KR101749844B1 - Copolymer and photosensitive resin composition and resin film containing said copolymer - Google Patents

Abstract

The copolymer of the present invention contains repeating units derived from hydroxyphenyl (meth) acrylate and repeating units derived from blocked isocyanate group-containing unsaturated compounds. It is preferable that the repeating unit derived from hydroxyphenyl (meth) acrylate is contained in an amount of 30 mol% to 90 mol%, and the blocked repeating unit derived from an isocyanate group-containing unsaturated compound is contained in an amount of 10 mol% to 70 mol%. The photosensitive resin composition containing the copolymer of the present invention is excellent in transparency, heat discoloration resistance and electrical characteristics, and is excellent in coatability, developability, curability and storage stability.

Description

TECHNICAL FIELD [0001] The present invention relates to a copolymer, a photosensitive resin composition containing the copolymer,

The present invention relates to a photosensitive resin composition, more particularly, a protective film for electronic components such as a liquid crystal display element, an integrated circuit element, and a solid-state imaging element, a method for forming a planarizing film or an interlayer insulating film, formation of a microlens or a microlens array, A diffuse reflection film, a projection or a spacer for orientation control, formation of a color filter, or formation of an optical waveguide.

Conventionally, the formation of a protective film for preventing deterioration or damage of an electronic part such as a TFT type liquid crystal display element, a magnetic head element, an integrated circuit element, or a solid-state image pickup element, or an interlayer insulating film for insulating between wirings arranged in layers A photosensitive resin composition has been used. In particular, in the case of a liquid crystal display element, since a transparent conductive circuit layer such as ITO is formed on an interlayer insulating film and a liquid crystal alignment film is further formed on the transparent conductive circuit layer, the interlayer insulating film is formed in a step of forming a transparent electrode film They are exposed to a high temperature condition or exposed to a stripping solution of a resist used for forming an electrode pattern, and therefore sufficient resistance to these is required. Accordingly, the photosensitive resin composition for forming the interlayer insulating film is required to be capable of forming a resin film excellent in developability and excellent in transparency, heat resistance, flatness, adhesion, chemical resistance and electrical characteristics.

On the other hand, as an optical system material of an imaging optical system or an optical fiber connector of an on-chip color filter such as a facsimile, an electronic copying machine, or a solid-state image pickup element, a microlens having a lens diameter of about 3 to 100 m, A lens array is used. Among them, CCD devices used in digital cameras and the like are progressing finer with the recent increase in the number of pixels, and the light receiving area per CCD device is reduced. Therefore, as means for increasing the amount of received light, it has been attempted to form a microlens on the convex lens on the CCD element. As a microlens used in a CCD device, there is a method of exposing and developing a photoresist film to form an irregular pattern, heating the irregular pattern at a temperature equal to or higher than the glass transition point, and forming a hemispherical microlens by surface tension It is known. Therefore, a photosensitive resin composition for forming a microlens is required to have high developability, transparency, melt flow and heat resistance, and a high refractive index from the viewpoint of light condensation.

As the photosensitive resin composition, for example, Patent Document 1 discloses a composition comprising (a) a copolymer of an unsaturated carboxylic acid and an epoxy group-containing polymerizable unsaturated compound, (b) a copolymer of an unsaturated carboxylic acid and other monoolefin- , (c) a quinone diazide group-containing compound, and (d) an organic solvent. Patent Document 2 discloses a composition comprising (a) a copolymer of an unsaturated carboxylic acid and an epoxy group-containing polymerizable unsaturated compound, (b) a copolymer of styrene and an unsaturated carboxylic acid, (c) a quinone diazide group- ) Organic solvent is described.

Patent Literature 3 discloses a composition comprising a copolymer of [A] an unsaturated carboxylic acid and an unsaturated compound containing an epoxy group and an olefinically unsaturated compound other than these, and [B] a condensate of a specific phenol compound and a 1,2-naphthoquinone diazidesulfonic acid halide By weight of a radiation-sensitive resin composition.

Patent Documents 4 and 5 disclose a photosensitive resin composition containing a copolymer of an unsaturated carboxylic acid and an alicyclic epoxy group-containing unsaturated compound and 1,2-naphthoquinone diazidesulfonic acid ester.

The above-mentioned conventional photosensitive resin is common in that an unsaturated carboxylic acid such as methacrylic acid is used as a component which exhibits alkali solubility. However, since these photosensitive resins have higher acidity as compared with those having a phenolic hydroxyl group, it is difficult to manage developability and reactivity with an epoxy group is excellent, but the development margin and storage stability are insufficient. This problem is improved by using the monoolefinically unsaturated compound as a part of the copolymerization component, but it can not be said to be sufficient as a means for solving the problem because it can cause scum.

Patent Document 6 discloses a photosensitive resin composition containing (A) a copolymer of hydroxystyrene and methyl methacrylate, (B) a quinone diazide group-containing compound, and (C) a thermosetting resin. This resin composition is characterized in that hydroxystyrene is used as a component for expressing alkali solubility. However, since this photosensitive resin composition has a phenolic hydroxyl group, it is effective as a means for solving the above problems, but has a drawback that it is colored by heating.

Patent Document 7 discloses a photosensitive resin composition containing a copolymer containing a hydroxyphenyl (meth) acrylate and an epoxy group-containing unsaturated compound as polymerization components and a quinonediazide group-containing compound. This photosensitive resin composition has been developed in order to overcome the technical problems of the above-described photosensitive resin composition, but it can not be said that the electric characteristics and the heat discoloration resistance are sufficient.

Japanese Patent Application Laid-Open No. 2003-330180 Japanese Patent Laid-Open No. 2005-107314 Japanese Laid-Open Patent Publication No. 2004-170566 Japanese Patent Application Laid-Open No. 2003-76012 Japanese Laid-Open Patent Publication No. 2005-49691 Japanese Patent Application Laid-Open No. 5-158232 Japanese Patent Application Laid-Open No. 2007-33518

The present invention provides a photosensitive resin composition which is excellent in transparency, heat discoloration resistance and electrical characteristics, and is excellent in coating properties, developability, curability and storage stability, and a copolymer for expressing the properties thereof .

DISCLOSURE OF THE INVENTION The present inventors have intensively studied in order to achieve the above object and as a result, they have found that a copolymer containing a repeating unit derived from hydroxyphenyl (meth) acrylate and a repeating unit derived from a blocked isocyanate group-containing unsaturated compound achieves the above object And thus the present invention has been accomplished.

That is, the present invention is represented by the following [1] to [9].

[1] A copolymer comprising a repeating unit derived from hydroxyphenyl (meth) acrylate and a blocked repeating unit derived from an isocyanate group-containing unsaturated compound.

[2] A thermosetting resin composition comprising 30 mol% to 90 mol% of repeating units derived from the above hydroxyphenyl (meth) acrylate and 10 mol% to 70 mol% of repeating units derived from the blocked isocyanate group-containing unsaturated compound Gt; is a hydrogen atom or a methyl group.

[3] The copolymer according to [1] or [2], wherein the blocked isocyanate group-containing unsaturated compound is blocked 2-isocyanatoethyl (meth) acrylate.

[4] The copolymer according to any one of [1] to [3], wherein the block is formed by methyl ethyl ketone oxime.

[5] The method according to any one of [1] to [4], wherein the blocked isocyanate group-containing unsaturated compound is 2- (O- [1'-methylpropylideneamino] carboxyamino) ethyl ≪ / RTI >

[6] A photosensitive resin composition comprising the copolymer according to any one of [1] to [5] and a quinone diazide group-containing compound.

[7] The photosensitive resin composition according to [6], wherein the quinone diazide group-containing compound is contained in an amount of 5 to 60 parts by mass based on 100 parts by mass of the copolymer.

[8] The photosensitive resin composition according to [6] or [7], wherein the photosensitive resin composition contains 30 to 4000 parts by mass of a solvent per 100 parts by mass of the total amount of components other than the solvent.

[9] A resin film obtained by applying the photosensitive resin composition described in any one of [6] to [8] on a substrate and drying the coated film.

According to the present invention, it is possible to provide a photosensitive resin composition which is excellent in transparency, heat discoloration resistance and electric characteristics, and has good spreadability, developability, curability and storage stability, and a copolymer for expressing these properties.

Hereinafter, the photosensitive resin composition of the present invention will be described in detail.

Further, in the specification and claims, (meth) acrylate means methacrylate or acrylate.

The copolymer [A] contained as an essential component in the photosensitive resin composition of the present invention is a copolymer comprising repeating units derived from (a1) hydroxyphenyl (meth) acrylate and repeating units derived from blocked isocyanate group-containing unsaturated compounds (a2) .

Specific examples of the (a1) hydroxyphenyl (meth) acrylate include o-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, o-hydroxyphenyl methacrylate, m- Hydroxyphenyl methacrylate, p-hydroxyphenyl methacrylate, and the like. These may be used alone or in combination of two or more. Of these, p-hydroxyphenyl methacrylate is preferable.

In the copolymer [A], the repeating unit derived from (a1) hydroxyphenyl (meth) acrylate is preferably contained in an amount of 30 mol% to 90 mol%, more preferably 40 mol% to 80 mol% . If the repeating unit derived from (a1) hydroxyphenyl (meth) acrylate is less than 30 mol%, the alkali solubility may be insufficient. On the other hand, if it exceeds 90 mol%, a good pattern may not be formed.

(a2) The blocked isocyanate group-containing unsaturated compound is easily obtained by blocking an isocyanate group by reacting an isocyanate group-containing unsaturated compound with a known or well-known blocking agent. Examples of the isocyanate group-containing unsaturated compound include isocyanate group-containing ethylenically unsaturated compounds such as 2-isocyanatoethyl (meth) acrylate and isopropenyl-?,? -Dimethylbenzyl isocyanate. As the blocking agent, alkyl ketoxime, phenols, alcohols, pyrazoles,? -Diketones and lactams are preferable, alkyl ketoximes, phenols, alcohols and pyrazoles are more preferable, alkyl ketoximes and pyrazoles Most preferred. Specific examples of the blocked isocyanate group-containing unsaturated compound include 2- (O- [1'- methylpropylideneamino] carboxyamino) ethyl acrylate, 2- (O- [1'- methylpropylideneamino] carboxyamino) ethyl Methacrylate, 2 - [(3,5-dimethylpyrazolyl) carbonylamino] ethyl acrylate, 2 - [(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, 2 - [(succinimide) carbonylamino] ethyl acrylate, 2 - [(phthalimido) carbonylamino] ethyl methacrylate, (O- [1'-methylpropylideneamino] carboxyamino) 3-isopropenyl (meth) acrylate in which an isocyanate group is blocked such as 2-isocyanatoethyl -α, α-dimethylbenzyl, 2- (O- [1'-methylpropylideneamino] carboxyamino) 4-isopropenyl- [(3,5-dimethylpyrazolyl) carbonylamino] 3-isopropenyl-α, α-dimethylbenzyl, 2- And isopropenyl-?,? -Dimethylbenzyl isocyanate in which isocyanate groups such as isopropenyl-α, α-dimethylbenzyl are blocked. These may be used alone or in combination of two or more. Among them, 2-isocyanatoethyl (meth) acrylate in which an isocyanate group is blocked from the viewpoint of copolymerization is preferable.

In the copolymer [A], the repeating unit derived from the blocked isocyanate group-containing unsaturated compound (a2) is preferably contained in an amount of 10 mol% to 70 mol%, more preferably 20 mol% to 60 mol%. (a2) If the blocked isocyanate group-containing unsaturated compound-derived repeating unit is less than 10 mol%, the heat resistance, chemical resistance and electrical properties may be lowered. On the other hand, when the amount exceeds 70 mol%, the alkali solubility becomes insufficient have.

The copolymer [A] may also be a copolymer consisting of only (a1) hydroxyphenyl (meth) acrylate and (a2) blocked isocyanate group-containing unsaturated compounds. (A1) hydroxyphenyl (meth) acrylate and Or a copolymer containing another ethylenically unsaturated compound capable of copolymerizing with the blocked isocyanate group-containing unsaturated compound as a copolymerization component. Examples of other unsaturated compounds include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, maleic anhydride, fumaric anhydride, citraconic anhydride, (Meth) acrylate, o-carboxyphenyl (meth) acrylate, m-carboxyphenyl (meth) acrylate, (Meth) acryloyloxyethyl], [omega] -carboxypoly (meth) acrylamide, p-carboxyphenyl (meth) acrylamide, mono [2- 2,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5- Methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, tricyclo [5.2.1.0 ^2,6] decane-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decane-8-oxyethyl (meth) acrylate, methyl (meth) (Meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (Meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate, n-stearyl (meth) acrylate, cyclohexyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Ah (Meth) acrylate, benzyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (Meth) acrylate, o-methoxyphenyl (meth) acrylate, m-methoxyphenyl (meth) acrylate, p- (Meth) acrylate, dimethylhydroxyphenyl (meth) acrylate, diethyl maleate, diethyl fumarate, diethyl itaconate, bicyclo [2.2.1] hept- 2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept- 2,6-diethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept- 2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5- 2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [2.2.1] hex- [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [ 2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- - ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy- 2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, styrene, methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, 1,3-butadiene, isoprene, -Butadiene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylic acid (Meth) acrylamide, p-hydroxyphenyl (meth) acrylamide, 3,5-dimethyl-4- Hydroxybenzyl (meth) acrylamide, phenylmaleimide, hydroxyphenylmaleimide, cyclohexylmaleimide, benzylmaleimide, and trifluoromethyl (meth) acrylate. These may be used alone or in combination of two or more. These unsaturated compounds are used in an arbitrary ratio within a range not adversely affecting each property in order to adjust transparency, heat resistance, adhesion, chemical resistance, electrical properties, refractive index, coating property, developability, storage stability, Can be used.

The weight average molecular weight (Mw) of the copolymer of the present invention is preferably 1,500 to 50,000, more preferably 2,000 to 20,000 in terms of polystyrene. If the weight-average molecular weight is less than 1,500, a flat resin film may not be obtained, the residual film ratio after development may deteriorate, or the pattern shape and heat resistance of the resulting resin film may deteriorate. On the other hand, The pattern shape may be deteriorated.

The molecular weight of the copolymer in the present invention is calculated by gel permeation chromatography (GPC) under the following conditions and calculated in terms of polystyrene. The weight average molecular weight and the molecular weight distribution are calculated from the rise time of GPC to 21 minutes as the calculation range.

Column: Shodex (registered trademark) KF-801 + KF-802 + KF-802 + KF-803

Column temperature: 40 DEG C

Developing solvent: tetrahydrofuran

Detector: Differential refractometer (Shodex (R) -I 101)

Flow rate: 1 ml / min

The polymerization reaction for obtaining the copolymer of the present invention is not particularly limited, and examples thereof include radical polymerization, cation polymerization, anionic polymerization, coordination anionic polymerization and the like. Concretely, it is preferable to use, as essential components, (a1) hydroxyphenyl (meth) acrylate and (a2) isocyanate group-containing unsaturated compounds as essential components, and if necessary, other unsaturated compounds as a total amount of preferably 10% by mass to 60% Can be polymerized by using a polymerization initiator in a reaction solvent containing the above-mentioned components. The molecular weight can be adjusted by adjusting the amount of the reaction solvent, the amount of the initiator used, and the polymerization temperature. The molecular weight can be adjusted by using a chain transfer agent typified by mercaptans.

Specific examples of the reaction solvent include methanol, ethanol, 1-propanol, isopropyl alcohol, butanol, ethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, toluene, xylene, ethyl acetate , Methoxybutyl acetate such as isopropyl acetate, n-propyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and 3-methoxybutyl acetate, ethylene glycol monobutyl Ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, 3-methoxybutanol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Dimethylsulfoxide, di Butyl may be mentioned dimethylformamide, dimethylacetamide, and ethyl lactate, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, methoxy methyl propionate, ethoxy ethyl propionate.

Examples of the polymerization initiator include azo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-butyronitrile), 2,2'-azobisisobutyl Azo-based initiators such as rhenitrile, dimethyl-2,2'-azobisisobutylate and 1,1'-azobis (cyclohexane-1-carbonitrile), benzoyl peroxides, lauryl peroxides, Organic peroxides such as oxides, acetyl peroxides, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, t-butyl peroxyacetate and t-butyl peroxybenzoate.

The quinonediazide group-containing compound [B] contained as an essential component in the photosensitive resin composition of the present invention is not particularly limited as long as it is a photosensitive agent and is a compound having a quinonediazide group. For example, an ester obtainable by condensation of a phenolic compound or an alcoholic compound with 1,2-naphthoquinone diazidesulfonic acid halide is preferable. Among them, 1,2-naphthoquinonediazidesulfonic acid halide corresponding to 30 to 85 mol% of the hydroxyl group in the phenolic compound or the alcoholic compound is more preferably condensed from the viewpoint of the transparency of the photosensitive film and the resin film, To 70 mol% of 1,2-naphthoquinonediazide sulfonic acid halide is most preferably condensed. Specific examples of the phenolic compound or the alcoholic compound include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxy Benzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methyl Benzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, 2,3,4,2 ', 6'-pentahydroxybenzophenone, 2,4,6,3' , 4 ', 5'-hexahydroxybenzophenone, 3,4,5,3', 4 ', 5'-hexahydroxybenzophenone, 2-methyl-2- (2,4-dihydroxyphenyl) Hydroxyphenyl) -7-hydroxychroman, 2- [bis {(5-isopropyl-4-hydroxy- 1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- 1-methylethyl} benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} Dihydroxybenzene bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p- hydroxyphenyl) methane, 1,1,1-tri (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (4-hydroxyphenyl) -3-phenylpropane, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [ ] Benzene, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3'3'-tetramethyl-1,1'-spirobindene- , 7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavone and the like. These may be used alone or in combination of two or more. Examples of the compound [B] having a quinone diazide group include 1,2-propanediol and 1,3-propanediol such as 1- [1- (4-hydroxyphenyl) Naphthoquinonediazidesulfonic acid esters are preferred.

In the photosensitive resin composition of the present invention, the compounding amount of the quinone diazide group-containing compound [B] is preferably 5 parts by mass to 60 parts by mass, more preferably 10 parts by mass to 50 parts by mass, per 100 parts by mass of the copolymer [A] Mass part is more preferable. If the amount of the quinone diazide group-containing compound [B] is less than 5 parts by mass, defective development may occur. On the other hand, if the amount exceeds 60 parts by mass, defective development may occur or transparency, insulation and flatness of the resin film may deteriorate .

The photosensitive resin composition of the present invention contains the copolymer [A] and the quinone diazide group-containing compound [B] as essential components, but may contain an ultraviolet absorber, a sensitizer, , A compound capable of crosslinking with a plasticizer, a thickener, an organic solvent, a dispersant, a defoaming agent, a surfactant, a adhesion aid, a thermosensitive acid generating compound, a copolymer [A] and a quinone diazide group- have.

The photosensitive resin composition of the present invention is prepared by homogeneously mixing the copolymer [A], the quinone diazide group-containing compound [B] and other optionally added components as described above, dissolved in a suitable solvent, .

As the solvent, a copolymer [A] and a quinone diazide group-containing compound [B] and optionally other components to be blended are uniformly dissolved, and those which are not reacted with each component are used, , The same solvents as those exemplified as the solvent can be used. Among them, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methoxybutyl acetate, methyl methoxypropionate and ethyl ethoxypropionate are used in order to determine the solubility, From the viewpoints of reactivity with the component, easiness of forming a coating film, and the like. In order to increase the in-plane uniformity of the film thickness together with these solvents, a high boiling solvent such as N-methylpyrrolidone,? -Butyrolactone, or N, N-dimethylacetamide may be used in combination.

When the photosensitive resin composition of the present invention is prepared into a solution, 100 parts by mass of the total amount of the copolymer [A] (solid component) and the quinone diazide group-containing compound [B] Or may be used in combination of two or more kinds) in an amount of 30 parts by mass to 4,000 parts by mass, preferably 50 parts by mass to 3,000 parts by mass.

The photosensitive resin composition of the present invention has good applicability, developability, curability and storage stability, and by using it, a resin film excellent in transparency, heat discoloration resistance and electrical characteristics can be formed. This resin film is used for forming a protective film for an electronic part, forming a planarizing film or an interlayer insulating film, forming a microlens or a microlens array, forming a light diffusing reflective film of a liquid crystal display element, forming a projection or a spacer for orientation control, forming a color filter, Can be preferably used.

Next, a method for forming a resin film using the photosensitive resin composition of the present invention will be described. First, the photosensitive resin composition of the present invention is applied onto a glass substrate, a silicon wafer, and a substrate on which various metals are formed, and dried to form a radiation-sensitive resin film. The method of applying the photosensitive resin composition is not particularly limited, and suitable methods such as a spray method, a roll coating method, a rotary coating method, a bar coating method, and a slit coating method can be mentioned. The drying conditions vary depending on the kind of each component, the use ratio, and the like. For example, the drying conditions can be set at 60 ° C to 110 ° C for 30 seconds to 30 minutes.

Next, patterning can be performed by irradiating the formed resin film with radiation through a mask having a predetermined pattern, and then developing it with a developing solution. As the radiation used at this time, for example, g-line (wavelength 436 nm), i-line (wavelength 365 nm), KrF excimer laser, ArF excimer laser, X-ray, electron beam, A low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, and an excimer laser generator. Examples of the developing solution used in the development treatment include aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, The amine compound may be at least one selected from the group consisting of amine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [ (Basic compound) such as undecyl-7-ene, 1,5-diazabicyclo [4,3,0] -one-5-ene can be used. An aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the aqueous alkali solution, or various organic solvents which dissolve the photosensitive resin composition of the present invention may be used as a developer. As the developing method, suitable methods such as liquid mounting method, dipping method, swing dipping method, and shower method can be used. The developing time at this time varies depending on the composition of the photosensitive resin composition, but may be, for example, from 30 seconds to 120 seconds.

Next, the patterned resin film is subjected to a rinsing treatment preferably by, for example, water washing, and preferably by irradiating the entire surface with radiation so that the amount of the quinone diazide group remaining in the resin film The decomposition treatment of the compound [B] is carried out. Since the quinone diazide group-containing compound [B] causes light absorption, the transparency of the resin film is improved by exposure.

Next, by performing a heat treatment (post-baking treatment) by a hot plate, an oven, or the like, a curing treatment can be performed. The sintering temperature in this curing treatment is, for example, 120 ° C to 250 ° C. The heating time varies depending on the type of the heating apparatus. For example, when the heating process is performed on the hot plate, the heating time may be from 5 minutes to 30 minutes. When the heating process is performed in the oven, the heating time may be from 30 minutes to 90 minutes. have. In particular, when forming the micro lens and the projection control projection, a step bake method in which two or more heating steps are performed may be used. Specifically, the pattern may be patterned by initial heating at a temperature higher than the glass transition temperature of the resin film Flowed into a semi-spherical shape by surface tension, and then subjected to heating by heating at a higher temperature to obtain a predetermined shape.

Thus, a patterned thin film corresponding to each application such as a target protective film, a planarizing film, an interlayer insulating film, a microlens or microlens array, a light diffusion reflecting film, a projection for alignment control, a spacer, a color filter, Can be formed on the surface. The resin film thus formed is excellent in transparency, heat discoloration resistance and electrical characteristics.

Example

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

≪ Synthesis of Copolymer >

[Example 1]

In a flask equipped with a reflux condenser and a stirrer, 42 parts by mass of p-hydroxyphenyl methacrylate, 58 parts by mass of 2- (O- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate, 400 parts by mass of methyl ether acetate and 6 parts by mass of 2,2'-azobisisobutyronitrile were charged and purged with nitrogen, and the temperature of the mixture was raised to 80 ° C while stirring, and the mixture was reacted at 80 ° C for 6 hours. The disappearance of the monomer was confirmed by gel permeation chromatography and the temperature was raised to 100 占 폚 and aging was carried out for 30 minutes. Propylene glycol monomethyl ether acetate was removed by distillation under reduced pressure at 80 캜 and the solid concentration was adjusted to 30 mass% to obtain a resin solution (S-1) containing the copolymer [A-1].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-1] contained in the resin solution was 8,700 and the molecular weight distribution (Mw / Mn) was 3.5.

[Example 2]

In a flask equipped with a reflux condenser and a stirrer, 41 parts by mass of p-hydroxyphenyl methacrylate, 59 parts by mass of 2 - [(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, (S-2) containing the copolymer [A-2] was obtained in the same manner as in Example 1, except that 400 parts by mass of the polyvinyl butyral resin, 400 parts by mass of the ether acetate and 6 parts by mass of 2,2'-azobisisobutyronitrile were added. ).

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-2] contained in the resin solution was 8,800 and the molecular weight distribution (Mw / Mn) was 3.5.

[Example 3]

, 36 parts by mass of p-hydroxyphenyl methacrylate, 51 parts by mass of 2- (O- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate, 50 parts by mass of n-butyl 13 parts by mass of acrylate, 400 parts by mass of propylene glycol monomethyl ether acetate, and 6 parts by mass of 2,2'-azobisisobutyronitrile were charged and reacted in the same manner as in Example 1 to obtain a copolymer [A-3 (S-3) was obtained.

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-3] contained in the resin solution was 8,300 and the molecular weight distribution (Mw / Mn) was 3.3.

[Comparative Example 1]

In a flask equipped with a reflux condenser and a stirrer, 56 parts by mass of p-hydroxyphenyl methacrylate, 44 parts by mass of glycidyl methacrylate, 600 parts by mass of propylene glycol monomethyl ether acetate and 2,2'-azobisisobutyl And 6 parts by mass of butyronitrile were purged with nitrogen, and the temperature of the mixture was elevated to 80 DEG C while stirring, and the mixture was reacted at 80 DEG C for 6 hours. The disappearance of the monomer was confirmed by gel permeation chromatography and the temperature was raised to 100 占 폚 and aging was carried out for 30 minutes. Propylene glycol monomethyl ether acetate was distilled off under reduced pressure at 100 占 폚 to adjust the solid concentration to 30 mass% to obtain a resin solution (S-4) containing the copolymer [A'-4].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A'-4] contained in the resin solution was 8,400 and the molecular weight distribution (Mw / Mn) was 3.1.

<Evaluation>

(1) Transparency

Resin solutions (S-1) to (S-4) were coated on a glass substrate to a film thickness of 3 占 퐉 and dried in an oven at 80 占 폚 for 30 minutes. For the glass substrate with the resin film thus obtained, the lowest transmittance at a wavelength of 400 to 800 nm was measured with a glass substrate as a blank by using a spectrophotometer. The higher the transmittance, the higher the transparency. The results are shown in Table 1.

(2) Curability

Resin solutions (S-1) to (S-4) were coated on a hot plate at 150 ° C to a film thickness of about 0.5 mm, and the time until gelation was measured. The shorter the time, the better the curability. The results are shown in Table 1.

(3) Electrical characteristics

Resin solutions (S-1) to (S-4) were coated on a metal substrate to a film thickness of 3 占 퐉 and dried in an oven at 80 占 폚 for 30 minutes. The dried coating film was heated and cured in an oven at 200 캜 for 30 minutes. The dielectric constant of the obtained cured coating film at 1 MHz was measured. The smaller the dielectric constant, the better the electrical characteristics. The results are shown in Table 1.

Example 1 Example 2 Example 3 Comparative Example 1 Transparency 99% 99% 99% 99% Gel time 85 seconds 108 seconds 93 seconds 163 seconds permittivity 3.6 3.3 3.5 4.5

&Lt; Preparation of Photosensitive Resin Composition &gt;

[Example 4]

100 parts by mass of the resin solution (S-1) obtained in Example 1, 100 parts by mass of 1- [1- (4-hydroxyphenyl) isopropyl] -4- [ -1,2-naphthoquinonediazide-5-sulfonic acid ester (6.25 parts by mass) and propylene glycol monomethyl ether acetate (75 parts by mass) were mixed and dissolved, and the mixture was filtered through a 0.2 占 퐉 membrane filter to obtain a photosensitive resin composition S-5) was prepared.

[Example 5]

Using the resin solution (S-2) obtained in Example 2, a photosensitive resin composition (S-6) in a solution state was prepared in the same manner as in Example 4.

[Example 6]

Using the resin solution (S-3) obtained in Example 3, a photosensitive resin composition (S-7) in a solution state was prepared in the same manner as in Example 4.

[Comparative Example 2]

Using the resin solution (S-4) obtained in Comparative Example 1, a photosensitive resin composition (S-8) in a solution state was prepared in the same manner as in Example 4.

<Evaluation>

(1) Storage stability

The viscosity after storage of the photosensitive resin compositions (S-5) to (S-8) at room temperature for one month was measured. The viscosity was measured at 25 캜 using an E-type viscometer. A viscosity increase rate after preservation for one month at room temperature was less than 10%, and a case where viscosity increase rate was 10% or more was evaluated as x. The results are shown in Table 2.

(2) Coating property

The photosensitive resin compositions (S-5) to (S-8) were coated on a glass substrate so as to have a film thickness of 3 탆 and dried in an oven at 80 캜 for 30 minutes. A transparent resin film having uniform thickness in all the photosensitive resin compositions was obtained, and the applicability was good (O).

(3) Developability

The dried resin film was exposed through a positive pattern mask with an ultra-high pressure mercury lamp, immersed in an aqueous solution of 2.38 wt% tetramethylammonium hydroxide for 1 minute for development, and rinsed with pure water. Positive patterns were transferred from all the photosensitive resin compositions, and the developability was good (O).

(4) Transparency

The dried resin film was exposed to the entire surface without passing through a positive pattern mask and heated and cured in an oven at 200 DEG C for 30 minutes. The glass substrate with the cured resin film thus obtained was measured using a spectrophotometer with the lowest transmittance at a wavelength of 400 to 800 nm with the glass substrate as a blank. The higher the transmittance, the higher the transparency. The results are shown in Table 2.

(5) Heat discoloration resistance

Cured at 200 占 폚 for 30 minutes, and further heat-treated at 230 占 폚 for 10 hours, and the transmittance at a wavelength of 400 nm was measured using a glass substrate as a blank. The higher the transmittance, the higher the heat discoloration resistance. The results are shown in Table 2.

Example 4 Example 5 Example 6 Comparative Example 2 Storage stability ○ ○ ○ ○ Application property ○ ○ ○ ○ Developability ○ ○ ○ ○ Transparency 99% 99% 99% 99% Heat discoloration property 84% 88% 85% 70%

Claims (9)

Wherein the copolymer comprises 30 mol% to 90 mol% of recurring units derived from hydroxyphenyl (meth) acrylate and 10 mol% to 70 mol% of recurring units derived from the blocked isocyanate group-containing unsaturated compound. delete The method according to claim 1,
Wherein the blocked isocyanate group-containing unsaturated compound is blocked 2-isocyanatoethyl (meth) acrylate. The method according to claim 1,
Lt; RTI ID = 0.0 &gt; methyl ethyl ketone oxime. &Lt; / RTI &gt; The method according to claim 1,
Wherein the blocked isocyanate group-containing unsaturated compound is 2- (O- [1'-methylpropylideneamino] carboxyamino) ethyl (meth) acrylate. A photosensitive resin composition comprising the copolymer according to claim 1 and a quinone diazide group-containing compound. The method according to claim 6,
Wherein the quinone diazide group-containing compound is contained in an amount of 5 to 60 parts by mass based on 100 parts by mass of the copolymer. 8. The method according to claim 6 or 7,
Wherein the photosensitive resin composition contains 30 to 4000 parts by mass of a solvent based on 100 parts by mass of the total amount of components other than the solvent. A resin film obtained by applying the photosensitive resin composition according to claim 6 or 7 onto a substrate and drying the coated film.