WO2014091818A1 - 共重合体、それを含有する感光性樹脂組成物及び樹脂膜 - Google Patents
共重合体、それを含有する感光性樹脂組成物及び樹脂膜 Download PDFInfo
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- WO2014091818A1 WO2014091818A1 PCT/JP2013/077643 JP2013077643W WO2014091818A1 WO 2014091818 A1 WO2014091818 A1 WO 2014091818A1 JP 2013077643 W JP2013077643 W JP 2013077643W WO 2014091818 A1 WO2014091818 A1 WO 2014091818A1
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- copolymer
- acrylate
- meth
- resin composition
- photosensitive resin
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
- C08K5/08—Quinones
Definitions
- the present invention relates to a photosensitive resin composition, specifically a protective film for electronic parts such as a liquid crystal display element, an integrated circuit element, a solid-state imaging element, a planarization film or an interlayer insulating film, a microlens or a microlens array,
- the present invention relates to a photosensitive resin composition suitable for formation of a light diffusive reflection film, alignment control protrusions or spacers of a liquid crystal display element, formation of a color filter, or formation of an optical waveguide.
- a protective film for preventing deterioration or damage of electronic parts such as TFT liquid crystal display elements, magnetic head elements, integrated circuit elements, solid-state imaging elements, or interlayers for insulating between wirings arranged in layers.
- a photosensitive resin composition has been used to form an insulating film.
- the interlayer insulating film is transparent.
- the electrode film forming process the film is exposed to a high temperature condition or exposed to a resist stripping solution used for forming an electrode pattern. Therefore, a photosensitive resin composition for forming an interlayer insulating film is required to be able to form a resin film having excellent developability and excellent transparency, heat resistance, flatness, adhesion, chemical resistance and electrical properties. .
- microlenses having a lens diameter of about 3 to 100 ⁇ m or those microlenses are used as an imaging optical system for on-chip color filters such as facsimiles, electronic copying machines, solid-state imaging devices, or optical fiber connectors.
- a regularly arranged microlens array is used.
- CCD elements used in digital cameras and the like have recently been miniaturized as the number of pixels has increased, and the light receiving area per CCD element has decreased. Therefore, as a means for increasing the amount of received light, it has been attempted to form a convex lens-shaped microlens on the CCD element.
- the photosensitive resin composition for forming the microlens is required to have excellent developability, transparency, melt flow property, and heat resistance, and a high refractive index from the viewpoint of light collection.
- Examples of the photosensitive resin composition include, for example, Patent Document 1, (a) a copolymer of an unsaturated carboxylic acid and an epoxy group-containing polymerizable unsaturated compound, and (b) an unsaturated carboxylic acid and other compounds.
- Patent Document 1 A photosensitive resin composition containing a copolymer with a monoolefin unsaturated compound, (c) a quinonediazide group-containing compound, and (d) an organic solvent is described.
- Patent Document 2 discloses (a) a copolymer of an unsaturated carboxylic acid and an epoxy group-containing polymerizable unsaturated compound, (b) a copolymer of styrenes and an unsaturated carboxylic acid, (c) a quinonediazide.
- Patent Document 3 discloses [A] a copolymer of an unsaturated carboxylic acid, an epoxy group-containing unsaturated compound, and another olefinic unsaturated compound, and [B] a specific phenol compound and 1,2-naphthoquinonediazide.
- a radiation sensitive resin composition containing a condensate with a sulfonic acid halide is described.
- Patent Documents 4 and 5 describe a photosensitive resin composition containing a copolymer of an unsaturated carboxylic acid and an alicyclic epoxy group-containing unsaturated compound, and a 1,2-naphthoquinonediazide sulfonic acid ester. ing.
- the above-described conventional photosensitive resins are common in that unsaturated carboxylic acids such as methacrylic acid are used as components that exhibit alkali solubility.
- these photosensitive resins have higher acidity than those having a phenolic hydroxyl group, so that it is difficult to manage developability and have excellent reactivity with epoxy groups, but development margin and storage stability. There is a problem that the property is insufficient. Although this problem can be improved by using a monoolefin unsaturated compound as a part of the copolymerization component, it can cause scum, so it cannot be said to be sufficient as a solution.
- Patent Document 6 describes a photosensitive resin composition containing (A) a copolymer of hydroxystyrene and methyl methacrylate, (B) a quinonediazide group-containing compound, and (C) a thermosetting resin. Yes.
- This resin composition is characterized in that hydroxystyrene is used as a component that exhibits alkali solubility.
- this photosensitive resin composition has a phenolic hydroxyl group, it is effective as a means for solving the above-mentioned problems, but has a drawback of being colored by heating.
- Patent Document 7 discloses a photosensitive resin composition containing a copolymer containing hydroxyphenyl (meth) acrylate and an epoxy group-containing unsaturated compound as polymerization components, and a quinonediazide group-containing compound. This photosensitive resin composition was developed to overcome the technical problems of the photosensitive resin composition described above, but it could not be said that the electrical characteristics and the heat discoloration were sufficient.
- the present invention expresses a photosensitive resin composition that is excellent in transparency, heat discoloration, and electrical characteristics, and has good coatability, developability, curability, and storage stability, and these characteristics.
- An object of the present invention is to provide a copolymer.
- [2] It is characterized by containing 30 mol% to 90 mol% of repeating units derived from the hydroxyphenyl (meth) acrylate and 10 mol% to 70 mol% of repeating units derived from the blocked isocyanate group-containing unsaturated compound [1] ]
- [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 made of methyl ethyl ketone oxime.
- the blocked isocyanate group-containing unsaturated compound is 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl (meth) acrylate, [1] to [4] ]
- the copolymer in any one of.
- a photosensitive resin composition comprising the copolymer according to any one of [1] to [5] and a quinonediazide group-containing compound.
- the photosensitive resin composition as described in [6] which contains 5 to 60 parts by mass of the quinonediazide group-containing compound with respect to 100 parts by mass of the copolymer.
- a photosensitive resin composition having excellent transparency, heat discoloration, and electrical characteristics, and good coating properties, developability, curability, and storage stability, and a co-polymer for exhibiting these characteristics. Coalescence can be provided.
- (meth) acrylate means methacrylate or acrylate.
- the copolymer [A] contained as an essential component in the photosensitive resin composition of the present invention is derived from (a1) a repeating unit derived from hydroxyphenyl (meth) acrylate and (a2) a blocked isocyanate group-containing unsaturated compound. The repeating unit is included.
- (a1) hydroxyphenyl (meth) acrylate examples include o-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, o-hydroxyphenyl methacrylate, m-hydroxyphenyl methacrylate, p-hydroxyphenyl methacrylate. Etc. These may be used alone or in combination of two or more. Of these, p-hydroxyphenyl methacrylate is preferred.
- 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%.
- (A1) When the repeating unit derived from hydroxyphenyl (meth) acrylate is less than 30 mol%, the alkali solubility may be insufficient. On the other hand, when it exceeds 90 mol%, a good pattern may not be formed. .
- the blocked isocyanate group-containing unsaturated compound can be easily obtained by blocking the isocyanate group by reacting the isocyanate group-containing unsaturated compound with a known or well-known blocking agent.
- the isocyanate group-containing unsaturated compound include isocyanate group-containing ethylenically unsaturated compounds such as 2-isocyanatoethyl (meth) acrylate and isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate.
- alkyl ketoximes, phenols, alcohols, pyrazoles, ⁇ -diketones and lactams are preferable, alkyl ketoximes, phenols, alcohols and pyrazoles are more preferable, alkyl ketoximes. And pyrazoles are most preferred.
- blocked isocyanate group-containing unsaturated compound examples include 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl acrylate, 2- (0- [1′-methylpropylideneamino] carboxyl Amino) ethyl methacrylate, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl acrylate, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, 2-[(phthalimido) carbonylamino] ethyl acrylate 2-isocyanato with blocked isocyanate groups such as 2-[(phthalimido) carbonylamino] ethyl methacrylate, 2-[(succinimide) carbonylamino] ethyl acrylate, 2-[(succinimide) carbonylamino] ethyl methacrylate Ethyl
- the repeating unit derived from the blocked isocyanate group-containing unsaturated compound is preferably contained in an amount of 10 mol% to 70 mol%, more preferably 20 mol% to 60 mol%. (A2) If the repeating unit derived from the blocked isocyanate group-containing unsaturated compound is less than 10 mol%, the heat resistance, chemical resistance and electrical properties may be deteriorated. May be insufficient.
- the copolymer [A] may be a copolymer composed only of (a1) hydroxyphenyl (meth) acrylate and (a2) blocked isocyanate group-containing unsaturated compound, or (a1) hydroxyphenyl (meta It may be a copolymer containing, as a copolymerization component, another ethylenically unsaturated compound that can be copolymerized with acrylate) and (a2) a blocked isocyanate group-containing unsaturated compound.
- Examples of other unsaturated compounds include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, maleic anhydride, fumaric anhydride, citraconic anhydride, mesaconic anhydride, Itaconic anhydride, vinyl benzoic acid, o-carboxyphenyl (meth) acrylate, m-carboxyphenyl (meth) acrylate, p-carboxyphenyl (meth) acrylate, o-carboxyphenyl (meth) acrylamide, m-carboxyphenyl (meta ) Acrylamide, p-carboxyphenyl (meth) acrylamide, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ⁇ -carboxypolycaprolactone mono (
- 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 remaining film ratio after development may be reduced, or the pattern shape and heat resistance of the resulting resin film may be deteriorated. On the other hand, if it exceeds 50,000, the sensitivity may decrease or the pattern shape may deteriorate.
- the value of the molecular weight of the copolymer in this invention is measured on the following conditions using gel permeation chromatography (GPC), and is calculated in polystyrene conversion.
- the weight average molecular weight and molecular weight distribution are calculated with the calculation range from the rise time of GPC to 21 minutes.
- Developing solvent Tetrahydrofuran Detector: Differential refractometer (Showex (registered trademark) RI-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, cationic polymerization, anionic polymerization, and coordinated anionic polymerization.
- (a1) hydroxyphenyl (meth) acrylate and (a2) an isocyanate group-containing unsaturated compound are essential components, and if necessary, another unsaturated compound is preferably added in a range of preferably 10% by mass to 60% by mass. It can superpose
- the molecular weight can be adjusted by adjusting the amount of reaction solvent used, the amount of initiator used, and the polymerization temperature.
- the molecular weight can also be adjusted by using a chain transfer agent typified by mercaptans.
- reaction solvent examples include methanol, ethanol, 1-propanol, isopropyl alcohol, butanol, ethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, toluene, xylene, ethyl acetate, isopropyl acetate, normal propyl acetate, Butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, methoxybutyl acetate such as 3-methoxybutyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, The Pyrene glycol monomethyl ether, ethylene glycol monoethyl ether, 3-methoxybut
- polymerization initiator examples include 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-butyronitrile), 2,2′-azobisisobutyronitrile, dimethyl- Azo initiators such as 2,2'-azobisisobutyrate and 1,1'-azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di Examples thereof include organic peroxides such as -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 a photosensitizer and is not particularly limited as long as it is a compound having a quinonediazide group.
- an ester that can be obtained by condensation of a phenolic compound or an alcoholic compound with 1,2-naphthoquinonediazide sulfonic acid halide is preferred.
- a product obtained by condensing 1,2-naphthoquinonediazidesulfonic acid halide corresponding to 50 to 70 mol% is more preferred.
- the phenolic compound or alcoholic compound include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2, 3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4,2′-tetrahydroxy-4′-methylbenzophenone, 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) -4- (4 Hydroxypheny
- the compound [B] having a quinonediazide group includes 1,2-naphthoquinonediazidesulfone of 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene. Acid esters are preferred.
- the amount of the quinonediazide group-containing compound [B] is 5 to 60 parts by mass with respect to 100 parts by mass of the copolymer [A] (solid content). Preferably, it is 10 to 50 parts by mass.
- the compounding amount of the quinonediazide group-containing compound [B] is less than 5 parts by mass, poor development may occur. On the other hand, when it exceeds 60 parts by mass, poor development may occur or the transparency and insulation of the resin film may occur. In addition, the flatness may be deteriorated.
- the photosensitive resin composition of the present invention contains a copolymer [A] and a quinonediazide group-containing compound [B] as essential components, and an ultraviolet absorber, if necessary, as long as the effects of the present invention are not impaired.
- Sensitizer, sensitization aid, plasticizer, thickener, organic solvent, dispersant, antifoaming agent, surfactant, adhesion aid, thermosensitive acid generating compound, copolymer [A] and quinonediazide group A compound capable of undergoing a crosslinking reaction with the compound [B] can be contained.
- the photosensitive resin composition of the present invention is prepared by uniformly mixing the copolymer [A] and the quinonediazide group-containing compound [B] and other components optionally added as described above. It can be used in a solution state after being dissolved in a solvent.
- a copolymer [A], a quinonediazide group-containing compound [B], and other components that are optionally blended are uniformly dissolved, and those that do not react with each component are used.
- the thing similar to what was illustrated as a solvent which can be used in order to manufacture [A] is mentioned.
- 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 soluble in each component, reactive with each component, It can be preferably used in terms of ease of forming a coating film.
- a high boiling point solvent such as N-methylpyrrolidone, ⁇ -butyrolactone, N, N-dimethylacetamide may be used in combination.
- the total amount of the copolymer [A] (solid content), the quinonediazide group-containing compound [B] and other components optionally added is 100 parts by mass.
- the above-mentioned solvent (which may be used alone or in combination of two or more) is 30 to 4,000 parts by mass, preferably 50 to 3,000 parts by mass. Can be blended in parts.
- the photosensitive resin composition of the present invention has good coatability, developability, curability and storage stability, and by using this, a resin film excellent in transparency, heat discoloration and electrical characteristics can be formed. it can.
- This resin film is a protective film for electronic parts, planarization film or interlayer insulation film formation, microlens or microlens array formation, light diffusive reflection film for liquid crystal display element, formation of alignment control projection or spacer, color filter Or the formation of an optical waveguide.
- the photosensitive resin composition of the present invention is applied on 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 for applying the photosensitive resin composition is not particularly limited, and examples thereof include appropriate methods such as a spray method, a roll coating method, a spin coating method, a bar coating method, and a slit coating method.
- the drying conditions vary depending on the type of each component, the use ratio, and the like, but can be, for example, 60 ° C. to 110 ° C. for about 30 seconds to 30 minutes.
- patterning can be performed by irradiating the formed resin film with radiation through a mask having a predetermined pattern and then developing using a developer.
- the radiation used at this time include g-line (wavelength 436 nm), i-line (wavelength 365 nm), KrF excimer laser, ArF excimer laser, X-ray, electron beam, and the like.
- Examples include mercury lamps, ultra-high pressure mercury lamps, chemical lamps, and excimer laser generators.
- Examples of the developer used for the development processing include sodium hydroxide, potassium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, and triethylamine.
- Methyldiethylamine dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -undec-7-ene, 1,5-
- An aqueous solution of an alkali (basic compound) such as diazabicyclo [4,3,0] -none-5-ene can be used.
- an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent or surfactant such as methanol or ethanol to the aqueous alkali solution described above, or various organic solvents that dissolve the photosensitive resin composition of the present invention may be used as a developing solution.
- a developing method an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used.
- the development time at this time varies depending on the composition of the photosensitive resin composition, but can be, for example, 30 seconds to 120 seconds.
- the patterned resin film is preferably rinsed, for example, by washing with running water, and more preferably by irradiating the entire surface with a quinonediazide group-containing compound [B] remaining in the resin film. Disassembling process. Since the quinonediazide group-containing compound [B] causes light absorption, the post-exposure improves the transparency of the resin film.
- a curing treatment can be performed by heat treatment (post-baking treatment) using a hot plate, an oven or the like.
- the firing temperature in this curing process is, for example, 120 ° C. to 250 ° C.
- the heating time varies depending on the type of heating equipment, for example, when heat treatment is performed on a hot plate, it may be 5 minutes to 30 minutes, and when heat treatment is performed in an oven, it may be 30 minutes to 90 minutes. it can.
- a step baking method in which the heating process is performed twice or more can be used. Specifically, the temperature is higher than the glass transition temperature of the patterned resin film.
- the pattern is made to flow by initial heating at, and made hemispherical by surface tension, and then the crosslinking is advanced by heating at a higher temperature to obtain a predetermined shape.
- a patterned thin film can be formed on the surface of the substrate.
- the resin film thus formed is excellent in transparency, heat discoloration, and electrical characteristics.
- the disappearance of the monomer was confirmed by gel permeation chromatography, and the temperature was raised to 100 ° C. and aging was performed for 30 minutes. Propylene glycol monomethyl ether acetate was removed by distillation at 80 ° C. under reduced pressure, and the solid content concentration was adjusted to 30% by mass to obtain a resin solution (S-1) containing the copolymer [A-1].
- the copolymer [A-1] contained in the resin solution had a polystyrene-reduced weight average molecular weight (Mw) of 8,700 and a molecular weight distribution (Mw / Mn) of 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, 400 parts by mass of propylene glycol monomethyl ether acetate and 2 parts , 2′-azobisisobutyronitrile was charged in an amount of 6 parts by mass and reacted in the same manner as in Example 1 to obtain a resin solution (S-2) containing the copolymer [A-2].
- the copolymer [A-2] contained in the resin solution had a polystyrene-reduced weight average molecular weight (Mw) of 8,800 and a molecular weight distribution (Mw / Mn) of 3.5.
- Example 3 In a flask equipped with a reflux condenser and a stirrer, 36 parts by mass of p-hydroxyphenyl methacrylate, 51 parts by mass of 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate, 13 parts by mass of n-butyl acrylate , 400 parts by mass of propylene glycol monomethyl ether acetate and 6 parts by mass of 2,2′-azobisisobutyronitrile were prepared and reacted in the same manner as in Example 1 to obtain a resin solution containing the copolymer [A-3] (S-3) was obtained.
- the copolymer [A-3] contained in the resin solution had a polystyrene-reduced weight average molecular weight (Mw) of 8,300 and a molecular weight distribution (Mw / Mn) of 3.3.
- Propylene glycol monomethyl ether acetate was removed by distillation at 100 ° C. under reduced pressure, and the solid content concentration was adjusted to 30% by mass to obtain a resin solution (S-4) containing the copolymer [A′-4].
- the copolymer [A′-4] contained in the resin solution had a polystyrene-reduced weight average molecular weight (Mw) of 8,400 and a molecular weight distribution (Mw / Mn) of 3.1.
- Example 4 100 parts by mass of the resin solution (S-1) obtained in Example 1, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene- 6.25 parts by mass of 1,2-naphthoquinonediazide-5-sulfonic acid ester and 75 parts by mass of propylene glycol monomethyl ether acetate are mixed and dissolved, filtered through a 0.2 ⁇ m membrane filter, and the photosensitive resin composition in a solution state (S-5) was prepared.
- Example 5 Using the resin solution (S-2) obtained in Example 2, a solution-form photosensitive resin composition (S-6) 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.
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Abstract
Description
特許文献3には、[A]不飽和カルボン酸とエポキシ基含有不飽和化合物とそれら以外のオレフィン系不飽和化合物との共重合体、及び[B]特定のフェノール化合物と1,2-ナフトキノンジアジドスルホン酸ハライドとの縮合物を含む感放射線性樹脂組成物が記載されている。
また、特許文献4及び5には、不飽カルボン酸と脂環式エポキシ基含有不飽和化合物との共重合体、及び1,2-ナフトキノンジアジドスルホン酸エステルを含む感光性樹脂組成物が記載されている。
即ち、本発明は、以下の[1]~[9]で示される。
[1]ヒドロキシフェニル(メタ)アクリレート由来の繰り返し単位と、ブロックされたイソシアネート基含有不飽和化合物由来の繰り返し単位とを含むことを特徴とする共重合体。
[2]前記ヒドロキシフェニル(メタ)アクリレート由来の繰り返し単位30mol%~90mol%と、前記ブロックされたイソシアネート基含有不飽和化合物由来の繰り返し単位10mol%~70mol%とを含むことを特徴とする[1]に記載の共重合体。
[3]前記ブロックされたイソシアネート基含有不飽和化合物が、ブロックされた2-イソシアナトエチル(メタ)アクリレートであることを特徴とする[1]又は[2]に記載の共重合体。
[4]前記ブロックが、メチルエチルケトンオキシムによるものであることを特徴とする[1]~[3]の何れかに記載の共重合体。
[5]前記ブロックされたイソシアネート基含有不飽和化合物が、2-(0-[1’-メチルプロピリデンアミノ]カルボキシアミノ)エチル(メタ)アクリレートであることを特徴とする[1]~[4]の何れかに記載の共重合体。
[6][1]~[5]の何れかに記載の共重合体及びキノンジアジド基含有化合物を含有することを特徴とする感光性樹脂組成物。
[7]前記共重合体100質量部に対して、前記キノンジアジド基含有化合物を5~60質量部含むことを特徴とする[6]に記載の感光性樹脂組成物。
[8]溶媒以外の成分の合計量100質量部に対して、溶媒を30~4000質量部含むことを特徴とする[6]又は[7]に記載の感光性樹脂組成物。
[9][6]~[8]の何れかに記載の感光性樹脂組成物を基板上に塗布し、乾燥して得られることを特徴とする樹脂膜。
なお、明細書及び特許請求の範囲において、(メタ)アクリレートとは、メタクリレート又はアクリレートを意味する。
本発明の感光性樹脂組成物において必須成分として含まれる共重合体[A]は、(a1)ヒドロキシフェニル(メタ)アクリレート由来の繰り返し単位と、(a2)ブロックされたイソシアネート基含有不飽和化合物由来の繰り返し単位とを含むものである。
(a1)ヒドロキシフェニル(メタ)アクリレートの具体例としては、o-ヒドロキシフェニルアクリレート、m-ヒドロキシフェニルアクリレート、p-ヒドロキシフェニルアクリレート、o-ヒドロキシフェニルメタクリレート、m-ヒドロキシフェニルメタクリレート、p-ヒドロキシフェニルメタクリレートなどが挙げられる。これらは単独で使用してもよいし、2種以上を組み合わせて使用してもよい。また、これらの中でも、p-ヒドロキシフェニルメタクリレートが好ましい。
カラム:ショウデックス(登録商標) KF-801+KF-802+KF-802+KF-803
カラム温度:40℃
展開溶媒:テトラヒドロフラン
検出器:示差屈折計(ショウデックス(登録商標) RI-101)
流速:1mL/min
重合開始剤としては、例えば、2,2’-アゾビス(2,4-ジメチルバレロニトリル)、2,2’-アゾビス(2-ブチロニトリル)、2,2’-アゾビスイソブチロニトリル、ジメチル-2,2’-アゾビスイソブチレート、1,1’-アゾビス(シクロヘキサン-1-カルボニトリル)等のアゾ系開始剤やベンゾイルパーオキサイド、ラウリルパーオキサイド、オクタノイルパーオキサイド、アセチルパーオキサイド、ジ-t-ブチルパーオキサイド、t-ブチルクミルパーオキサイド、ジクミルパーオキサイド、t-ブチルパーオキシアセテート、t-ブチルパーオキシベンゾエート等の有機過酸化物が挙げられる。
〔実施例1〕
還流冷却器及び攪拌機を備えたフラスコに、p-ヒドロキシフェニルメタクリレート42質量部、2-(0-[1’-メチルプロピリデンアミノ]カルボキシアミノ)エチルメタクリレート58質量部、プロピレングリコールモノメチルエーテルアセテート400質量部及び2,2’-アゾビスイソブチロニトリル6質量部を仕込み、窒素置換した後、攪拌しながら液温を80℃に上昇させ、80℃で6時間反応させた。ゲル・パーミエーション・クロマトグラフィーによりモノマーの消失を確認し、100℃に昇温して30分間エージングを行った。80℃、減圧下でプロピレングリコールモノメチルエーテルアセテートを蒸留により取り除き、固形分濃度を30質量%に調整して、共重合体[A-1]を含む樹脂溶液(S-1)を得た。
樹脂溶液中に含まれる共重合体[A-1]のポリスチレン換算重量平均分子量(Mw)は8,700であり、分子量分布(Mw/Mn)は3.5であった。
還流冷却器及び攪拌機を備えたフラスコに、p-ヒドロキシフェニルメタクリレート41質量部、2-[(3,5-ジメチルピラゾリル)カルボニルアミノ]エチルメタクリレート59質量部、プロピレングリコールモノメチルエーテルアセテート400質量部及び2,2'-アゾビスイソブチロニトリル6質量部を仕込み、実施例1と同様に反応を行って、共重合体[A-2]を含む樹脂溶液(S-2)を得た。
樹脂溶液中に含まれる共重合体[A-2]のポリスチレン換算重量平均分子量(Mw)は8,800であり、分子量分布(Mw/Mn)は3.5であった。
還流冷却器及び攪拌機を備えたフラスコに、p-ヒドロキシフェニルメタクリレート36質量部、2-(0-[1'-メチルプロピリデンアミノ]カルボキシアミノ)エチルメタクリレート51質量部、n-ブチルアクリレート13質量部、プロピレングリコールモノメチルエーテルアセテート400質量部及び2,2'-アゾビスイソブチロニトリル6質量部を仕込み、実施例1と同様に反応を行って、共重合体[A-3]を含む樹脂溶液(S-3)を得た。
樹脂溶液中に含まれる共重合体[A-3]のポリスチレン換算重量平均分子量(Mw)は8,300であり、分子量分布(Mw/Mn)は3.3であった。
還流冷却器及び攪拌機を備えたフラスコに、p-ヒドロキシフェニルメタクリレート56質量部、グリシジルメタクリレート44質量部、プロピレングリコールモノメチルエーテルアセテー600質量部及び2,2’-アゾビスイソブチロニトリル6質量部を仕込み、窒素置換した後、攪拌しながら液温を80℃に上昇させ、80℃で6時間反応した。ゲル・パーミエーション・クロマトグラフィーによりモノマーの消失を確認し、100℃に昇温して30分間エージングを行った。100℃、減圧下でプロピレングリコールモノメチルエーテルアセテートを蒸留により取り除き、固形分濃度を30質量%に調整して、共重合体[A’-4]を含む樹脂溶液(S-4)を得た。
樹脂溶液中に含まれる共重合体[A’-4]のポリスチレン換算重量平均分子量(Mw)は8,400であり、分子量分布(Mw/Mn)は3.1であった。
(1)透明性
樹脂溶液(S-1)~(S-4)を、ガラス基板上に膜厚3μmとなるように塗布し、オーブンにて80℃で30分間乾燥した。得られた樹脂膜付きのガラス基板について、分光光度計を使用して、波長400~800nmでの最低透過率をガラス基板をブランクとして測定した。透過率が大きいほど透明性が高い。結果を表1に示す。
樹脂溶液(S-1)~(S-4)を、150℃のホットプレート上に膜厚約0.5mmとなるように塗布し、ゲル化するまでの時間を測定した。時間が短いほど硬化性が良好である。結果を表1に示す。
樹脂溶液(S-1)~(S-4)を、金属基板上に膜厚3μmとなるように塗付し、オーブンにて80℃で30分間乾燥した。乾燥した塗膜を200℃のオーブンで30分間加熱硬化させた。得られた硬化塗膜の1MHzでの誘電率を測定した。誘電率が小さいほど電気特性が良好である。結果を表1に示す。
〔実施例4〕
実施例1で得られた樹脂溶液(S-1)100質量部、1-[1-(4-ヒドロキシフェニル)イソプロピル]-4-[1,1-ビス(4-ヒドロキシフェニル)エチル]ベンゼン-1,2-ナフトキノンジアジド-5-スルホン酸エステル6.25質量部及びプロピレングリコールモノメチルエーテルアセテート75質量部を混合溶解し、0.2μmのメンブランフィルターで濾過を行い、溶液状態の感光性樹脂組成物(S-5)を調製した。
実施例2で得られた樹脂溶液(S-2)を用い、実施例4と同様に溶液状態の感光性樹脂組成物(S-6)を調製した。
実施例3で得られた樹脂溶液(S-3)を用い、実施例4と同様に溶液状態の感光性樹脂組成物(S-7)を調製した。
比較例1で得られた樹脂溶液(S-4)を用い、実施例4と同様に溶液状態の感光性樹脂組成物(S-8)を調製した。
(1)保存安定性
感光性樹脂組成物(S-5)~(S-8)を室温で1ヶ月間保存した後の粘度を測定した。なお、粘度は、E型粘度計を用いて25℃で測定を行った。調製直後の粘度に対し、室温1ヶ月間保存後の粘度上昇率が10%未満の場合を○、10%以上の場合を×とした。結果を表2に示す。
感光性樹脂組成物(S-5)~(S-8)を、ガラス基板上に膜厚3μmとなるように塗布し、オーブンにて80℃で30分間乾燥した。何れの感光性樹脂組成物でも厚さが均一な透明な樹脂膜が得られ、塗布性は良好(○)であった。
乾燥した樹脂膜にポジパターンマスクを介して超高圧水銀灯で露光し、2.38重量%テトラメチルアンモニウムヒドロキシドの水溶液にて1分間浸漬して現像し、純水でリンスを行った。何れの感光性樹脂組成物でもポジパターンが転写され、現像性は良好(○)であった。
乾燥した樹脂膜にポジパターンマスクを介さずに全面露光し、オーブンにて200℃で30分間加熱硬化させた。得られた硬化樹脂膜付きのガラス基板について、分光光度計を使用して、波長400~800nmでの最低透過率をガラス基板をブランクとして測定した。透過率が大きいほど透明性が高い。結果を表2に示す。
200℃で30分間加熱硬化させた後、再び230℃で10時間加熱処理し、波長400nmでの透過率をガラス基板をブランクとして測定した。透過率が大きいほど耐熱変色性が高い。結果を表2に示す。
Claims (9)
- ヒドロキシフェニル(メタ)アクリレート由来の繰り返し単位と、ブロックされたイソシアネート基含有不飽和化合物由来の繰り返し単位とを含むことを特徴とする共重合体。
- 前記ヒドロキシフェニル(メタ)アクリレート由来の繰り返し単位30mol%~90mol%と、前記ブロックされたイソシアネート基含有不飽和化合物由来の繰り返し単位10mol%~70mol%とを含むことを特徴とする請求項1に記載の共重合体。
- 前記ブロックされたイソシアネート基含有不飽和化合物が、ブロックされた2-イソシアナトエチル(メタ)アクリレートであることを特徴とする請求項1又は2に記載の共重合体。
- 前記ブロックが、メチルエチルケトンオキシムによるものであることを特徴とする請求項1~3の何れか一項に記載の共重合体。
- 前記ブロックされたイソシアネート基含有不飽和化合物が、2-(0-[1'-メチルプロピリデンアミノ]カルボキシアミノ)エチル(メタ)アクリレートであることを特徴とする請求項1~4の何れか一項に記載の共重合体。
- 請求項1~5の何れか一項に記載の共重合体及びキノンジアジド基含有化合物を含有することを特徴とする感光性樹脂組成物。
- 前記共重合体100質量部に対して、前記キノンジアジド基含有化合物を5~60質量部含むことを特徴とする請求項6に記載の感光性樹脂組成物。
- 溶媒以外の成分の合計量100質量部に対して、溶媒を30~4000質量部含むことを特徴とする請求項6又は7に記載の感光性樹脂組成物。
- 請求項6~8の何れか一項に記載の感光性樹脂組成物を基板上に塗布し、乾燥して得られることを特徴とする樹脂膜。
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