WO2008056750A1 - Composition de résine photosensible - Google Patents

Composition de résine photosensible Download PDF

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Publication number
WO2008056750A1
WO2008056750A1 PCT/JP2007/071739 JP2007071739W WO2008056750A1 WO 2008056750 A1 WO2008056750 A1 WO 2008056750A1 JP 2007071739 W JP2007071739 W JP 2007071739W WO 2008056750 A1 WO2008056750 A1 WO 2008056750A1
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WIPO (PCT)
Prior art keywords
photosensitive resin
resin composition
meth
copolymer
molecule
Prior art date
Application number
PCT/JP2007/071739
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English (en)
Japanese (ja)
Inventor
Takehiro Kinoshita
Hikaru Sato
Takayuki Yanai
Original Assignee
Showa Highpolymer Co., Ltd.
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Application filed by Showa Highpolymer Co., Ltd. filed Critical Showa Highpolymer Co., Ltd.
Priority to KR1020097004881A priority Critical patent/KR101356950B1/ko
Priority to CN2007800354678A priority patent/CN101517486B/zh
Priority to JP2008543128A priority patent/JP5026435B2/ja
Publication of WO2008056750A1 publication Critical patent/WO2008056750A1/fr

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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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • 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
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • the present invention relates to a photosensitive resin composition. More specifically, it can be suitably used for solder resists, various coatings, adhesives, binders for printing inks, binders for color filters, etc., and a cured coating film excellent in heat resistance, adhesion to the substrate, and development characteristics. It is related with the photosensitive resin composition which can form.
  • Patent Document 1 a method of mixing an inorganic filler into a photosensitive resin composition using a (meth) acrylic copolymer has been proposed (for example, Patent Document 1).
  • the power of color filters used in color liquid crystal display devices and solid-state image sensors have red (R), green (G), blue (B), etc. in a predetermined pattern on the substrate. It consists of a colored paint film and a black black matrix between them. Usually, a black matrix is formed on a transparent substrate such as glass, and then a colored coating pattern such as R, G, and B is sequentially formed.
  • a color filter is manufactured by a manufacturing method such as a dyeing method, a printing method, a pigment dispersion method, or an electrodeposition method.
  • a manufacturing method such as a dyeing method, a printing method, a pigment dispersion method, or an electrodeposition method.
  • the pigment dispersion method is a photo-resisting method that uses a photocurable resin composition mainly composed of a photopolymerization initiator, pigment, and solvent, and is applied on a transparent substrate and is repeatedly exposed, developed, and post-cured. ⁇ Excellent durability such as heat resistance, and few defects such as pinholes.
  • the pigment dispersion method has the above-mentioned advantages, it repeatedly forms a pattern such as a black matrix, R, G, B, etc., so that it can be applied to an alkali-soluble resin as a binder for a coating film. Heat resistance and adhesion to the substrate are required.
  • the latter resin composition comprising a monomer containing maleimide as a copolymerization component is colored from yellow to tan due to the nitrogen atoms contained in the molecule, which deteriorates the transparency of the coating film. Let me. Furthermore, there has been a problem that coloring further proceeds during post-curing after heat treatment.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2006-190848
  • Patent Document 2 JP 2004-240396 A
  • Patent Document 3 Japanese Unexamined Patent Publication No. 2003-29018
  • An object of the present invention is to provide a photosensitive resin composition capable of forming a cured coating film having development characteristics that can be used in a photolithographic process and having excellent heat resistance, adhesion, and transparency.
  • the present inventors have intensively studied to solve the above problems. As a result, it has a polymerizable monomer (a-1) having two or more hydroxyl groups in the molecule and a bridge structure having 6 to 20 carbon atoms in the molecule! /, May! /, Alicyclic
  • a resin composition containing a copolymer containing a polymerizable monomer (a-2) having a formula skeleton as an essential component can solve the above problems, and completed the present invention based on this finding.
  • the photosensitive resin composition of the present invention comprises a polymer component (A) and a photopolymerizable monomer.
  • the polymer component (A) comprises a polymerizable monomer (a-1) having two or more hydroxyl groups in the molecule, and a carbon number in the molecule. It has a 6 to 20 bridge structure! /, May! /, A copolymer comprising a monomer component which essentially comprises a polymerizable monomer (a-2) having an alicyclic skeleton. It is a polymer.
  • a photosensitive resin composition capable of forming a cured coating film having development characteristics that can be used in a photolithographic process and having excellent heat resistance, adhesion, and transparency. Can do.
  • the cured coating film formed from the photosensitive resin composition of the present invention has excellent heat resistance and adhesion to glass substrates and semiconductor substrates, and has alkali developability, so that it can be used in various resist fields.
  • the utility value is extremely high.
  • the photosensitive resin composition of the present invention comprises a polymerizable monomer (a-1) having two or more hydroxyl groups in the molecule, and a fat having a crosslinked structure having 6 to 20 carbon atoms in the molecule.
  • Development characteristics that can be used in the photolithographic process by including as a polymer component (A) a copolymer containing a monomer component that essentially contains a polymerizable monomer (a-2) having a cyclic skeleton.
  • a cured coating film excellent in heat resistance, adhesion, and transparency can be formed.
  • the polymerizable monomer (a-1) having two or more hydroxyl groups in the molecule is not particularly limited.
  • Specific examples include alkylene polyols such as glycerol mono (meth) acrylate, butanetriol mono (meth) acrylate, pentane triol mono (meth) acrylate, mono (meth) acrylates, caffeic acid, shikimi An acid etc. can be mentioned.
  • alkylene polyols such as glycerol mono (meth) acrylate, butanetriol mono (meth) acrylate, pentane triol mono (meth) acrylate, mono (meth) acrylates, caffeic acid, shikimi An acid etc.
  • glycerol mono (meth) acrylate is particularly preferred from the viewpoint of adhesion and development characteristics.
  • the ratio of the polymerizable monomer (a-1) having two or more hydroxyl groups in the molecule in the monomer component when obtaining the polymer component (A) is not particularly limited. It is 3 to 30% by mole, preferably 5 to 20%, more preferably 5 to 15% by mole in the body component.
  • the coating performance such as adhesion is sufficient, and the amount of hydroxyl group introduced is kept appropriate, so that the viscosity of the photosensitive resin composition solution is high. It is not necessary to increase the solvent ratio in the photosensitive resin composition, so that the degree of freedom in blending can be kept high.
  • the blending ratio of other monomers can be made relatively high, the heat resistance is not lowered, and the introduction amount of carboxyl groups necessary for alkali development and photosensitive groups necessary for photocuring described later is limited. There is nothing.
  • the polymerizable monomer (a1) has a high function of imparting developability and adhesion, and therefore requires a small proportion of compounding. Therefore, the polymerizable monomer (a1) has relatively high heat resistance and developability. It is possible to increase the blending ratio of the polymerizable monomer to be imparted and the polymerizable monomer to impart photosensitivity, and it is possible to achieve both developability / photosensitivity and heat resistance'adhesion as the polymer component (A). become.
  • the polymerizable monomer (a-2) having an alicyclic skeleton that may have a bridging structure having 6 to 20 carbon atoms in the molecule cyclohexyl (meth) atally , Methyl cyclohexyl (meth) acrylate, ethyl cyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, 1,4-cyclohexane dimethanol mono (meth) acrylate, tricyclodeca Nyl (meth) acrylate, tricyclodecanyloxychetyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentuloxychetyl (meth) acrylate, isobornyl (meta) ) Atalylate, adamantyl (meth) acrylate, rosin (meth) acrylate, norbornyl (meth) atally , Methyl
  • alpha Binen alpha monoterpenes with C C2 bond in the molecule, such as Tabineoru And cycloalkenes such as norbornene, 5-methylnorbornene, 5-norbornene-2-strong rubonic acid, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic anhydride, and the like.
  • cyclohexyl (meth) acrylate, tricyclodecanyl (meth) acrylate, rosin (meth) acrylate and norbornene are preferable.
  • the molecule in the monomer component has a bridge structure having 6 to 20 carbon atoms! /, May! /, An alicyclic skeleton.
  • the proportion of the polymerizable monomer (a- 2) having is not limited especially, total monomer components in the 3 to 30 mole 0/0, preferably from 5 to 20 mole 0/0, more preferably 5; 15 It should be mol%. If the compound (a-2) is within this range, the adhesion ratio with other substrates will be relatively low and the adhesion to the substrate will be sufficient. There is no limitation on the amount of photosensitive groups required for photocuring.
  • the amount of the alicyclic skeleton that may have a bridge structure does not increase, the solubility of the resin in the developer does not decrease, the development process does not take long, and development is impossible. A predetermined pattern can be obtained without becoming. In addition, the coating performance such as heat resistance is sufficient.
  • the polymer component (A) has an acid value of 20 to 180 mgKOH / g, preferably 30 to 150 mg KOH / g, more preferably 40 to 140 mgKOH / g.
  • the acid value is within this range, sufficient alkali development characteristics can be obtained. That is, the acid value strength S is within this range, the solubility in an alkaline developer is sufficient, and the cured portion is dissolved in an alkaline developer or swelled in an alkaline developer.
  • the polymer component (A) preferably has a weight average molecular weight (a numerical value in terms of polystyrene by GPC method) of 000 to 80,000. If the weight average molecular weight is within this range, the heat resistance and the solubility in an alkali developer that does not deteriorate the flexibility are sufficient.
  • an unsaturated monobasic acid (a-3) is used as a copolymerization component (copolymer (A-1) or copolymer (A — 2)), formed after reacting an unsaturated monobasic acid (a-3) with the epoxy group of a copolymer using a radically polymerizable compound (a-5) having an epoxy group as a copolymerization component
  • a method of reacting a polybasic acid anhydride (a-6) with a hydroxyl group or a hydroxyl group of a copolymer component (a-1) (copolymer (A-3)) is known!
  • Copolymer (A-1) is a force obtained by copolymerizing (a-1) with (a-2), (a-3) and (a-4).
  • (A-1) is 3 to 30 mol%, preferably 5 to 20 mol, based on all monomer components.
  • / o more preferably 5 to 15 mol%, (a- 2) 3 to 30 mol%, preferably from 5 to 20 Mo Honoré 0 / o, more preferably (or 5; 15 Monore 0/0, (a - 3) power 20-70 Monore 0/0, preferably (or 20-60 Monore 0 / o, more preferably (or 20-50 Monore 0/0, (a- 4) power 0-75 Monore 0/0, preferably (Also 20 to 60 mol%, more preferably 25 to 50 mol%, and the total is 100 mol%.
  • (a-3) is used to give a carboxyl group to the side chain of the copolymer (A-1) to give an acid value.
  • the unsaturated monobasic acid (a-3) of the present invention is not particularly limited, and examples thereof include (meth) acrylic acid, crotonic acid, cinnamic acid and the like.
  • polyfunctional (meth) acrylates having one hydroxyl group and one or more (meth) atalyloyl groups for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) ) Atarylate, trimethylolpropane di (meth) acrylate, etc.
  • (meth) acrylic acid is preferably used. These may be used alone or in combination of two or more.
  • the radical polymerizable compound (a4) other than (a-1), (a2) and (a3) is not particularly limited as long as it has an ethylenically unsaturated group.
  • Specific examples thereof include gens such as butagen, 2,3 dimethylbutadiene, isoprene and black-opened plane; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso Propyl (meth) acrylate, n butyl (meth) acrylate, sec butyl (meth) acrylate, tert butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, benzyl (meth) ate Rate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, lauryl
  • benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, styrene or butyltoluene are preferably used from the viewpoint of adhesion and transparency of the cured coating film. These may be used alone or in combination of two or more.
  • the radical copolymerization reaction for obtaining the copolymer (A-1) is not particularly limited, and a conventional radical polymerization method conventionally performed can be applied.
  • a darikol ether solvent such as propylene glycol monomethino ethenore acetate or propylene glycol monomethino ethenore acetate, a hydrocarbon group such as toluene or xylene, or a functional group such as ethyl acetate.
  • a-1), (a-2), preferably (a-3) and (a-4) copolymer components are dissolved in a desired ratio, Polymerization initiators such as tyronitrile, azobisisovaleronitryl, benzoyl peroxide, t-butylperoxy 2-ethylhexanoate are mixed and refluxed at about 50-130 ° C, 1-20 By polymerizing for about an hour, an organic solvent solution of the copolymer (A-1) can be obtained.
  • the amount of the polymerization initiator used is usually about 0.5 to 20 parts by mass with respect to 100 parts by mass of the total amount of (a-1), (a-2), (a-3) and (a-4). Preferably, 1.0 to 10 parts by mass.
  • Bulk polymerization may be carried out by using only (a-1), (a-2), (a-3) and (a-4) and a polymerization initiator without using an organic solvent.
  • the amount of the organic solvent used is usually about 30 to about 1000 parts by mass with respect to 100 parts by mass of the total amount of (a-1), (a-2), (a-3) and (a-4).
  • the amount is preferably about 50 to 800 parts by mass.
  • an abnormal polymerization reaction can be prevented and a stable polymerization reaction can be promoted, and the resin can be prevented from being colored or gelled.
  • the copolymer (A-1) of the present invention is mainly used as an electronic material such as a resist as a photosensitive resin composition in which a reactive diluent and a solvent described later are mixed.
  • a glycol ester solvent such as propylene glycol monomethyl ether acetate is preferably used.
  • Copolymer (A-2) is obtained by copolymerizing (a-1), (a-2), (a-3) and (a-4). Obtained by reacting component (a-5) with a carboxyl group.
  • the copolymerization ratio of (a-1), (a-2), (a-3), and (a-4) is the same as that of copolymer (A-1), but is also present in the side chain.
  • a radically polymerizable compound having an epoxy group (a-5) a part of the carboxyl group is converted to an unsaturated group.
  • the amount of the radically polymerizable compound having an epoxy group (a-5) used is 5 to 80 mol with respect to 100 mol of carboxyl groups present in the side chain of the copolymer.
  • the curability of the copolymer (A-2) having a good balance between the carboxyl group and the unsaturated group and the developability with alkali are appropriately maintained.
  • copolymerization reaction of (a-1), (a-2), (a-3) and (a-4) can be carried out under the same conditions as for copolymer (A-1).
  • the radically polymerizable compound having an epoxy group (a-5) is not particularly limited.
  • 3, 4-epoxycyclohexane having glycidyl (meth) acrylate and cyclic epoxy is used.
  • Xylmethyl (meth) atalylate and its rataton adduct eg, Cyclomer A200, M100, manufactured by Daicel Chemical Industries, Ltd.
  • Acrylic acid ester, dicyclopentuyl (meth) acrylated epoxidized product, dicyclopentuoxychetyl (meth) acrylated epoxidized compound S, and glycidyl (meta) ) Atallate and 3,4-epoxycyclohexylmethyl (meth) acrylate are preferably used. These may be used alone or in combination of two or more.
  • the reaction of the radical polymerizable compound having the epoxy group (a-5) with the carboxyl group in the copolymer is carried out as follows. That is, in order to prevent gelation due to the polymerization of unsaturated monobasic acid or the unsaturated group-containing copolymer to be produced, in the presence of a polymerization inhibitor such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, oxygen, etc., and In the presence of a catalyst such as a tertiary amine such as triethylbenzyl ammonium chloride, a quaternary ammonium salt such as triphenylbenzyl ammonium, a phosphorus compound such as triphenylphosphine, or a chelating compound of chromium, usually about 50 to about 150 ° C
  • the reaction is preferably carried out at 80 ° C; 130 ° C.
  • Copolymer (A-3) is obtained by copolymerizing (a-1), (a-2), (a-5) and (a-4). After (a-3) is reacted with an epoxy group, the resulting hydroxyl group or (a-1) is reacted with polybasic acid anhydride (a6).
  • the copolymerization ratio of (a-1), (a2), (a-5) and (a-4) is such that (a-1) is 3 to 30 mol%, preferably 5 to 20 mole 0/0, more preferably 5 to; 15 mole 0/0, (a- 2) 3 to 30 mole 0/0, the good Mashiku 5-20 mole 0/0, more preferably 5; 15 mole 0/0, (& -5) 30 to 85 mol%, favorable Mashiku (or 30-70 Monore 0/0, more preferably (or 30-60 Monore 0/0, (a- 4) power 0 65 Monore 0/0, preferably 15 to 55 mol%, more preferably 25 to 50 mol%, the sum is 100 mode Honoré%.
  • (a-5) is used to introduce an unsaturated group by introducing an epoxy group into the side chain of the copolymer and reacting with the subsequent carboxyl group of (a-3).
  • polybasic acid It is also used to introduce acid value by reacting with anhydride (a-6). Therefore, the function is different from that of (a-5) introduced into the side chain of the copolymer (A-2), and the introduction amount is also different! /,
  • the same epoxy compound as 1S can be used.
  • the introduction amount of epoxy groups that is, the introduction amount of unsaturated groups derived from the unsaturated monobasic acid of (a-3) is controlled.
  • the curability of the copolymer (A-3) can be controlled.
  • the copolymer (A-3) is obtained by radical copolymerization of the above (a-1), (a-2), preferably (a-5) and (a-4). After the formation, it is obtained by reacting the unsaturated monobasic acid (a-3) and then reacting the polybasic acid anhydride (a-6). The carboxyl group of the unsaturated monobasic acid (a-3) reacts with the side chain epoxy group derived from (a-5) to open the epoxy group, forming a hydroxyl group and unsaturated at the end A group is attached.
  • the polybasic acid anhydride of (a-6) is obtained by reacting the hydroxyl group of (a-1) or the carboxyl group in (a-3) with the side chain epoxy group derived from (a-5). It reacts with the generated hydroxyl group to open the anhydride group and convert it to a carboxyl group.
  • the amount of the unsaturated monobasic acid that is (a-3) is the side chain epoxy group derived from (a-5)
  • 100 to 100 monoles preferably 30 to 100 monoles, more preferably 50 to 100 monoles.
  • the amount of unsaturated monobasic acid used By setting the amount of unsaturated monobasic acid used to 10 mol or more, the minimum amount of unsaturated groups necessary for the resin to cure can be introduced, and the amount of unsaturated monobasic acid used is 100 mol. By making the following, the amount of unreacted unsaturated monobasic acid in the obtained copolymer (A-3) of the present invention can be reduced.
  • the amount of the polybasic acid anhydride (a-6) to be reacted is such that the hydroxyl group of (a-1) and the carboxyl group in (a-3) and the side chain derived from (a-5)
  • the total of hydroxyl groups generated by the reaction with epoxy groups is 5 to 00 monolayers, preferably 10 to 90 monolayers, more preferably 20 to 90 mol, relative to 100 monolayers.
  • the acid value (JIS K6901) of the resulting copolymer ( ⁇ -3) is 20 It can be controlled in the range of ⁇ 180mgKOH / g.
  • the reaction between the hydroxyl group of the copolymer and the polybasic acid anhydride (a-6) is performed on the side chain epoxy group derived from (a-5) in the copolymer. After the reaction with the unsaturated monobasic acid, a predetermined amount of (a-6) is added as it is, and the reaction is usually performed at about 50 to 150 ° C, preferably 80 to 130 ° C. There is no need to add a new catalyst.
  • the polybasic acid anhydride (a-6) in the copolymer (A-3) of the present invention is not particularly limited.
  • succinic anhydride maleic anhydride, citraconic anhydride, anhydrous Itaconic acid
  • phthalic anhydride tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like.
  • tetrahydrophthalic anhydride and succinic anhydride are preferably used. These may be used alone or in combination of two or more.
  • the photosensitive material of the present invention comprising the polymer component (A) of the copolymers (A-1) to (A-3) obtained as described above and a photopolymerizable monomer (B).
  • the photopolymerization initiator (C) and the solvent (D) can be added to the conductive resin composition.
  • the photopolymerizable monomer (B) that can be used is not particularly limited as long as it can react with the polymer component (A).
  • aromatic butyl monomers such as styrene, ⁇ -methyl styrene, ⁇ -chloromethyl styrene, butyltoluene, dibutylbenzene, diallyl phthalate, and diallylbenzene phosphate; butyl acetate, butyl adipate, etc.
  • Polycarboxylic acid monomers Methyl (meth) acrylate, Ethyl (meth) acrylate, Propinole (meth) acrylate, Butyl (meth) acrylate, ⁇ -Hydroxyethyl (meth) acrylate, Hydroxypropyl (meth) Atalylate, ethylene glycol di (meth) acrylate, jetylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate , Trimethyl low (Meth) acrylic monomers such as tripropane (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (hydroxyethyl) isocyanurate ; Skill to raise triarylcyanurate.
  • the amount of the photopolymerizable monomer ( ⁇ ) added is usually 100 parts by mass of the polymer component ( ⁇ ). 10 to 200 parts by mass, preferably 20 to 150 parts by mass.
  • the photocurability can be maintained in an appropriate range, and the viscosity can be adjusted.
  • the solvent (D) to be added to the photosensitive resin composition is not limited as long as it does not react with the polymer component (A) and the photopolymerizable monomer (B)! can do
  • Solvents (D) that can be used include propylene glycol monomethyl ether, propylene glycol monomethino ethenore acetate, dipropylene glycol monomono methinoate acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethenoate, Dipropylene glycol monomethylenoate etherate, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl enoate etherate acetate, Examples thereof include diethyleneglycolenoretinoyl acetate. Among these, propylene glycol monomethyl ether acetate preferably used in the radical polymerization reaction is preferably used.
  • the addition amount of the solvent (D) is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass with respect to 100 parts by mass of the polymer component (A). By setting it in the above range, the viscosity can be kept moderate.
  • a photopolymerization initiator (C) is added.
  • the photopolymerization initiator (C) that can be used is not particularly limited.
  • benzoin such as benzoin, benzoin methyl ether, and benzoin ether, and alkyl ethers thereof; acetophenone, 2,2 dimethoxy-2-phenylacetophenone 1, 1-dichloroacetophenone, acetophenones such as 4- (1-t-butyldioxy 1-methylethyl) acetophenone; 2-methylanthraquinone, 2-amylanthraquinone, 2-tbutylanthraquinone, 1-clone anthraquinone, etc.
  • Anthraquinones such as 2,4 dimethylthioxanthone, 2,4 diisopropylthioxanthone, 2-chlorothixanthone; Acetophenone Ketals such as dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 41- (l-tert-butyldioxy 1-methylethyl) benzophenone, 3, 3 ', 4, 4'-tetrax (t-butyldioxycarbonyl) benzophenone 2-Methinore 1 [4 (Methylthio) phenone] 2 Morpholinopropane 1one or 2Benzyl2 Dimethylamino-1- 1- (4 Morpholinophenol) butanone 1; Acylphosphine oxides and xanthones Can be mentioned.
  • Thioxanthones such as 2,4 dimethylthioxanthone, 2,4 diisopropylthioxanthone, 2-ch
  • the blending amount of the photopolymerization initiator (C) is usually 0 .;! To 30 parts by mass, more preferably 0. 5 to 20 parts by mass, more preferably;! To 10 parts by mass. By setting the content to 0 to 30 parts by mass, the photocurability can be maintained in an appropriate range.
  • the photosensitive resin composition of the present invention may contain a known colorant, antifoaming agent, coupling agent, leveling agent, and the like, if necessary.
  • colorant a known colorant such as an inorganic pigment, an organic pigment, or a dye can be used.
  • usable pigments include, for example, C. I. Pigment Yellow 1, 3, 12, 13, 1
  • Orange pigments such as 5, 71, 73; CI pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, Red pigments such as 254, 255, 26 4, and 265; CI pigment pigments, 15 pigments, 15: 3, 15: 4, 15: 6, 16, 60, etc .; CI pigment nozzles 1, 19, 23, 29 32, 36, 38, etc. Color pigments; CI pigment green 7, 36 etc. green pigments; CI pigment brown 23, 25 etc. brown pigments; CI pigment black 1, 7, carbon black, titanium black And black pigments such as iron oxide. These colorants may be used alone or in combination of two or more depending on the target pixel color.
  • the blending amount of the colorant is not particularly limited, but is preferably 20 to 70 parts by weight, more preferably 25 to 60 parts by weight with respect to 100 parts by weight of the solid content in the photosensitive resin composition of the present invention. Part, more preferably 30 to 50 parts by weight.
  • a known dispersant may be further added.
  • the dispersant it is preferable to use a polymer dispersant because it is excellent in dispersion stability over time.
  • polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified ester dispersants. The ability to list dispersants etc.
  • dispersants are trade names such as EFKA (manufactured by EFKA Chemicals buoy (EFKA)), Disperbyk (manufactured by Big Chemi Co., Ltd.), Disparon (manufactured by Enomoto Kasei Co., Ltd.), SOLSPERSE (manufactured by General Power Company) Etc.
  • EFKA manufactured by EFKA Chemicals buoy
  • Disperbyk manufactured by Big Chemi Co., Ltd.
  • Disparon manufactured by Enomoto Kasei Co., Ltd.
  • SOLSPERSE manufactured by General Power Company
  • the blending amount of the dispersant is not particularly limited, but is preferably 100 parts by mass or less, preferably 100 parts by mass or less based on 100 parts by mass of the pigment to be used; It is.
  • the polymer component (A) of the present invention has an acid value of 20 to 180 mg KOH / g, resists using the photosensitive resin composition containing them are developed using an alkaline aqueous solution. Can be performed.
  • the photosensitive resin composition of the present invention is applied to, for example, a printed wiring board, a glass substrate, or an array substrate by a screen printing method, a roll coater method, a curtain coater method, a spray coater method, a spin coat method, or the like.
  • development is carried out by washing away the uncured (unexposed) portion with an alkaline aqueous solution.
  • alkaline aqueous solutions used for development include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, etc., and amine-based compounds such as aminophenol-based compounds.
  • Typical examples are 3-methyl-4-amino-N, N-demethylaniline, 3-methyl-4-amino-1-N-ethyl N- ⁇ -hydroxy-ethylaniline, 3-methylenoyl 4-amino-one ethenoreone ⁇ - ⁇ -methane Sulfonamidoethylaniline, 3-methylenoyl 4-amino-ethynolein- ⁇ -methoxyethylaurine, and their sulfate, hydrochloride, or ⁇ -toluenesulfonate aqueous solutions.
  • a light source used for curing the coated surface by light irradiation a low-pressure mercury lamp, Pressure mercury lamp, high pressure mercury lamp, xenon lamp, metalno, ride lamp, etc. are used.
  • the molecular weight of the copolymer is a weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography).
  • copolymer (A 1) 2 photosensitive material having a solid content acid value of 81.7 mgKOH / g and a weight average molecular weight of 9500.
  • a resin 2) solution was obtained.
  • a photosensitive resin composition prepared by adding 30 parts of pentaerythritol tetraacrylate and 4 parts of 2,2-dimethoxy-2-phenylacetophenone as a photopolymerization initiator to 100 parts of the solid content of each photosensitive resin solution The product is applied on a glass substrate with a thickness of 10 m when wet with an applicator, and low boiling point substances are volatilized in a hot air dryer at 100 ° C.
  • the green photosensitive resin composition 1 was used, and as the comparative example 7, the green photosensitive resin composition 2 was used, respectively, so that the thickness when dried on a glass substrate with an applicator was 2 in.
  • a cured coating film of 2 ⁇ m was obtained, and alkali development was carried out with the following! /.
  • the coating film formed on the glass substrate was left in a dryer at 230 ° C for 1 hour, and the color of the coating film before and after the heat treatment was compared with a color difference meter and evaluated according to the following criteria.
  • a E * ab is 0.3 or less
  • the coating film formed on the glass substrate is left in a dryer at 230 ° C for 1 hour, and the transmittance at 400 nm of the coating film before and after the heat treatment is measured with a spectrophotometer. evaluated.
  • ⁇ Change rate of transmittance is 1% or less
  • the cured coating film exposed through the mask was spray-developed with a 0.1% aqueous sodium carbonate solution at 23 ° C, and the presence or absence of the coating film after rinsing was observed and evaluated according to the following criteria.
  • the cured coating film formed from the photosensitive resin composition of the present invention has excellent heat resistance and adhesion to glass substrates and semiconductor substrates, and has alkali developability, so that it can be used in various resist fields.
  • the utility value is extremely high.

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  • Physics & Mathematics (AREA)
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  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition de résine photosensible qui peut former un film de revêtement durci doté de propriétés de développement suffisamment bonnes pour être utilisable dans un procédé photolithographique tout en présentant une résistance à la chaleur, une adhésion et une transparence excellentes. La composition de résine photosensible contient un composant polymère (A) et un monomère photopolymérisable (B). Le composant polymère (A) est un polymère comprenant un composant monomère. Le composant monomère comprend un monomère polymérisable (a-1) contenant deux groupes hydroxyle ou plus dans sa molécule en tant que composants indispensables ; et un monomère polymérisable (a-2) doté d'un squelette alicyclique pouvant présenter une structure en pont dont la molécule contient 6 à 20 atomes de carbone.
PCT/JP2007/071739 2006-11-10 2007-11-08 Composition de résine photosensible WO2008056750A1 (fr)

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CN2007800354678A CN101517486B (zh) 2006-11-10 2007-11-08 感光性树脂组合物
JP2008543128A JP5026435B2 (ja) 2006-11-10 2007-11-08 感光性樹脂組成物

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JP2009067900A (ja) * 2007-09-13 2009-04-02 The Inctec Inc アルカリ可溶型樹脂、アルカリ可溶型感光性着色組成物、およびカラーフィルタ
JP2013011784A (ja) * 2011-06-30 2013-01-17 Nippon Shokubai Co Ltd 感光性樹脂組成物
JP2013049802A (ja) * 2011-08-31 2013-03-14 Hitachi Chemical Co Ltd 活性エネルギー線硬化型樹脂及びそれを用いたハードコート材
JP2013133459A (ja) * 2011-12-27 2013-07-08 Tamura Seisakusho Co Ltd 樹脂および当該樹脂を含む感光性組成物

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JP6135063B2 (ja) * 2011-08-30 2017-05-31 住友化学株式会社 硬化性樹脂組成物
JP6112891B2 (ja) * 2013-02-08 2017-04-12 デクセリアルズ株式会社 粘着テープ用樹脂組成物、粘着テープ及び粘着テープの製造方法
JP6218393B2 (ja) * 2013-02-28 2017-10-25 東京応化工業株式会社 層間絶縁膜用感光性樹脂組成物
KR20150029921A (ko) * 2013-09-11 2015-03-19 동우 화인켐 주식회사 디스플레이 장치의 전면 차광층 형성용 착색 감광성 수지 조성물
CN105669892B (zh) * 2016-03-17 2019-07-26 上海昭和高分子有限公司 一种溶剂型共聚树脂及其组合物
CN115710328A (zh) * 2022-10-28 2023-02-24 江苏艾森半导体材料股份有限公司 一种高分子量丙烯酸树脂

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WO2003007078A2 (fr) * 2001-07-13 2003-01-23 Coates Brothers Plc Ameliorations apportees ou relatives a des encres de resine photodurcissables
JP2006124664A (ja) * 2004-09-29 2006-05-18 Sumitomo Chemical Co Ltd 着色感光性樹脂組成物
JP2006145750A (ja) * 2004-11-18 2006-06-08 Toray Ind Inc 感光性ペースト、それを用いたプラズマディスプレイ用パネルの製造方法およびプラズマディスプレイ用パネル

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JP2005316388A (ja) * 2004-03-30 2005-11-10 Jsr Corp カラーフィルタ用感放射線性組成物、カラーフィルタおよびカラー液晶表示装置
TWI396042B (zh) * 2004-09-29 2013-05-11 Sumitomo Chemical Co 著色感光性樹脂組成物

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WO2003007078A2 (fr) * 2001-07-13 2003-01-23 Coates Brothers Plc Ameliorations apportees ou relatives a des encres de resine photodurcissables
JP2006124664A (ja) * 2004-09-29 2006-05-18 Sumitomo Chemical Co Ltd 着色感光性樹脂組成物
JP2006145750A (ja) * 2004-11-18 2006-06-08 Toray Ind Inc 感光性ペースト、それを用いたプラズマディスプレイ用パネルの製造方法およびプラズマディスプレイ用パネル

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009067900A (ja) * 2007-09-13 2009-04-02 The Inctec Inc アルカリ可溶型樹脂、アルカリ可溶型感光性着色組成物、およびカラーフィルタ
JP2013011784A (ja) * 2011-06-30 2013-01-17 Nippon Shokubai Co Ltd 感光性樹脂組成物
JP2013049802A (ja) * 2011-08-31 2013-03-14 Hitachi Chemical Co Ltd 活性エネルギー線硬化型樹脂及びそれを用いたハードコート材
JP2013133459A (ja) * 2011-12-27 2013-07-08 Tamura Seisakusho Co Ltd 樹脂および当該樹脂を含む感光性組成物

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TWI430020B (zh) 2014-03-11
CN101517486A (zh) 2009-08-26
KR101356950B1 (ko) 2014-01-28
JP5026435B2 (ja) 2012-09-12
CN101517486B (zh) 2012-06-27
KR20090080500A (ko) 2009-07-24
TW200900854A (en) 2009-01-01

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