WO2013172432A1 - アルカリ現像型の熱硬化性樹脂組成物、プリント配線板 - Google Patents

アルカリ現像型の熱硬化性樹脂組成物、プリント配線板 Download PDF

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WO2013172432A1
WO2013172432A1 PCT/JP2013/063725 JP2013063725W WO2013172432A1 WO 2013172432 A1 WO2013172432 A1 WO 2013172432A1 JP 2013063725 W JP2013063725 W JP 2013063725W WO 2013172432 A1 WO2013172432 A1 WO 2013172432A1
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resin composition
thermosetting resin
resin
alkali
group
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PCT/JP2013/063725
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English (en)
French (fr)
Japanese (ja)
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遠藤　新
峰岸　昌司
有馬　聖夫
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太陽インキ製造株式会社
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Priority to CN201380025731.5A priority Critical patent/CN104380197B/zh
Priority to KR1020147034930A priority patent/KR102073440B1/ko
Priority to JP2014515677A priority patent/JP6078535B2/ja
Publication of WO2013172432A1 publication Critical patent/WO2013172432A1/ja

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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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • 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 an alkali development type thermosetting resin composition and a printed wiring board.
  • an alkali development type photocurable resin composition using an alkaline aqueous solution as a developing solution has become mainstream in consideration of environmental problems.
  • an epoxy acrylate-modified resin hereinafter, abbreviated as epoxy acrylate
  • a photocurable resin composition is applied to a substrate and dried to form a resin layer, and the resin layer is patterned.
  • thermosetting resin and a flexible printed wiring board are mounted and used in various apparatuses. For this reason, it is required to have resistance against abrupt changes in the environment such as temperature. Therefore, high resistance to temperature change is also required for the solder resist.
  • CTE coefficient of linear expansion
  • the CTE of the thermosetting resin is matched with the CTE of the material of the peripheral member.
  • an object of the present invention is to provide an alkali development type thermosetting resin composition and printed wiring which can suppress the occurrence of cracks and obtain a resin layer having good stability in a B-stage state in the form of a dry film. To provide a board.
  • the alkali-developable thermosetting resin composition of the present invention includes an alkali-developable resin, a heat-reactive compound, a polymer resin, and a photobase generator,
  • the alkali-developable resin and the heat-reactive compound undergo an addition reaction by selective light irradiation, whereby a negative pattern can be formed by alkali development.
  • the polymer resin preferably contains one or more selected from the group consisting of block copolymers, elastomers, rubber particles, and binder polymers.
  • the alkali development type thermosetting resin composition of the present invention generates an exothermic peak in DSC measurement by light irradiation, or starts heat generation in DSC measurement of the alkali development type thermosetting resin composition irradiated with light.
  • the temperature is lower than the heat generation start temperature in the DSC measurement of the unirradiated alkali development type thermosetting resin composition, or the heat generation peak temperature in the DSC measurement of the light irradiated alkali development type thermosetting resin composition is It is preferable that the temperature is lower than the exothermic peak temperature in DSC measurement of the unirradiated alkali development type thermosetting resin composition.
  • the printed wiring board of the present invention is characterized by having a pattern layer made of any one of the alkali development type thermosetting resin compositions described above.
  • an alkali development type thermosetting resin composition capable of suppressing the generation of cracks and obtaining a resin layer having good stability in a B-stage state in the form of a dry film. Furthermore, according to the present invention, an alkali development type thermosetting resin composition capable of obtaining a pattern layer excellent in curability and cooling cycle characteristics can be provided.
  • FIG. 1 is a diagram showing an example of a pattern forming method using the alkali development type thermosetting resin composition of the present invention.
  • FIG. 2 is a diagram showing a DSC chart for the resin layer made of the alkali development type thermosetting resin composition of Example 1 of the present invention.
  • FIG. 3 is a diagram showing an example of a pattern forming method using the alkali development type thermosetting resin composition of the present invention.
  • thermosetting resin composition includes an alkali developing resin, a thermoreactive compound, a polymer resin, and It contains a photobase generator, and is characterized in that a negative pattern can be formed by alkali development by an addition reaction between an alkali-developable resin and a heat-reactive compound by selective light irradiation.
  • pattern formation means forming a patterned cured product, that is, a pattern layer.
  • a base is generated on the surface by light irradiation. The generated base destabilizes the photobase generator and further generates a base.
  • thermosetting resin composition of the present invention has an alkali-developable resin and a thermoreactive compound that are cured by addition reaction and contains a polymer resin. A pattern layer with less can be obtained.
  • thermosetting resin composition may be a composition that does not cure even when heated in an unirradiated state, and can be cured by heat only after irradiation with light.
  • thermosetting resin composition of the present invention generates a heat generation peak in DSC measurement by light irradiation, or the heat generation start temperature in DSC measurement of the light-cured thermosetting resin composition is an unirradiated thermosetting resin.
  • the exothermic peak temperature in the DSC measurement of the uncured thermosetting resin composition is lower than the exothermic peak temperature in the DSC measurement of the thermosetting resin composition that is lower than the exothermic start temperature in the DSC measurement of the composition or is irradiated with light. Is also preferably low.
  • thermosetting resin composition of the present invention is also referred to as a temperature difference ( ⁇ T start) of the heat generation starting temperature in DSC measurement between the light-irradiated thermosetting resin composition and the non-irradiated thermosetting resin composition.
  • ⁇ T start the exothermic peak temperature difference
  • ⁇ T peak is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, and even more preferably 30 ° C. or higher.
  • ⁇ T start is a thermosetting resin composition having the same composition, one is irradiated with light, and the other is not irradiated with light, and the DSC (Differential Scanning Calorimetry) is left as it is.
  • Each measurement refers to the temperature difference between the heat generation start temperature indicating the start of the curing reaction of the resin composition irradiated with light and the heat generation start temperature of the unirradiated resin composition.
  • ⁇ T peak refers to the temperature difference between the exothermic peak temperatures of the resin composition irradiated and unirradiated when DSC measurement is similarly performed.
  • the light irradiation amount in DSC measurement of the thermosetting resin composition irradiated with light increases the light irradiation amount, and the shift of the exothermic peak temperature due to the light irradiation of the thermosetting resin composition does not occur (saturation). Irradiation amount.
  • ⁇ T start or ⁇ T peak is 10 ° C.
  • ⁇ T start or ⁇ T peak is 10 ° C. or more, it is possible to widen the range of heating temperatures that can be taken in the heating step (B1) described later.
  • thermosetting resin composition Asinafter, each component of the thermosetting resin composition will be described in detail.
  • the alkali-developable resin is a resin that contains one or more functional groups among phenolic hydroxyl groups, thiol groups, and carboxyl groups and that can be developed with an alkaline solution, preferably a compound having two or more phenolic hydroxyl groups, carboxyl Examples thereof include a group-containing resin, a compound having a phenolic hydroxyl group and a carboxyl group, and a compound having two or more thiol groups.
  • Examples of the compound having two or more phenolic hydroxyl groups include phenol novolac resin, alkylphenol volac resin, bisphenol A novolac resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene modified phenol resin, polyvinylphenols, bisphenol F, Examples thereof include known and commonly used phenol resins such as bisphenol S-type phenol resin, poly-p-hydroxystyrene, a condensate of naphthol and aldehydes, and a condensate of dihydroxynaphthalene and aldehydes.
  • a phenol resin a compound having a biphenyl skeleton or a phenylene skeleton, or both, and as a phenolic hydroxyl group-containing compound, phenol, orthocresol, paracresol, metacresol, 2,3-xylenol, 2,4- Xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, phloroglucinol You may use the phenol resin which synthesize
  • the carboxyl group-containing resin a known resin containing a carboxyl group can be used. Due to the presence of the carboxyl group, the resin composition can be made alkali developable.
  • a compound having an ethylenically unsaturated bond in the molecule may be used, but in the present invention, as the carboxyl group-containing resin, for example, ethylenically unsaturated as shown in (1) below. It is preferable to use only a carboxyl group-containing resin having no double bond.
  • the lower alkyl refers to an alkyl group having 1 to 5 carbon atoms.
  • Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers
  • carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
  • Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A type Terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with the terminal of urethane resin by polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group
  • Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its partial acid anhydride modified product, carboxyl group-containing dialcohol compound and diol compound.
  • one isocyanate group and one or more (meth) acryloyl groups are present in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate.
  • the carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.
  • An unsaturated monocarboxylic acid such as (meth) acrylic acid is reacted with the polyfunctional (solid) epoxy resin as described above, and phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride is added to the hydroxyl group present in the side chain.
  • a carboxyl group-containing resin to which a dibasic acid anhydride such as an acid is added.
  • a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is reacted with a saturated monocarboxylic acid on the polyfunctional (solid) epoxy resin as described above, and the hydroxyl group present in the side chain.
  • a carboxyl group-containing resin to which is added is added.
  • a carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin as described later with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.
  • a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide is reacted with a saturated monocarboxylic acid.
  • Reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, with an unsaturated group-containing monocarboxylic acid.
  • a carboxyl group-containing resin obtained by reacting a polybasic acid anhydride with a product.
  • An epoxy compound having a plurality of epoxy groups in one molecule a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and a saturated monocarboxylic acid React with acid and react with polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid etc. to the alcoholic hydroxyl group of the resulting reaction product Carboxyl group-containing resin obtained by making it.
  • polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid etc.
  • An epoxy compound having a plurality of epoxy groups in one molecule a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and (meth) Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and then reacting with the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride such as an acid.
  • Such an alkali-developable resin has a large number of carboxyl groups, hydroxyl groups, and the like in the side chain of the backbone polymer, so that development with an alkaline aqueous solution becomes possible.
  • the hydroxyl group equivalent or carboxyl group equivalent of the carboxyl group-containing resin is 80 to 900 g / eq. And more preferably 100 to 700 g / eq. It is. Hydroxyl group equivalent or carboxyl group equivalent is 900 g / eq. If it exceeds 1, the adhesion of the pattern layer may not be obtained, or alkali development may be difficult.
  • the hydroxyl group equivalent or the carboxyl group equivalent is 80 g / eq.
  • the line becomes thinner than necessary, or in some cases, the light irradiation part and the unirradiated part are dissolved and peeled off with the developer, This is not preferable because it may be difficult to draw a normal resist pattern. Further, it is preferable that the carboxyl group equivalent or the phenol group equivalent is large because development is possible even when the content of the alkali-developable resin is small.
  • the weight average molecular weight of the alkali-developable resin used in the present invention varies depending on the resin skeleton, but is preferably in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. If the weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the resin layer after light irradiation may be poor, film thickness may be reduced during development, and resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.
  • (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
  • Examples of the compound having a thiol group include trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, ethylene glycol bisthioglycolate, 1,4-butanediol bisthioglycolate, trimethylolpropane tris.
  • Thioglycolate pentaerythritol tetrakisthioglycolate, di (2-mercaptoethyl) ether, 1,4-butanedithiol, 1,3,5-trimercaptomethylbenzene, 1,3,5-trimercaptomethyl-2 , 4,6-trimethylbenzene, terminal thiol group-containing polyether, terminal thiol group-containing polythioether, thiol compound obtained by reaction of epoxy compound with hydrogen sulfide, and reaction of polythiol compound with epoxy compound. Thiol compounds having a resultant terminal thiol group.
  • the alkali developable resin is preferably a carboxyl group-containing resin or a compound having a phenolic hydroxyl group.
  • the alkali-developable resin is preferably non-photosensitive without a photocurable structure such as epoxy acrylate. Such a non-photosensitive alkali-developable resin does not have an ester bond derived from epoxy acrylate, and therefore has high resistance to desmear liquid. Therefore, a pattern layer having excellent curing characteristics can be formed. Moreover, since it does not have a photocurable structure, curing shrinkage can be suppressed.
  • the alkali-developable resin is a carboxyl group-containing resin, development can be performed with a weak alkaline aqueous solution as compared with the case of a phenol resin.
  • Examples of the weak alkaline aqueous solution include a solution in which sodium carbonate or the like is dissolved. By developing with weak alkaline aqueous solution, it can suppress that a light irradiation part will be developed. Moreover, the light irradiation time in a process (B) and the heating time in a process (B1) can be shortened.
  • thermoreactive compound is a resin having a functional group that can be cured by heat.
  • An epoxy resin, a polyfunctional oxetane compound, etc. are mentioned.
  • the epoxy resin is a resin having an epoxy group, and any known one can be used. Examples thereof include a bifunctional epoxy resin having two epoxy groups in the molecule, and a polyfunctional epoxy resin having many epoxy groups in the molecule. In addition, a hydrogenated bifunctional epoxy compound may be used.
  • Polyfunctional epoxy compounds include bisphenol A type epoxy resin, brominated epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, alicyclic ring Epoxy resin, trihydroxyphenylmethane type epoxy resin, bixylenol type or biphenol type epoxy resin or mixtures thereof, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylolethane type epoxy resin, heterocyclic epoxy Resin, diglycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin, epoxy resin having dicyclopentadiene skeleton, glycidyl methacrylate Acrylate copolymer epoxy resins, copolymerized epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, and
  • liquid bifunctional epoxy resins include vinylcyclohexene diepoxide, (3 ′, 4′-epoxycyclohexylmethyl) -3,4-epoxycyclohexanecarboxylate, (3 ′, 4′-epoxy-6′-methyl) And alicyclic epoxy resins such as (cyclohexylmethyl) -3,4-epoxy-6-methylcyclohexanecarboxylate.
  • a naphthalene group-containing epoxy resin is preferable because it can suppress the thermal expansion of the cured product.
  • the above epoxy resins may be used alone or in combination of two or more.
  • polyfunctional oxetane compound examples include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl)
  • polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene
  • thermosetting resin composition contains a white pigment, it is preferable that a thermoreactive compound is an alicyclic skeleton. Thereby, photoreactivity can be improved.
  • the blending amount of the heat-reactive compound is preferably such that the equivalent ratio with the alkali-developable resin (heat-reactive group: alkali-developable group) is 1: 0.1 to 1:10, and 1: 0 More preferably, it is 2 to 1: 5. When the ratio is within such a range, the development is good.
  • One or more photobase generators can function as a catalyst for the addition reaction of the above-mentioned thermoreactive compound when the molecular structure is changed by irradiation with light such as ultraviolet rays or visible light, or when the molecule is cleaved. It is a compound that produces a basic substance. Examples of basic substances include secondary amines and tertiary amines. Examples of photobase generators include ⁇ -aminoacetophenone compounds, oxime ester compounds, acyloxyimino groups, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzyl carbamate groups, alkoxybenzyl carbamates. And compounds having a substituent such as a group.
  • the ⁇ -aminoacetophenone compound has a benzoin ether bond in the molecule, and when irradiated with light, cleavage occurs in the molecule to produce a basic substance (amine) that exhibits a curing catalytic action.
  • ⁇ -aminoacetophenone compounds include (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, manufactured by BASF Japan Ltd.) and 4- (methylthiobenzoyl) -1-methyl.
  • -1-morpholinoethane (Irgacure 907, trade name, manufactured by BASF Japan Ltd.), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl]-
  • a commercially available compound such as 1-butanone (Irgacure 379, trade name, manufactured by BASF Japan Ltd.) or a solution thereof can be used.
  • any compound that generates a basic substance by light irradiation can be used.
  • the oxime ester compound include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, NCI-831 manufactured by Adeka, and the like as commercially available products.
  • numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.
  • X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms).
  • Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon atom having 1 carbon atom), substituted with an alkyl group having a C 1-8 alkyl group or a dialkylamino group.
  • X and Y are each a methyl group or an ethyl group
  • Z is methyl or phenyl
  • n is 0, and Ar is a bond, phenylene, naphthylene, thiophene or thienylene. It is preferable.
  • the compound which can be represented by the following general formula can also be mentioned as a preferable carbazole oxime ester compound.
  • R 1 represents an alkyl group having 1 to 4 carbon atoms, or a phenyl group optionally substituted with a nitro group, a halogen atom, or an alkyl group having 1 to 4 carbon atoms).
  • R 2 represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group.
  • R 3 may be linked with an oxygen atom or a sulfur atom, and may be substituted with an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 4 carbon atoms which may be substituted with a phenyl group.
  • R 4 represents a nitro group or an acyl group represented by X—C ( ⁇ O) —.
  • X represents an aryl group, a thienyl group, a morpholino group, a thiophenyl group, or a structure represented by the following formula, which may be substituted with an alkyl group having 1 to 4 carbon atoms.
  • the compound having an acyloxyimino group include OO′-diacetphenone oxime succinate, O, O′-dinaphthophenone oxime succinate, and benzophenone oxime acrylate-styrene copolymer.
  • the compound having an N-formylated aromatic amino group and an N-acylated aromatic amino group include, for example, di-N- (p-formylamino) diphenylmethane, di-N (p-aceethylamino) Diphenylmelane, di-N- (p-benzamido) diphenylmethane, 4-formylaminotoluylene, 4-acetylaminotoluylene, 2,4-diformylaminotoluylene, 1-formylaminonaphthalene, 1-acetylaminonaphthalene, 1,5-diformylaminonaphthalene, 1-formylaminoanthracene, 1,4-diformylaminoanthracene, 1-acetylaminoanthracene, 1,4-diformylaminoanthracene, 1,4-diformylaminoanthracene, 1,4-diformylaminoanthr
  • the compound having a nitrobenzyl carbamate group or an alkoxybenzyl carbamate group include, for example, bis ⁇ (2-nitrobenzyl) oxy ⁇ carbonyl ⁇ diaminodiphenylmethane, 2,4-di ⁇ (2-nitrobenzyl) Oxy ⁇ toluylene, bis ⁇ (2-nitrobenzyloxy) carbonyl ⁇ hexane-1,6-diamine, m-xylidine ⁇ (2-nitro-4-chlorobenzyl) oxy ⁇ amide ⁇ and the like.
  • oxime ester compounds and ⁇ -aminoacetophenone compounds are preferable.
  • ⁇ -aminoacetophenone compound those having two or more nitrogen atoms are particularly preferable.
  • WPBG-018 Product name: 9-anthrylmethyl N, N'-diethylcarbamate
  • WPBG-027 Product name: (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine
  • WPBG-082 Product name: guanidinium2- (3-benzoylphenyl) propionate
  • WPBG-140 Product name: 1- (anthraquinon-2-yl) ethyl imidazolecarboxylate), etc.
  • the above photobase generators may be used alone or in combination of two or more.
  • the blending amount of the photobase generator in the thermosetting resin composition is preferably 1 to 50 parts by mass, more preferably 1 to 40 parts by mass with respect to 100 parts by mass of the thermoreactive compound. When the amount is less than 1 part by mass, development becomes difficult, which is not preferable.
  • the thermosetting resin composition of the present invention may contain a maleimide compound.
  • maleimide compounds include polyfunctional aliphatic / alicyclic maleimides and polyfunctional aromatic maleimides. Bifunctional or higher maleimide compounds (polyfunctional maleimide compounds) are preferred.
  • polyfunctional aliphatic / alicyclic maleimide include N, N′-methylene bismaleimide, N, N′-ethylene bismaleimide, tris (hydroxyethyl) isocyanurate, and aliphatic / alicyclic maleimide carboxylic acid.
  • aromatic polymaleimide ester compounds obtained by dehydrating esterification of maleimide carboxylic acid and various aromatic polyols, or transesterification reaction of maleimide carboxylic acid ester and various aromatic polyols; Aromatic polymaleimide ester compounds obtained by ether ring-opening reaction of carboxylic acid and various aromatic polyepoxides; Aromatic polymaleimide urethane compounds obtained by urethanization reaction of maleimide alcohol and various aromatic polyisocyanates, etc. And aromatic polyfunctional maleimides.
  • polyfunctional aromatic maleimide examples include, for example, N, N ′-(4,4′-diphenylmethane) bismaleimide, N, N′-2,4-tolylene bismaleimide, N, N′-2, 6-tolylene bismaleimide, 1-methyl-2,4-bismaleimide benzene, N, N′-m-phenylene bismaleimide, N, N′-p-phenylene bismaleimide, N, N′-m-toluylene Bismaleimide, N, N′-4,4′-biphenylenebismaleimide, N, N′-4,4 ′-[3,3′-dimethyl-biphenylene] bismaleimide, N, N′-4,4′- [3,3′-dimethyldiphenylmethane] bismaleimide, N, N′-4,4 ′-[3,3′-diethyldiphenylmethane] bismaleimide, N, N′-4,4′-diphenylme
  • the blending amount of the maleimide compound is preferably such that the equivalent ratio to the alkali-developable resin (maleimide group: alkali-developable group) is 1: 0.1 to 1:10, and 1: 0.2 to 1: 5. It is more preferable that With such a blending ratio, development is facilitated.
  • thermosetting resin composition of the present invention a conventionally known polymer resin can be blended for the purpose of improving the flexibility and dryness of the touch of the resulting cured product.
  • the polymer resin include cellulose-based, polyester-based, phenoxy-resin-based, polyvinyl acetal-based, polyvinyl butyral-based, polyamide-based, polyamide-imide-based binder polymers, block copolymers, elastomers, and rubber particles.
  • One type of polymer resin may be used alone, or two or more types may be used in combination.
  • the melt viscosity of the thermosetting resin composition is increased, and the fluidity of the resin in the through-hole portion can be suppressed during post-exposure heating. As a result, a flat substrate that is not recessed on the through hole can be manufactured.
  • the amount of the polymer resin added is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, and particularly preferably 5 to 30 parts by mass with respect to 100 parts by mass of the thermoreactive compound.
  • the amount of the polymer resin exceeds 50 parts by mass, there is a concern about deterioration of desmear resistance of the thermosetting resin composition, which is not preferable.
  • the block copolymer is a copolymer having a molecular structure in which two or more kinds of polymers having different properties are connected by a covalent bond to form a long chain.
  • the block copolymer used in the present invention is preferably an ABA or ABA ′ type block copolymer.
  • the central B is a soft block and has a low glass transition point Tg, preferably less than 0 ° C. Is a hard block and has a high Tg, and is preferably composed of polymer units of 0 ° C. or higher.
  • the glass transition point Tg is measured by differential scanning calorimetry (DSC).
  • a or A ′ is composed of polymer units having a Tg of 50 ° C. or more
  • B is a polymer unit having a Tg of ⁇ 20 ° C.
  • a or A ′ preferably includes polymethyl (meth) acrylate (PMMA), polystyrene (PS) or the like, and B preferably includes poly n-butyl acrylate (PBA), polybutadiene (PB) or the like.
  • PMMA polymethyl (meth) acrylate
  • PS polystyrene
  • PBA poly n-butyl acrylate
  • PB polybutadiene
  • a hydrophilic unit excellent in compatibility with the matrix described above represented by a styrene unit, a hydroxyl group-containing unit, a carboxyl group-containing unit, an epoxy-containing unit, an N-substituted acrylamide unit, etc. as part of the A or A ′ component It becomes possible to introduce and further improve the compatibility.
  • the block copolymer used in the present invention is preferably a ternary or more block copolymer, and a block copolymer having a precisely controlled molecular structure synthesized by a living polymerization method is effective for obtaining the effects of the present invention. More preferred. This is considered to be because the block copolymer synthesized by the living polymerization method has a narrow molecular weight distribution, and the characteristics of each unit have been clarified.
  • the molecular weight distribution (Mw / Mn) of the block copolymer used is preferably 3 or less, more preferably 2.5 or less, and still more preferably 2.0 or less.
  • the block copolymers containing the (meth) acrylate polymer block as described above are, for example, the methods described in JP-A-2007-516326 and JP-A-2005-515281, particularly the following formulas (1) to (4).
  • the Y unit is polymerized using the alkoxyamine compound represented by any of the above as an initiator, it can be suitably obtained by polymerizing the X unit.
  • n 2 and Z represents a divalent organic group, preferably 1,2-ethanedioxy, 1,3-propanedioxy, 1,4-butanedioxy, 1,6-hexanedioxy Selected from among oxy, 1,3,5-tris (2-ethoxy) cyanuric acid, polyaminoamines such as polyethyleneamine, 1,3,5-tris (2-ethylamino) cyanuric acid, polythioxy, phosphonate or polyphosphonate Ar represents a divalent aryl group.
  • the weight average molecular weight of the block copolymer is preferably in the range of 20,000 to 400,000, more preferably 50,000 to 300,000.
  • the weight average molecular weight is less than 20,000, the desired toughness and flexibility effects cannot be obtained, and when the thermosetting resin composition is formed into a dry film or applied to a substrate and temporarily dried. Inferior to tackiness.
  • the weight average molecular weight exceeds 400,000, the viscosity of the thermosetting resin composition becomes high, and the printability and processability may be remarkably deteriorated.
  • the weight average molecular weight is 50000 or more, an excellent effect is obtained in terms of relaxation against external impact.
  • a block copolymer is preferable because it is excellent in crack resistance during a thermal cycle and can suppress warping after curing.
  • the block copolymer is particularly preferable because it can suppress a dent on the through hole and create a substrate having a flat surface. Moreover, it is excellent in the crack tolerance at the time of a thermal cycle by combining with an inorganic filler.
  • An elastomer having a functional group can be added to the thermosetting resin composition of the present invention. By adding an elastomer having a functional group, it is expected that the coating property is improved and the strength of the coating film is also improved. Further, polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyester amide elastomers, acrylic elastomers, olefin elastomers, and the like can be used. In addition, resins in which a part or all of epoxy groups of epoxy resins having various skeletons are modified with carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can be used.
  • epoxy-containing polybutadiene elastomers acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers, and the like can also be used.
  • these elastomers may be used individually by 1 type, and may use 2 or more types together.
  • the rubber particles may be any particles as long as they are formed from organic substances such as polymers having a crosslinked structure.
  • a copolymer of acrylonitrile butadiene a crosslinked acrylonitrile and butadiene are copolymerized.
  • NBR particles Copolymerized acrylonitrile, butadiene and carboxylic acid such as acrylic acid; cross-linked polybutadiene, cross-linked silicon rubber, or cross-linked rubber particles having a so-called core-shell structure using NBR as a core layer and cross-linked acrylic resin as a shell layer (Also referred to as “core-shell rubber particles”).
  • a core-shell structured crosslinked rubber particle is preferable.
  • Cross-linked NBR particles are particles obtained by partially cross-linking acrylonitrile and butadiene at the stage of copolymerization and copolymerization. It is also possible to obtain carboxylic acid-modified crosslinked NBR particles by copolymerizing together carboxylic acids such as acrylic acid and methacrylic acid.
  • Cross-linked butadiene rubber-cross-linked acrylic resin core-shell rubber particles can be obtained by a two-stage polymerization method in which butadiene particles are polymerized by emulsion polymerization, followed by addition of monomers such as acrylic acid ester and acrylic acid. .
  • Cross-linked silicone rubber-cross-linked acrylic resin core-shell rubber particles can be obtained by a two-stage polymerization method in which silicon particles are polymerized by emulsion polymerization, followed by addition of monomers such as acrylic acid ester and acrylic acid. .
  • the size of the rubber particles is 1 ⁇ m or less in terms of primary average particle diameter, and is preferably 50 nm to 1 ⁇ m. If the primary average particle diameter exceeds 1 ⁇ m, the adhesive strength is lowered and the insulation reliability in fine wiring is impaired.
  • the “primary average particle diameter” here refers to the aggregated particle diameter, that is, the secondary particle diameter, not the aggregated single particle diameter.
  • the primary average particle diameter can be determined by measuring with a laser diffraction particle size distribution meter, for example.
  • the rubber particles as described above may be used alone or in combination of two or more.
  • the content of the rubber particles is preferably 50% by mass or less in the resin composition, and more preferably 1 to 30% by mass.
  • a commercially available product of carboxylic acid-modified acrylonitrile butadiene rubber particles is XER-91 manufactured by Nippon Synthetic Rubber Co., Ltd.
  • Examples of the core-shell particles of butadiene rubber-acrylic resin include Paraloid EXL2655 manufactured by Rohm and Haas Co., Ltd. and AC-3832 manufactured by Ganz Kasei Kogyo Co., Ltd.
  • Examples of the core-shell rubber particles of the crosslinked silicone rubber-acrylic resin include GENIOPERLP52 manufactured by Asahi Kasei Wacker Silicone Co., Ltd. By using rubber particles, it is possible to improve the crack resistance during the cooling and heating cycle.
  • the thermosetting resin composition preferably contains an inorganic filler.
  • the inorganic filler is used for suppressing the curing shrinkage of the cured product of the thermosetting resin composition and improving the properties such as adhesion and hardness.
  • Examples of the inorganic filler include barium sulfate, amorphous silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, boron nitride, and Neuburg Examples include rich earth.
  • the average particle size (D50) of the inorganic filler is preferably 1 ⁇ m or less, more preferably 0.7 ⁇ m or less, and even more preferably 0.5 ⁇ m. When the average particle diameter exceeds 1 ⁇ m, the pattern layer may become cloudy, which is not preferable.
  • the lower limit of the average particle diameter (D50) of the inorganic filler is not particularly limited, it is, for example, 0.01 ⁇ m or more.
  • the average particle diameter (D50) means an average primary particle diameter.
  • the average particle diameter (D50) can be measured by a laser diffraction / scattering method.
  • the refractive index is close to that of the resin component, the permeability is improved, and the generation efficiency of the base from the photobase generator by light irradiation is increased.
  • the difference in refractive index between the inorganic filler and the alkali developable resin is preferably 0.3 or less. By setting the difference in refractive index to 0.3 or less, it is possible to suppress light scattering and obtain good deep-curing characteristics.
  • the refractive index of the inorganic filler is preferably 1.4 or more and 1.8 or less.
  • the refractive index of an inorganic filler can be measured based on JISK7105.
  • the blending ratio of the inorganic filler is preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 80% by mass or less based on the total solid content of the thermosetting resin composition.
  • the blending ratio of the inorganic filler exceeds 80% by mass, the viscosity of the composition increases, and the applicability may decrease or the cured product of the thermosetting resin composition may become brittle.
  • the resolution decreases, but in the present invention, since it is a curing reaction by the generated base, the inclusion of the inorganic filler Even when the amount is increased, good resolution can be maintained.
  • the specific gravity of an inorganic filler is 3 or less, More preferably, it is 2.8 or less, More preferably, it is 2.5 or less.
  • the specific gravity of the inorganic filler is 3 or less, thermal expansion can be suppressed.
  • the inorganic filler of 3 or less include silica and aluminum hydroxide, and silica is particularly preferable.
  • the shape of the inorganic filler include an indeterminate shape, a needle shape, a disc shape, a scale piece, a spherical shape, and a hollow shape.
  • the spherical shape is preferable because it can be blended in the composition at a high ratio.
  • the inorganic filler is more preferably treated with a surface treatment agent such as a silane coupling agent.
  • a surface treatment agent such as a silane coupling agent.
  • the crack tolerance at the time of a thermal cycle can be improved by containing an inorganic filler. By containing a large amount of the inorganic filler, warping after curing can be suppressed.
  • cured material is 40 ppm or less, More preferably, it is 30 ppm or less, More preferably, it is 20 ppm or less.
  • thermosetting resin composition of the present invention an organic solvent can be used for preparing the resin composition or adjusting the viscosity for application to a substrate or a carrier film.
  • organic solvents examples include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. Such an organic solvent may be used individually by 1 type, and may be used as a 2 or more types of mixture.
  • thermosetting resin composition of the present invention may contain a photopolymerizable monomer as long as the effects of the present invention are not impaired.
  • Photopolymerizable monomers include alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate; hydroxyalkyl such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate (Meth) acrylates; mono- or di (meth) acrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, Polyhydric alcohols such as trishydroxyethyl isocyanurate or polyvalent (meth)
  • the blending amount of the photopolymerizable monomer is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably based on the solid content excluding the solvent of the thermosetting resin composition. 15 mass% or less.
  • the blending amount of the photopolymerizable monomer exceeds 50% by mass, the curing shrinkage increases, so that the warpage may increase.
  • the photopolymerizable monomer is derived from (meth) acrylate, it contains an ester bond. In this case, since the ester bond is hydrolyzed by the desmear treatment, the electrical characteristics may be deteriorated.
  • thermosetting resin composition of the present invention may further contain components such as a mercapto compound, an adhesion promoter, a colorant, an antioxidant, and an ultraviolet absorber.
  • a mercapto compound such as a mercapto compound, an adhesion promoter, a colorant, an antioxidant, and an ultraviolet absorber.
  • thermosetting resin composition includes a known and commonly used thickening agent such as finely divided silica, hydrotalcite, organic bentonite, and montmorillonite, an antifoaming agent such as silicone, fluorine, and polymer, and / or Known and commonly used additives such as leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, rust preventives, and the like can be blended.
  • blend well-known and usual thermosetting resins such as a block isocyanate compound, an amino resin, a benzoxazine resin, a carbodiimide resin, a cyclocarbonate compound, an episulfide resin, etc.
  • thermosetting component As a thermosetting component. Furthermore, by containing a phenol resin as the alkali-developable resin and an epoxy resin as the heat-reactive compound, a Tg can be increased, and a cured product having excellent HAST resistance can be obtained without depending on the softening point of the raw material. It can be set as a resin composition.
  • a photopolymerizable monomer (a low molecular compound compounded to promote photocuring in a photocurable resin composition containing an ethylenically unsaturated group in the molecule and containing a carboxyl group-containing resin as a main component) When it is set as the composition which does not mix
  • the alkali development type thermosetting resin composition of the present invention is not limited to Tg before the curing reaction, and can be expected to have a high Tg. Further, the alkali development type thermosetting resin composition of the present invention can be expected to be cured without being inhibited by oxygen.
  • thermosetting resin composition of the present invention is useful for forming a pattern layer of a printed wiring board, and is particularly useful as a material for a solder resist or an interlayer insulating layer.
  • the pattern formation method which can use the thermosetting resin composition of this invention suitably is the process (A) of forming the resin layer which consists of a thermosetting resin composition in a base material, and light irradiation to a negative pattern shape Then, the step (B) of activating the photobase generator contained in the thermosetting resin composition to cure the light irradiated portion, and the step of forming the negative pattern layer by removing the unirradiated portion by alkali development. (C) is included.
  • the light irradiation part can be cured by generating a base in the light irradiation part of the thermosetting resin composition by pattern light irradiation.
  • the unirradiated part is removed and a negative pattern layer is formed.
  • a process (A) is a process of forming the resin layer which consists of a thermosetting resin composition in a base material.
  • the method of forming the resin layer is based on a method of applying and drying a liquid thermosetting resin composition on a base material, or a method of laminating a thermosetting resin composition in a dry film on a substrate. Can do.
  • thermosetting resin composition As a method for applying the thermosetting resin composition to the substrate, a known method such as a blade coater, a lip coater, a comma coater, or a film coater can be appropriately employed. Also, the drying method is a method using a hot-air circulation type drying furnace, IR furnace, hot plate, convection oven, etc., equipped with a heat source of the heating method by steam, and the hot air in the dryer is counter-contacted and supported by the nozzle Known methods such as a method of spraying on the body can be applied.
  • Step (B) is a step of activating the photobase generator contained in the thermosetting resin composition by light irradiation with a negative pattern to cure the light irradiation part.
  • the photobase generator is destabilized by the base generated in the light irradiation part, and further the base is generated. In this way, the base can be sufficiently cured to the deep part of the light irradiation part by chemically growing.
  • a light irradiator used for light irradiation for example, a direct drawing apparatus capable of irradiating laser light, lamp light, and LED light can be used.
  • a negative mask can be used as the patterned light irradiation mask.
  • the active energy ray it is preferable to use laser light or scattered light having a maximum wavelength in the range of 350 to 410 nm. By setting the maximum wavelength within this range, the thermal reactivity of the thermosetting resin composition can be improved efficiently. If a laser beam in this range is used, either a gas laser or a solid laser may be used. The amount of light irradiation varies depending on the film thickness and the like, but can be generally in the range of 100 to 1500 mJ / cm 2 , preferably 300 to 1500 mJ / cm 2 .
  • the direct drawing apparatus for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any apparatus that oscillates laser light having a maximum wavelength of 350 to 410 nm may be used. .
  • Step (B1) the light irradiation part is cured by heating.
  • Step (B1) can be cured to a deep portion by the base generated in step (B).
  • the heating temperature is preferably a temperature at which the light-irradiated portion of the thermosetting resin composition is thermally cured, but the non-irradiated portion is not thermally cured.
  • the heat generation start temperature or the heat generation peak temperature of the unirradiated thermosetting resin composition is lower than the heat generation start temperature or the heat generation peak temperature of the light irradiated thermosetting resin composition. Heating at a high temperature is preferred. By heating in this way, only the light irradiation part can be selectively cured.
  • the heating temperature is, for example, 80 to 140 ° C.
  • the heating temperature is 80 ° C. or higher.
  • the heating temperature is set to 140 ° C. or lower, only the light irradiation part can be selectively cured.
  • the heating time is, for example, 10 to 100 minutes.
  • the heating method is the same as the drying method. In the unirradiated portion, no base is generated from the photobase generator, so that thermosetting is suppressed.
  • Step (C) is a step of forming a negative pattern layer by removing unirradiated portions by development.
  • a developing method a known method such as a dipping method, a shower method, a spray method, or a brush method can be used.
  • Developers include potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines such as ethanolamine, and alkalis such as tetramethylammonium hydroxide aqueous solution (TMAH).
  • TMAH tetramethylammonium hydroxide aqueous solution
  • An aqueous solution or a mixed solution thereof can be used.
  • the pattern forming method preferably further includes an ultraviolet irradiation step (D) after the step (C).
  • an ultraviolet irradiation step (D) after the step (C) By further irradiating with ultraviolet rays after the step (C), the photobase generator remaining without being activated at the time of light irradiation can be activated.
  • the wavelength of ultraviolet rays and the light irradiation amount (exposure amount) in the ultraviolet irradiation step (D) after the step (C) may be the same as or different from those in the step (B).
  • a suitable light irradiation amount (exposure amount) is 150 to 2000 mJ / cm 2 .
  • the pattern formation method preferably further includes a thermosetting (post-cure) step (E) after the step (C).
  • a thermosetting (post-cure) step (E) after the step (C).
  • the pattern layer is sufficiently heat-cured by the base generated from the photobase generator in the step (B) or the steps (B) and (D). Since the unirradiated portion has already been removed at the time of the step (E), the step (E) can be performed at a temperature equal to or higher than the curing reaction start temperature of the unirradiated thermosetting resin composition. Thereby, a pattern layer can fully be thermosetted.
  • the heating temperature is, for example, 160 ° C. or higher.
  • the pattern forming method may further include a laser processing step (F). Fine openings can be formed by laser processing.
  • a known laser such as a YAG laser, a CO2 laser, or an excimer laser can be used.
  • the step (F) is preferably performed after the step (C) or after the steps (D) and (E) when the step (F) includes the steps (D) and (E).
  • Step (G) The pattern forming method of the present invention preferably further includes a desmear process (G) after the process (F).
  • Step (G) includes a smear swelling step for swelling smear to facilitate removal, a removal step for removing smear, and a neutralization step for neutralizing sludge generated from the desmear liquid used in the removal step.
  • the swelling step is performed using an alkali chemical such as sodium hydroxide, and facilitates smear removal with a desmear chemical.
  • removing step smear is removed using an acidic chemical solution containing an oxidizing agent such as dichromic acid or permanganic acid.
  • the neutralization step the oxidizing agent used in the removal step is reduced and removed using an alkaline chemical such as sodium hydroxide.
  • thermosetting resin composition ⁇ Preparation of alkali development type thermosetting resin composition> According to the formulations shown in Tables 1 to 3 below, the materials described in Examples / Comparative Examples were respectively mixed, premixed with a stirrer, and then kneaded with a three-roll mill to prepare a thermosetting resin composition. The values in the table are parts by mass unless otherwise specified.
  • thermosetting resin composition As a carrier film, a thermosetting resin composition was applied on a PET film having a thickness of 38 ⁇ m using an applicator, and then dried at 90 ° C. for 30 minutes to prepare a dry film. The coating amount was adjusted so that the thickness of the thermosetting resin composition was about 20 ⁇ m after drying. Thereafter, the obtained dry film was slit to a predetermined size.
  • ⁇ Laminate> Prepare a double-sided printed wiring board with a copper thickness of 15 ⁇ m and a circuit formed on it, and print it on a base material that has been pre-treated with MEC CZ-8100 using a vacuum laminator MVLP-500 A dry film was laminated on the plate. Lamination conditions were temperature 80 ° C., was conducted at a pressure 5kg / cm 2 / 60sec.
  • ⁇ Evaluation of dent on through hole> As shown in FIG. 3, a double-sided printed wiring board having a diameter of 300 ⁇ m and a pitch of 1 mm with copper-plated through-holes formed at a thickness of 0.3 mm was prepared, and MEC CZ-8100 was used. The pretreatment was performed. Thereafter, dry film of 50 ⁇ m thickness produced by the method shown in the paragraph of dry film production is simultaneously dried on both sides of the printed wiring board on which through holes are formed, using a vacuum laminator MVLP-500 of Meiki Co., Ltd. The film was laminated. Lamination conditions were temperature 80 ° C., was conducted at a pressure 5kg / cm 2 / 60sec.
  • the entire surface of the base material provided with the thermosetting resin layer was irradiated with ORC HMW680GW (metal halide lamp, scattered light) on the entire surface with a solid exposure.
  • the light irradiation amount was set as shown in Tables 1 to 3 with reference to the exothermic peak temperature by DSC.
  • the substrate was subjected to heat treatment for 60 to 80 minutes under the temperature conditions shown in Table 1.
  • UV irradiation was carried out with an energy amount of 1 J / cm 2 using an ORC UV irradiation device, followed by longitudinal curing at 170 ° C./60 min in a hot air circulating drying furnace to complete curing.
  • the surface roughness measuring device SE-700 manufactured by Kosaka Laboratories was used to confirm the amount of dent on the through hole. (Evaluation methods) ⁇ : The maximum dent on the through hole is 5 ⁇ m or less. ⁇ : The maximum recess on the through hole exceeds 5 ⁇ m
  • the substrate provided with the resin layer obtained above was irradiated with a negative pattern with an aperture design size of 100 ⁇ m by ORC HMW680GW (metal halide lamp, scattered light).
  • the light irradiation amount was set as described in Tables 1 to 3 below with reference to the exothermic peak temperature by DSC.
  • heat treatment was performed for 60 to 80 minutes under the temperature conditions shown in Tables 1 to 3.
  • the substrate was immersed in a 3 wt% TMAH / 5 wt% ethanolamine mixed aqueous solution at 35 ° C. and developed for 3 minutes, and development and patterning were evaluated according to the following criteria. The obtained results are shown in Tables 1 to 3.
  • the obtained results are shown in Tables 1 to 3. (Evaluation methods) ⁇ : The top length of the line was 100 ⁇ m and the bottom length was 100 ⁇ m, and a pattern as designed was obtained. ⁇ : The top length of the line was 100 ⁇ m and the bottom length was 60 ⁇ m or more and less than 100 ⁇ m, and a slight undercut was observed. X: The top length of the line was 100 ⁇ m, the bottom length was less than 60 ⁇ m, and a large undercut was observed at the bottom.
  • the base material produced by the same method as the base material for which the formation of the opening pattern was evaluated was further irradiated with ultraviolet rays at an energy amount of 1 J / cm 2 using an ORC ultraviolet irradiation device, and then subjected to Table 1 in a hot air circulation drying furnace. It was cured for 60 minutes at the post-cure temperature described in (3) (post-cure). Then, laser processing was performed on the light irradiation surface.
  • the light source was processed with a CO 2 laser (Hitachi Via Mechanics, light source 10.6 ⁇ m). Evaluation was made according to the following criteria. In order to give superiority or inferiority in workability, laser processing was performed under the same conditions.
  • the target of the processing diameter is a top diameter of 65 ⁇ m / bottom of 50 ⁇ m.
  • the substrate subjected to laser processing is further desmeared with a permanganate desmear aqueous solution (wet method). Processed.
  • desmear resistance confirmation of the surface roughness of the substrate surface and the state around the laser opening were evaluated according to the following criteria. For confirmation of the surface roughness, each surface roughness Ra was measured with a laser microscope VK-8500 (Keyence Corporation, measurement magnification 2000 times, Z-axis direction measurement pitch 10 nm).
  • the substrate was heat-treated for 60 to 80 minutes under the temperature conditions shown in Tables 1 to 3. Further, UV irradiation was performed with an energy amount of 1 J / cm 2 using an ORC UV irradiation device, followed by curing at 170 ° C./60 min in a hot air circulating drying oven to obtain a copper foil having a thermosetting resin composition on one side. It was. Thereafter, as an evaluation of the warped state of the obtained cured product, the amount of warpage at four end portions was measured with a caliper. (Evaluation methods) ⁇ ⁇ : Almost no warpage. The amount of warpage of the maximum warp portion among the four end portions is less than 5 mm.
  • the warp amount of the maximum warp portion of the four end portions is 5 mm or more and less than 20 mm.
  • O The warp amount of the maximum warp portion of the four end portions is 20 mm or more.
  • ⁇ The cured product contracted into a cylindrical shape. The amount of warp at the end could not be measured with calipers
  • each dry film with a thickness of 40 ⁇ m was produced. Thereafter, a dry film was laminated on the glossy surface side of the 18 ⁇ m copper foil by using a vacuum laminator MVLP-500 of Meiki Co., Ltd. Lamination conditions were temperature 80 ° C., was conducted at a pressure 5kg / cm 2 / 60sec. Thereafter, the entire surface was exposed with ORC HMW680GW (metal halide lamp, scattered light). The light irradiation amount was set as described in Tables 1 to 3 below with reference to the exothermic peak temperature by DSC. Next, heat treatment was performed for 60 to 80 minutes under the temperature conditions shown in Tables 1 to 3.
  • the printed wiring board subjected to the permanganate desmear treatment as described above was further subjected to conditions of nickel 0.5 ⁇ m and gold plating 0.03 ⁇ m using a commercially available electroless nickel plating bath and electroless gold plating bath. Plating was performed, and a gold plating process was performed on the pattern forming portion. About the obtained printed wiring board, the thermal cycle characteristic evaluation was performed.
  • the processing conditions are as follows: -65 ° C for 30 min, 150 ° C for 30 min, heat history is added, and after 2000 cycles, the surface of the pattern layer and the periphery are observed with an optical microscope, and cracks are observed according to the following criteria: Was evaluated. The number of observation patterns was 100 holes.
  • Measuring apparatus Appe refractometer Measuring conditions: Wavelength 589.3 nm, temperature 25 ° C.
  • Tables 1 to 3 The components in Tables 1 to 3 are as follows. (Thermo-reactive compound) * 828: Bis-A type liquid epoxy (equivalent 190 g / eq), Mitsubishi Chemical Corporation * HP-7200 H60: dicyclopentadiene type epoxy (equivalent 265 g / eq), DIC was dissolved in cyclohexanone. 60% solids * HF-1M H60: phenol novolak (hydroxyl equivalent: 105 g / eq), Meiwa Kasei Co., Ltd. dissolved in cyclohexanone.
  • the alkali developing resin, the polymer resin, and the photobase generator are essential components, so that they have excellent curing characteristics and B-stage state stability. It was found that the patterning by can be performed. Further, in Examples 14 to 18 containing the inorganic filler, it was found that the thermal cycle characteristics were excellent. Also, by blending the polymer resin, the melt viscosity of the thermosetting resin composition is increased, and the flow of the resin in the through-hole portion can be suppressed during heating after exposure. As a result, a flat substrate that is not recessed on the through hole can be manufactured. On the other hand, with the photoradical composition of Comparative Example 4, pattern formation by alkali development became difficult. The line shape was also poor. Furthermore, it was inferior in curability at the time of a cold-heat cycle.
  • the substrate provided with the resin layer obtained in Example 1 was irradiated with a negative pattern with ORC HMW680GW (metal halide lamp, scattered light). Each substrate was subjected to pattern light irradiation with a light irradiation amount of 1000 mJ / cm 2 . After light irradiation, the resin layer is scraped off from the substrate and immediately heated to 30-300 ° C. at a temperature increase rate of 5 ° C./min in DSC-6200 of Seiko Instruments Inc. Measurements were made. Moreover, DSC measurement was similarly performed with respect to the cured layer which consists of a thermosetting resin composition immediately after ultraviolet irradiation and before postcure.
  • ORC HMW680GW metal halide lamp, scattered light
  • the unirradiated portions, the light irradiation portion of the light irradiation amount 1000 mJ / cm 2 is a DSC chart of the light emitting units to the UV irradiation further 1000 mJ / cm 2 after irradiation with light irradiation amount 1000 mJ / cm 2 .
  • the film was irradiated with a negative pattern with ORC HMW680GW (metal halide lamp, scattered light) at an irradiation amount of 300 mJ / cm 2 . Thereafter, development was performed with a 1 wt% sodium carbonate aqueous solution for 60 seconds, followed by heat treatment at 150 ° C./60 min using a hot-air circulating drying oven to obtain a patterned cured coating film. Thereafter, desmear resistance was evaluated in the same manner as in Example 2 above. As a result, the desmear resistance was “x”.

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CN115145112A (zh) * 2021-03-30 2022-10-04 太阳油墨（苏州）有限公司 光固化性热固化性树脂组合物、干膜、固化物和电子部件
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