temperature for 3 hours and making it a uniform solution.

For each of the positive photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3, the sensitivity of the coating film, the film reduction (in the unexposed part), the presence or absence of a tack after prebaking, and the cured film Pencil hardness, transmittance, adhesion with ITO, and solvent resistance were measured, and these were evaluated.

[Sensitivity evaluation]

Each of the positive photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was applied onto a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness. A coating film having a thickness of 2.5 μm was formed. The film thickness was measured using Filmetrics, Inc. F20, including various evaluation tests described below.

This coating film was irradiated with the ultraviolet-ray whose light intensity in 365 nm is 5.5 mW / cm <2> for a fixed time using the ultraviolet-ray irradiation apparatus PLA-600FA by Canon Inc .. Thereafter, the development was performed by immersing in a 0.4% by mass aqueous tetramethylammonium hydroxide (hereinafter referred to as TMAH) solution for 60 seconds, followed by washing with running water for 20 seconds with ultrapure water. The minimum exposure amount (mJ / cm <2>) which a residue disappears in an exposure part was made into the sensitivity.

[Membrane reduction evaluation]

Each of the positive photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was applied onto a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness. A coating film having a thickness of 2.5 μm was formed.

This membrane was immersed in 0.4 mass% TMAH aqueous solution for 60 seconds, and the water wash | cleaned with ultrapure water for 20 second. Subsequently, by measuring the thickness of this film, the film reduction degree of the unexposed part due to development was evaluated. The film thickness in this evaluation was measured using Filmetrics, Inc. F20.

[Tax presence evaluation]

Each of the positive photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was applied onto a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness. A coating film having a thickness of 2.5 μm was formed.

When tweezers was made to contact the surface of this coating film, it was set as (circle) that the tweezers trace did not remain and that the trace remained.

[Pencil hardness evaluation]

Each of the positive photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was applied onto a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness. A coating film having a thickness of 2.5 μm was formed. Post-baking was performed by heating this coating film at 230 degreeC for 30 minutes, and the cured film with a film thickness of 2.2 micrometers was formed.

The hardness of the pencil used when no scratches were formed on the surface of this coating film at a load of 500 g was defined as the pencil hardness.

[Transmittance Evaluation]

Each of the positive photosensitive compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was applied onto a quartz substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to give a film thickness of 2.5. A coating film having a thickness was formed.

This coating film was irradiated with the ultraviolet-ray whose light intensity in 5.5 nm was 5.5 mW / cm <2> for 90 second using Canon Inc. ultraviolet irradiation device PLA-600FA. This film was post-baked on a hot plate at a temperature of 230 ° C. for 30 minutes to form a cured film.

The transmittance | permeability of the wavelength of 400 nm was measured for this cured film using the ultraviolet-visible spectrophotometer (Shimadzu Corporation make, SIMADZU UV-2550 model number).

[Evaluation of adhesion with ITO]

Each of the positive photosensitive compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was applied onto an ITO substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to give a film thickness of 2.5. A coating film having a thickness was formed. This film was post-baked on a hot plate at a temperature of 230 ° C. for 30 minutes to form a cured film.

The cured film was cut with a cutter knife so as to be 10 × 10 squares at 1 mm intervals. The cellophane tape peeling test was done on this sheath using a scotch tape. The thing which peeled off even if it was one or 100 space | pieces was made into 100 what remained without peeling all 100 cells.

[Solvent Resistance Evaluation]

Each of the positive photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was applied onto a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness. A coating film having a thickness of 2.5 μm was formed. Post-baking was performed by heating this coating film at 230 degreeC for 30 minutes, and the cured film with a film thickness of 2.1 micrometers was formed.

This coating film was immersed in NMP for 1 minute at room temperature, and it was set that (circle) and that the decrease in film thickness were observed that there is no change in the film thickness before and behind immersion.

[Pattern Formability Evaluation]

Each of the positive photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was applied onto a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 2.5. A coating film having a thickness was formed.

Using this Canon film UV irradiation apparatus PLA-600FA, UV light having a light intensity of 5.5 mW / cm 2 at 365 nm was changed to 200 mJ / cm 2 through a 20 µm line and space pattern mask. Respectively. Subsequently, after developing by immersing in 0.4 mass% of tetramethylammonium hydroxide aqueous solution for 60 second, and developing, a pattern was formed by performing 20-second washing with ultrapure water.

The produced pattern was baked in 230 degreeC oven for 30 minutes. The thing in which the line pattern of 20 micrometers +/- 2 micrometers was formed (circle) and a pattern was not obtained, or the line width differed significantly was made into x.

[Evaluation results]

Table 2 shows the results of the above evaluation.

As can be seen from the results shown in Table 2, all of the positive photosensitive resin compositions of Examples 1 to 7 were highly sensitive, and there was very little film reduction in the unexposed areas, and no tack after prebaking was observed. . Moreover, the pencil hardness after hardening was 2H or more, and it was high hardness, was excellent also in light transmittance, adhesiveness with ITO, solvent resistance, and the pattern formation property was also obtained.

On the other hand, with respect to Comparative Example 1, good results were obtained with sensitivity, transmittance, adhesion, and solvent resistance, but the pencil hardness was low at B. In Comparative Example 2, subsequent evaluation was not achieved due to the tack after the prebaking. Moreover, although the result of favorable sensitivity, a transmittance | permeability, and adhesiveness with respect to the comparative example 3 was obtained, the pencil hardness was low as H, and the result that the solvent tolerance was lacking came out.

(Industrial applicability)

The positive type photosensitive resin composition which concerns on this invention is suitable as a material which forms a protective film, a planarization film, an insulating film, etc. in the display apparatus provided with a thin film transistor (TFT) type liquid crystal display element or organic electroluminescent element, Especially, a touch It is suitable for a display device provided with a panel or a display device using a resin substrate. For example, it is not only suitable as a material for forming an interlayer insulating film of a TFT type liquid crystal element, a protective film of a color filter, an array planarizing film, an interlayer insulating film of a capacitive touch panel, an insulating film of an organic EL element, but also a micro lens material. It is also suitable as various electronic materials.

Claims (11)

An alkali-soluble acrylic polymer having a side chain having an unsaturated bond at the terminal,
A quinonediazide compound,
Silsesquioxane,
A solvent is contained, The photosensitive resin composition characterized by the above-mentioned.
The method of claim 1,
The alkali-soluble acrylic polymer has a number average molecular weight of 2,000 to 50,000 in terms of polystyrene, The photosensitive resin composition.
3. The method according to claim 1 or 2,
The said alkali-soluble acrylic polymer is a photosensitive resin composition characterized by the terminal of a side chain being acryloyl group, methacryloyl group, vinylphenyl group, or isopropenyl phenyl group.
4. The method according to any one of claims 1 to 3,
The said quinone diazide compound is contained in the quantity used as 5-100 mass parts with respect to 100 mass parts of said alkali-soluble acrylic polymers, The photosensitive resin composition characterized by the above-mentioned.
5. The method according to any one of claims 1 to 4,
The said silsesquioxane is contained in the quantity used as 5-100 mass parts with respect to 100 mass parts of said alkali-soluble acrylic polymers, The photosensitive resin composition characterized by the above-mentioned.
The method according to any one of claims 1 to 5,
The photosensitive resin composition which contains a thermal-acid generator in the amount which becomes 0.1-30 mass parts further with respect to 100 mass parts of said alkali-soluble acrylic polymers.
7. The method according to any one of claims 1 to 6,
The photosensitive resin composition which contains the compound which has 2 or more vinyl groups directly couple | bonded with the benzene ring in the quantity used as 1-40 mass parts with respect to 100 mass parts of said alkali-soluble acrylic polymers further.
8. The method according to any one of claims 1 to 7,
The photosensitive resin composition which contains the acrylic polymer which has an epoxy group in a side chain further with respect to 100 mass parts of said alkali-soluble acrylic polymers in the quantity used as 0.5-40 mass parts.
The method according to any one of claims 1 to 8,
A photosensitive resin composition, further comprising an adhesion promoter in an amount of 20 parts by mass or less, based on 100 parts by mass of the alkali-soluble acrylic polymer.
10. The method according to any one of claims 1 to 9,
Furthermore, surfactant is contained in the quantity of 1.0 mass part or less with respect to 100 mass parts of said photosensitive resin compositions, The photosensitive resin composition characterized by the above-mentioned.
The display apparatus which has a film | membrane which hardens the photosensitive resin composition of any one of Claims 1-10.