JP2024065048A - CURABLE RESIN COMPOSITION, DRY FILM, CURED PRODUCT, AND PRINTED WIRING BOARD - Google Patents
CURABLE RESIN COMPOSITION, DRY FILM, CURED PRODUCT, AND PRINTED WIRING BOARD Download PDFInfo
- Publication number
- JP2024065048A JP2024065048A JP2023182833A JP2023182833A JP2024065048A JP 2024065048 A JP2024065048 A JP 2024065048A JP 2023182833 A JP2023182833 A JP 2023182833A JP 2023182833 A JP2023182833 A JP 2023182833A JP 2024065048 A JP2024065048 A JP 2024065048A
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- Prior art keywords
- resin composition
- curable resin
- alkali
- film
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011342 resin composition Substances 0.000 title claims abstract description 65
- 229920005989 resin Polymers 0.000 claims abstract description 110
- 239000011347 resin Substances 0.000 claims abstract description 110
- 239000003822 epoxy resin Substances 0.000 claims abstract description 30
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 16
- 239000011256 inorganic filler Substances 0.000 claims abstract description 16
- 125000005462 imide group Chemical group 0.000 claims abstract 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 238000000576 coating method Methods 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 11
- 238000004381 surface treatment Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 abstract description 9
- 239000010408 film Substances 0.000 description 87
- -1 monocarboxylic acid compounds Chemical class 0.000 description 38
- 239000010410 layer Substances 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 28
- 239000000758 substrate Substances 0.000 description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000000203 mixture Substances 0.000 description 22
- 239000000049 pigment Substances 0.000 description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 19
- 239000007787 solid Substances 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
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- 238000001723 curing Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- 150000003949 imides Chemical group 0.000 description 11
- 229920003986 novolac Polymers 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
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- 125000002947 alkylene group Chemical group 0.000 description 8
- 239000003086 colorant Substances 0.000 description 8
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 7
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- 239000007864 aqueous solution Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 229930003836 cresol Natural products 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 5
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- 238000003756 stirring Methods 0.000 description 5
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- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
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- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
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- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
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- MKRBAPNEJMFMHU-UHFFFAOYSA-N 1-benzylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC1=CC=CC=C1 MKRBAPNEJMFMHU-UHFFFAOYSA-N 0.000 description 2
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
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Landscapes
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Abstract
【課題】解像性を低下させることなく、現像性および耐溶剤性が向上した硬化性樹脂組成物の提供。【解決手段】本発明による硬化性樹脂組成物は、(A)重量平均分子量3000以下であるアルカリ可溶性感光性樹脂および(B)イミド骨格を含むアルカリ可溶性感光性樹脂の少なくとも1種、(C)エポキシ樹脂、(D)光重合開始剤、(E)光重合性モノマー、および(F)無機フィラーを含有することを特徴とする。【選択図】なし[Problem] To provide a curable resin composition that has improved developability and solvent resistance without reducing resolution. [Solution] The curable resin composition according to the present invention is characterized by containing at least one of (A) an alkali-soluble photosensitive resin having a weight average molecular weight of 3000 or less and (B) an alkali-soluble photosensitive resin containing an imide skeleton, (C) an epoxy resin, (D) a photopolymerization initiator, (E) a photopolymerizable monomer, and (F) an inorganic filler. [Selected Figure] None
Description
本発明は、硬化性樹脂組成物に関する。さらに、本発明は、該硬化性樹脂組成物を用いたドライフィルム、硬化物、およびプリント配線板に関する。 The present invention relates to a curable resin composition. Furthermore, the present invention relates to a dry film, a cured product, and a printed wiring board using the curable resin composition.
プリント配線基板の層間絶縁材としては、従来より、アミドイミド樹脂を含む硬化性樹脂組成物を用いることにより、硬化物の耐熱性等の諸特性を向上させている。特に、アミドイミド樹脂がカルボキシル基を含有する場合は、硬化性樹脂組成物の塗膜をアルカリ現像することが可能となる。
例えば、特許文献1では、希アルカリ水溶液でパターニングが可能な、カルボキシル基を有する重合性ポリイミド樹脂を含有する、活性エネルギー線硬化型ポリイミド樹脂組成物が提案されている。
Conventionally, a curable resin composition containing an amide-imide resin has been used as an interlayer insulating material for a printed wiring board to improve various properties such as heat resistance of the cured product. In particular, when the amide-imide resin contains a carboxyl group, it becomes possible to develop the coating film of the curable resin composition with an alkali.
For example, Patent Document 1 proposes an active energy ray-curable polyimide resin composition that contains a polymerizable polyimide resin having a carboxyl group and that can be patterned with a dilute alkaline aqueous solution.
上記の硬化性樹脂組成物においては、解像度を向上させるために、アミドイミド樹脂に対して更にカルボキシル基含有樹脂を多量に含ませることが考えられるが、この場合硬化物のTgが下がり、硬化物の耐薬品性が低下することがある。
特許文献2では、脂肪族構造を有するイソシアネートから合成されたイソシアヌレート型ポリイソシアネートとトリカルボン酸無水物との反応生成物であり、かつ数平均分子量が500~1000であることを特徴とするアミドイミド樹脂を用いることによって耐薬品性を損なうことなく、解像性と現像性を併せ持った硬化物を形成し得る硬化性樹脂組成物が提案されている。
In the above-mentioned curable resin composition, in order to improve the resolution, it is conceivable to further include a large amount of a carboxyl group-containing resin in addition to the amide-imide resin. In this case, however, the Tg of the cured product may decrease, and the chemical resistance of the cured product may decrease.
Patent Document 2 proposes a curable resin composition that can form a cured product that has both resolution and developability without impairing chemical resistance by using an amide-imide resin that is a reaction product of an isocyanurate-type polyisocyanate synthesized from an isocyanate having an aliphatic structure and a tricarboxylic acid anhydride and has a number-average molecular weight of 500 to 1,000.
また、半導体部品のパッケージ形式の一つとしてウエハーレベルパッケージが知られており、このウエハーレベルパッケージを製造する際に微細な絶縁パターンを一括で形成するためにアルカリ現像型の感光性絶縁材料の要求が高まっている。 In addition, wafer-level packaging is known as one type of packaging format for semiconductor components, and there is an increasing demand for alkaline-developable photosensitive insulating materials to form fine insulating patterns all at once when manufacturing this wafer-level packaging.
上記の様な電子部品においては配線の高密度化の要求があり、感光性絶縁材料の解像性のさらなる改善が課題となっている。特許文献2に記載の樹脂組成物では、小径のビアを開口した際の現像性が不十分であり、ビア底面に残渣が生じるという課題を見出した。 In electronic components such as those described above, there is a demand for higher density wiring, and further improvement in the resolution of photosensitive insulating materials is an issue. With the resin composition described in Patent Document 2, the developability is insufficient when opening small diameter vias, and a problem has been found in that residues are generated on the bottom of the vias.
また、工程の変更に伴いアセトンを用いた処理を行う際に、従来のアミドイミド樹脂では、当該アミドイミド樹脂が光反応しないことから硬化物中の架橋密度が低く、アセトンによる硬化塗膜上にクラックが生じるという課題を見出した。 In addition, when the process was changed to use acetone, the company found that the conventional amide-imide resin did not react with light, resulting in a low crosslink density in the cured product, and cracks would form on the cured coating film caused by the acetone.
本発明は、上記の課題に鑑みてなされたものであり、解像性を低下させることなく、現像性および耐溶剤性が向上した硬化性樹脂組成物を提供することを目的とする。また、本発明は、該樹脂組成物の乾燥塗膜からなる樹脂層を有するドライフィルム、該樹脂組成物または該ドライフィルムの樹脂層の硬化物、および、該硬化物を有するプリント配線板を提供することも目的とする。 The present invention has been made in view of the above problems, and aims to provide a curable resin composition that has improved developability and solvent resistance without reducing resolution. The present invention also aims to provide a dry film having a resin layer consisting of a dried coating film of the resin composition, a cured product of the resin composition or the resin layer of the dry film, and a printed wiring board having the cured product.
本発明者らは、上記目的を達成すべく、鋭意検討した結果、重量平均分子量3000以下であるアルカリ可溶性感光性樹脂およびイミド骨格を含むアルカリ可溶性感光性樹脂の少なくとも1種を用いて樹脂組成物中の反応性を向上させることによって上記課題を解決し得ることを見出した。 The inventors conducted intensive research to achieve the above object and discovered that the above problem can be solved by improving the reactivity of the resin composition using at least one of an alkali-soluble photosensitive resin having a weight average molecular weight of 3000 or less and an alkali-soluble photosensitive resin containing an imide skeleton.
すなわち、本発明によれば、以下の発明が提供される。
[1] (A)重量平均分子量3000以下であるアルカリ可溶性感光性樹脂および(B)イミド骨格を含むアルカリ可溶性感光性樹脂の少なくとも1種、(C)エポキシ樹脂、(D)光重合開始剤、(E)光重合性モノマー、および(F)無機フィラーを含有する硬化性樹脂組成物。
[2] (A)重量平均分子量3000以下であるアルカリ可溶性感光性樹脂および(B)イミド骨格を含むアルカリ可溶性感光性樹脂を含有する、[1]に記載の硬化性樹脂組成物。
[3] 前記(F)無機フィラーの平均粒径が、10nm以上500nm以下である、[1]または[2]に記載の硬化性樹脂組成物。
[4] 前記(F)無機フィラーは、表面処理を施していないシリカである、[1]~[3]のいずれかに記載の硬化性樹脂組成物。
[5] 第一のフィルムと、前記第一のフィルム上に形成された[1]~[4]のいずれかに記載の硬化性樹脂組成物の乾燥塗膜からなる樹脂層とを備えることを特徴とする、ドライフィルム。
[6] [1]~[4]のいずれかに記載の硬化性樹脂組成物を硬化させて得られることを特徴とする、硬化物。
[7] [5]に記載のドライフィルムの樹脂層を硬化させて得られることを特徴とする、硬化物。
[8] [6]に記載の硬化物を備えることを特徴とする、プリント配線板。
[9] [7]に記載の硬化物を備えることを特徴とする、プリント配線板。
That is, according to the present invention, the following inventions are provided.
[1] A curable resin composition comprising: (A) at least one of an alkali-soluble photosensitive resin having a weight average molecular weight of 3,000 or less and (B) an alkali-soluble photosensitive resin containing an imide skeleton; (C) an epoxy resin; (D) a photopolymerization initiator; (E) a photopolymerizable monomer; and (F) an inorganic filler.
[2] The curable resin composition according to [1], comprising (A) an alkali-soluble photosensitive resin having a weight average molecular weight of 3,000 or less and (B) an alkali-soluble photosensitive resin having an imide skeleton.
[3] The curable resin composition according to [1] or [2], wherein the inorganic filler (F) has an average particle size of 10 nm or more and 500 nm or less.
[4] The curable resin composition according to any one of [1] to [3], wherein the (F) inorganic filler is silica that has not been subjected to a surface treatment.
[5] A dry film comprising a first film and a resin layer formed on the first film and comprising a dry coating film of the curable resin composition according to any one of [1] to [4].
[6] A cured product obtained by curing the curable resin composition according to any one of [1] to [4].
[7] A cured product obtained by curing the resin layer of the dry film according to [5].
[8] A printed wiring board comprising the cured product according to [6].
[9] A printed wiring board comprising the cured product according to [7].
本発明によれば、解像性を低下させることなく、現像性および耐溶剤性が向上した硬化性樹脂組成物を提供することができる。また、本発明によれば、該樹脂組成物の乾燥塗膜からなる樹脂層を有するドライフィルム、該樹脂組成物または該ドライフィルムの樹脂層の硬化物、および、該硬化物を有するプリント配線板を提供することができる。 According to the present invention, it is possible to provide a curable resin composition having improved developability and solvent resistance without reducing resolution. In addition, according to the present invention, it is possible to provide a dry film having a resin layer formed of a dried coating film of the resin composition, a cured product of the resin composition or the resin layer of the dry film, and a printed wiring board having the cured product.
[硬化性樹脂組成物]
本発明による硬化性樹脂組成物は、少なくとも、(A)重量平均分子量3000以下であるアルカリ可溶性感光性樹脂および(B)イミド骨格を含むアルカリ可溶性感光性樹脂の少なくとも1種、(C)エポキシ樹脂、(D)光重合開始剤、(E)光重合性モノマー、および(F)無機フィラーを含有するものである。本発明による硬化性樹脂組成物は、硬化剤や着色剤等をさらに含有してもよい。以下、本発明による硬化性樹脂組成物を構成する各成分について説明する。
[Curable resin composition]
The curable resin composition according to the present invention contains at least one of (A) an alkali-soluble photosensitive resin having a weight average molecular weight of 3000 or less and (B) an alkali-soluble photosensitive resin containing an imide skeleton, (C) an epoxy resin, (D) a photopolymerization initiator, (E) a photopolymerizable monomer, and (F) an inorganic filler. The curable resin composition according to the present invention may further contain a curing agent, a colorant, etc. Each component constituting the curable resin composition according to the present invention will be described below.
((A)、(B)アルカリ可溶性感光性樹脂)
アルカリ可溶性感光性樹脂は、アルカリ可溶される樹脂であれば何れでもよく、公知のものが使用される。アルカリ可溶性感光性樹脂は、1種を単独で用いてもよいし、2種以上を組み合わせて用いることができる。アルカリ可溶性感光性樹脂としては、例えば、カルボキシル基含有樹脂や、フェノール性水酸基含有樹脂のような水溶性樹脂等が挙げられる。なかでも現像性に優れることより、カルボキシル基含有樹脂やフェノール性水酸基含有樹脂が好ましく、カルボキシル基含有樹脂がより好ましい。アルカリ可溶性感光性樹脂が、カルボキシル基を含むことにより、アルカリ現像性とすることができる。また、カルボキシル基の他に、分子内にエチレン性不飽和二重結合を有することにより、感光性とすることができるエチレン性不飽和二重結合としては、アクリル酸もしくはメタアクリル酸またはそれらの誘導体由来のものが好ましい。
((A) and (B) Alkali-soluble photosensitive resin)
The alkali-soluble photosensitive resin may be any resin that is alkali-soluble, and known ones are used. The alkali-soluble photosensitive resin may be used alone or in combination of two or more. Examples of the alkali-soluble photosensitive resin include water-soluble resins such as carboxyl group-containing resins and phenolic hydroxyl group-containing resins. Among them, carboxyl group-containing resins and phenolic hydroxyl group-containing resins are preferred because of their excellent developability, and carboxyl group-containing resins are more preferred. The alkali-soluble photosensitive resin can be made alkaline developable by containing a carboxyl group. In addition to the carboxyl group, the ethylenically unsaturated double bond in the molecule can be photosensitive, and is preferably derived from acrylic acid or methacrylic acid or a derivative thereof.
カルボキシル基含有樹脂の具体例としては、以下のような化合物(オリゴマーおよびポリマーのいずれでもよい)を挙げることができる。なお、本明細書において、(メタ)アクリレートとは、アクリレート、メタクリレートおよびそれらの混合物を総称する用語で、他の類似の表現についても同様である。 Specific examples of carboxyl group-containing resins include the following compounds (which may be either oligomers or polymers). Note that in this specification, (meth)acrylate is a general term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
(1)ジイソシアネートと、ビスフェノールA型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、ビキシレノール型エポキシ樹脂、ビフェノール型エポキシ樹脂等の2官能エポキシ樹脂と(メタ)アクリル酸等のエチレン性不飽和二重結合を有するモノカルボン酸化合物との反応物の部分酸無水物変性物、カルボキシル基含有ジアルコール化合物およびジオール化合物の重付加反応によるカルボキシル基含有感光性ウレタン樹脂。 (1) Carboxylic acid-containing photosensitive urethane resins obtained by polyaddition reaction of diisocyanates with bifunctional epoxy resins such as bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bixylenol epoxy resins, and biphenol epoxy resins, and monocarboxylic acid compounds having ethylenically unsaturated double bonds such as (meth)acrylic acid, partially acid anhydride-modified products, carboxyl-containing dialcohol compounds, and diol compounds.
(2)脂肪族ジイソシアネート、分岐脂肪族ジイソシアネート、脂環式ジイソシアネート、芳香族ジイソシアネート等のジイソシアネートと、ジメチロールプロピオン酸、ジメチロールブタン酸等のカルボキシル基含有ジアルコール化合物およびポリカーボネート系ポリオール、ポリエーテル系ポリオール、ポリエステル系ポリオール、ポリオレフィン系ポリオール、アクリル系ポリオール、ビスフェノールA系アルキレンオキサイド付加体ジオール、フェノール性ヒドロキシル基およびアルコール性ヒドロキシル基を有する化合物等のジオール化合物の重付加反応によるカルボキシル基含有ウレタン樹脂、または前記(1)の樹脂の合成中に、ヒドロキシアルキル(メタ)アクリレート等の分子内に1つの水酸基と1つ以上の(メタ)アクリロイル基を有する化合物を加え、末端(メタ)アクリル化したカルボキシル基含有感光性ウレタン樹脂。 (2) Carboxyl group-containing urethane resins obtained by polyaddition reaction of diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and diol compounds such as polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups, or carboxyl group-containing photosensitive urethane resins obtained by adding compounds having one hydroxyl group and one or more (meth)acryloyl groups in the molecule such as hydroxyalkyl (meth)acrylates during the synthesis of the resin of (1) above, resulting in terminal (meth)acrylation.
(3)脂肪族ジイソシアネート、分岐脂肪族ジイソシアネート、脂環式ジイソシアネート、芳香族ジイソシアネート等のジイソシアネートと、ジメチロールプロピオン酸、ジメチロールブタン酸等のカルボキシル基含有ジアルコール化合物およびポリカーボネート系ポリオール、ポリエーテル系ポリオール、ポリエステル系ポリオール、ポリオレフィン系ポリオール、アクリル系ポリオール、ビスフェノールA系アルキレンオキサイド付加体ジオール、フェノール性ヒドロキシル基およびアルコール性ヒドロキシル基を有する化合物等のジオール化合物の重付加反応によるカルボキシル基含有ウレタン樹脂、または前記(1)の樹脂の合成中に、イソホロンジイソシアネートとペンタエリスリトールトリアクリレートの等モル反応物など、分子内に1つのイソシアネート基と1つ以上の(メタ)アクリロイル基を有する化合物を加え末端(メタ)アクリル化したカルボキシル基含有感光性ウレタン樹脂。 (3) Carboxyl group-containing urethane resins obtained by polyaddition reaction of diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and diol compounds such as polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups, or carboxyl group-containing photosensitive urethane resins obtained by adding a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate, during the synthesis of the resin of (1) above, to obtain terminal (meth)acrylation.
(4)2官能またはそれ以上の多官能(固形)エポキシ樹脂に(メタ)アクリル酸を反応させ、側鎖に存在する水酸基に2塩基酸無水物を付加させたカルボキシル基含有感光性樹脂。 (4) A carboxyl group-containing photosensitive resin obtained by reacting a difunctional or more polyfunctional (solid) epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride to the hydroxyl groups present in the side chains.
(5)2官能(固形)エポキシ樹脂の水酸基をさらにエピクロロヒドリンでエポキシ化した多官能エポキシ樹脂に(メタ)アクリル酸を反応させ、生じた水酸基に2塩基酸無水物を付加させたカルボキシル基含有感光性樹脂。 (5) A carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy resin, in which the hydroxyl groups of a bifunctional (solid) epoxy resin are further epoxidized with epichlorohydrin, with (meth)acrylic acid, and then adding a dibasic acid anhydride to the resulting hydroxyl groups.
(6)1分子中に複数のエポキシ基を有するエポキシ化合物に、p-ヒドロキシフェネチルアルコール等の1分子中に少なくとも1個のアルコール性水酸基と1個のフェノール性水酸基を有する化合物と、(メタ)アクリル酸等の不飽和基含有モノカルボン酸とを反応させ、得られた反応生成物のアルコール性水酸基に対して、無水マレイン酸、テトラヒドロ無水フタル酸、無水トリメリット酸、無水ピロメリット酸、アジピン酸等の多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。 (6) A carboxyl group-containing photosensitive resin obtained by reacting an epoxy compound having multiple epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and an unsaturated group-containing monocarboxylic acid, such as (meth)acrylic acid, and then reacting the alcoholic hydroxyl group of the resulting reaction product with a polybasic acid anhydride, such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic acid.
(7)1分子中に複数のフェノール性水酸基を有する化合物とエチレンオキサイド、プロピレンオキサイド等のアルキレンオキサイドとを反応させて得られる反応生成物に不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。 (7) A carboxyl group-containing photosensitive resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, reacting the reaction product obtained with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.
(8)1分子中に複数のフェノール性水酸基を有する化合物とエチレンカーボネート、プロピレンカーボネート等の環状カーボネート化合物とを反応させて得られる反応生成物に不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。 (8) A carboxyl group-containing photosensitive resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, reacting the reaction product obtained with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.
(9)前記(1)~(8)の樹脂にさらに1分子内に1つのエポキシ基と1つ以上の(メタ)アクリロイル基を有する化合物を付加してなるカルボキシル基含有感光性樹脂。 (9) A carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins (1) to (8).
これらカルボキシル基含有樹脂は、前記列挙したもの限らず使用することができ、1種類を単独で用いてもよく、複数種を混合して用いてもよい。 These carboxyl group-containing resins are not limited to those listed above, and one type may be used alone, or multiple types may be mixed together.
本発明においては、上記のアルカリ可溶性感光性樹脂の中でも、特に、(A)重量平均分子量3000以下であるアルカリ可溶性感光性樹脂および(B)イミド骨格を含むアルカリ可溶性感光性樹脂の少なくとも1種を用いることで、解像性を低下させることなく、現像性および耐溶剤性が向上させることができる。本発明の好ましい態様においては、(A)重量平均分子量3000以下であるアルカリ可溶性感光性樹脂および(B)イミド骨格を含むアルカリ可溶性感光性樹脂を併用することで、解像性を低下させることなく、特に現像性をより向上させることができる。 In the present invention, among the above-mentioned alkali-soluble photosensitive resins, by using at least one of (A) an alkali-soluble photosensitive resin having a weight-average molecular weight of 3000 or less and (B) an alkali-soluble photosensitive resin containing an imide skeleton, it is possible to improve developability and solvent resistance without reducing resolution. In a preferred embodiment of the present invention, by using (A) an alkali-soluble photosensitive resin having a weight-average molecular weight of 3000 or less and (B) an alkali-soluble photosensitive resin containing an imide skeleton in combination, it is possible to further improve developability in particular without reducing resolution.
(A)アルカリ可溶性感光性樹脂の重量平均分子量は、3000以下であり、好ましくは1000以上2800以下であり、より好ましくは1200以上2600以下である。アルカリ可溶性感光性樹脂の重量平均分子量が3000以下のであることで、現像性に優れるため、特に現像時の残渣の改善に効果的である。なお、重量平均分子量は、ゲル浸透クロマトグラフィー(GPC)により測定することができる。 (A) The weight average molecular weight of the alkali-soluble photosensitive resin is 3000 or less, preferably 1000 or more and 2800 or less, and more preferably 1200 or more and 2600 or less. When the weight average molecular weight of the alkali-soluble photosensitive resin is 3000 or less, the resin has excellent developability and is particularly effective in improving residues during development. The weight average molecular weight can be measured by gel permeation chromatography (GPC).
(B)イミド骨格を含むアルカリ可溶性感光性樹脂としては、例えば、上記のアルカリ可溶性感光性樹脂の一部にマレイミド系単量体由来の構成単位を含むものが挙げられる。このようなアルカリ可溶性感光性樹脂は、上記のアルカリ可溶性感光性樹脂の反応工程において、不飽和カルボン酸単量等の他の単量体と、マレイミド系単量体とを共重合させて合成することができる。マレイミド系単量体としては、N-フェニルマレイミド、N-(2-メチルフェニル)マレイミド、N-(4-メチルフェニル)マレイミド、N-(2,6-ジエチルフェニル)マレイミド、N-(2-クロロフェニル)マレイミド、N-メチルマレイミド、N-エチルマレイミド、N-イソプロピルマレイミド、N-ラウリルマレイミド、N-シクロヘキシルマレイミド、N-ベンジルマレイミド、N-フェニルメチルマレイミド、N-(2,4,6-トリブロモフェニル)マレイミド、N-[3-(トリエトキシシリル)プロピル]マレイミド、N-オクタデセニルマレイミド、N-ドデセニルマレイミド、N-(2-メトキシフェニル)マレイミド、N-(2,4,6-トリクロロフェニル)マレイミド、N-(4-ヒドロキシフェニル)マレイミド、N-(1-ヒドロキシフェニル)マレイミド等のN-置換マレイミドや無置換マレイミドが挙げられ、これらの1種または2種以上を組み合わせて用いることができる。マレイミド系単量体由来の構成単位の含有量は、樹脂を構成する全構成単位中に10質量%以上60質量%以下であることが好ましい。アルカリ可溶性感光性樹脂はイミド骨格を含むことで、機械物性が向上する。 (B) Examples of alkali-soluble photosensitive resins containing an imide skeleton include those containing structural units derived from maleimide monomers as part of the above-mentioned alkali-soluble photosensitive resins. Such alkali-soluble photosensitive resins can be synthesized by copolymerizing other monomers such as unsaturated carboxylic acid monomers with maleimide monomers in the reaction process of the above-mentioned alkali-soluble photosensitive resin. Examples of maleimide monomers include N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(2-chlorophenyl)maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmethylmaleimide, N-(2,4,6-tribromophenyl)maleimide, N-phenylmethyl ... Examples of N-substituted or unsubstituted maleimides include N-(2-methoxyphenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, and N-(1-hydroxyphenyl)maleimide, and these may be used alone or in combination of two or more. The content of the structural unit derived from the maleimide monomer is preferably 10% by mass or more and 60% by mass or less of the total structural units constituting the resin. The mechanical properties of the alkali-soluble photosensitive resin are improved by including an imide skeleton.
(A)重量平均分子量3000以下であるアルカリ可溶性感光性樹脂および(B)イミド骨格を含むアルカリ可溶性感光性樹脂の合計配合量は、硬化性樹脂組成物全量あたり固形分換算で、好ましくは5質量%以上50質量%以下であり、より好ましくは10質量%以上45質量%以下であり、さらに好ましくは20質量%以上40質量%以下である。5質量%以上とすることにより、硬化被膜の強度を向上させることができる。また50質量%以下とすることにより、組成物の粘性が適当であり塗付性等を向上させることができる。 The total amount of (A) the alkali-soluble photosensitive resin having a weight average molecular weight of 3000 or less and (B) the alkali-soluble photosensitive resin containing an imide skeleton is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 45% by mass or less, and even more preferably 20% by mass or more and 40% by mass or less, calculated as solid content based on the total amount of the curable resin composition. By making it 5% by mass or more, the strength of the cured coating can be improved. Also, by making it 50% by mass or less, the viscosity of the composition is appropriate and the application property, etc. can be improved.
((C)エポキシ樹脂)
エポキシ樹脂としては、1個以上のエポキシ基を有する公知の化合物を使用することができる。エポキシ樹脂としては、例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、臭素化ビスフェノールA型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールAのノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂等が挙げられる。
((C) Epoxy Resin)
As the epoxy resin, a known compound having one or more epoxy groups can be used. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin, etc.
市販されるエポキシ樹脂としては、例えば、三菱ケミカル株式会社製のjER 828、806、807、YX8000、YX8034、834、日鉄ケミカル&マテリアル株式会社製のYD-128、YDF-170、ZX-1059、ST-3000、DIC株式会社製のEPICLON 830、835、840、850、N-730A、N-695、および日本化薬株式会社製のRE-306等が挙げられる。 Commercially available epoxy resins include, for example, jER 828, 806, 807, YX8000, YX8034, and 834 manufactured by Mitsubishi Chemical Corporation, YD-128, YDF-170, ZX-1059, and ST-3000 manufactured by Nippon Steel Chemical & Material Co., Ltd., EPICLON 830, 835, 840, 850, N-730A, and N-695 manufactured by DIC Corporation, and RE-306 manufactured by Nippon Kayaku Co., Ltd.
エポキシ樹脂の配合量は、(A)重量平均分子量3000以下であるアルカリ可溶性感光性樹脂および(B)イミド骨格を含むアルカリ可溶性感光性樹脂の合計100質量部に対して、固形分換算で、好ましくは50質量部以上150質量部以下であり、より好ましくは70質量部以上120質量部以下であり、さらに好ましくは90質量部以上110質量部以下である。エポキシ樹脂の配合量を上記の範囲とすることにより、より現像性に優れ、かつ硬化物の柔軟性、密着性及び耐熱性により優れた硬化物を得ることができる。 The amount of epoxy resin is, in terms of solid content, preferably 50 parts by mass or more and 150 parts by mass or less, more preferably 70 parts by mass or more and 120 parts by mass or less, and even more preferably 90 parts by mass or more and 110 parts by mass or less, per 100 parts by mass of the total of (A) the alkali-soluble photosensitive resin having a weight average molecular weight of 3000 or less and (B) the alkali-soluble photosensitive resin containing an imide skeleton. By setting the amount of epoxy resin in the above range, it is possible to obtain a cured product that is more excellent in developability and has more excellent flexibility, adhesion, and heat resistance.
((D)光重合開始剤)
光重合開始剤は、アルカリ可溶性感光性樹脂や光重合性モノマーを露光により反応させるためのものである。光重合開始剤としては、公知のものをいずれも用いることができる。光重合開始剤は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
((D) Photopolymerization initiator)
The photopolymerization initiator is used to react the alkali-soluble photosensitive resin or the photopolymerizable monomer by exposure to light. Any known photopolymerization initiator can be used. The photopolymerization initiator may be used alone or in combination of two or more.
光重合開始剤としては、具体的には例えば、ビス-(2,6-ジクロロベンゾイル)フェニルフォスフィンオキサイド、ビス-(2,6-ジクロロベンゾイル)-2,5-ジメチルフェニルフォスフィンオキサイド、ビス-(2,6-ジクロロベンゾイル)-4-プロピルフェニルフォスフィンオキサイド、ビス-(2,6-ジクロロベンゾイル)-1-ナフチルフォスフィンオキサイド、ビス-(2,6-ジメトキシベンゾイル)フェニルフォスフィンオキサイド、ビス-(2,6-ジメトキシベンゾイル)-2,4,4-トリメチルペンチルフォスフィンオキサイド、ビス-(2,6-ジメトキシベンゾイル)-2,5-ジメチルフェニルフォスフィンオキサイド、ビス-(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド等のビスアシルフォスフィンオキサイド類;2,6-ジメトキシベンゾイルジフェニルフォスフィンオキサイド、2,6-ジクロロベンゾイルジフェニルフォスフィンオキサイド、2,4,6-トリメチルベンゾイルフェニルフォスフィン酸メチルエステル、2-メチルベンゾイルジフェニルフォスフィンオキサイド、ピバロイルフェニルフォスフィン酸イソプロピルエステル、2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド等のモノアシルフォスフィンオキサイド類;フェニル(2,4,6-トリメチルベンゾイル)フォスフィン酸エチル、1-ヒドロキシ-シクロヘキシルフェニルケトン、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-ヒドロキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]フェニル}-2-メチル-プロパン-1-オン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン等のヒドロキシアセトフェノン類;ベンゾイン、ベンジル、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインn-プロピルエーテル、ベンゾインイソプロピルエーテル、ベンゾインn-ブチルエーテル等のベンゾイン類;ベンゾインアルキルエーテル類;ベンゾフェノン、p-メチルベンゾフェノン、ミヒラーズケトン、メチルベンゾフェノン、4,4’-ジクロロベンゾフェノン、4,4’-ビスジエチルアミノベンゾフェノン等のベンゾフェノン類;アセトフェノン、2,2-ジメトキシ-2-フェニルアセトフェノン、2,2-ジエトキシ-2-フェニルアセトフェノン、1,1-ジクロロアセトフェノン、1-ヒドロキシシクロヘキシルフェニルケトン、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノ-1-プロパノン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1、2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル)-1-[4-(4-モルホリニル)フェニル]-1-ブタノン、N,N-ジメチルアミノアセトフェノン等のアセトフェノン類;チオキサントン、2-エチルチオキサントン、2-イソプロピルチオキサントン、2,4-ジメチルチオキサントン、2,4-ジエチルチオキサントン、2-クロロチオキサントン、2,4-ジイソプロピルチオキサントン等のチオキサントン類;アントラキノン、クロロアントラキノン、2-メチルアントラキノン、2-エチルアントラキノン、2-tert-ブチルアントラキノン、1-クロロアントラキノン、2-アミルアントラキノン、2-アミノアントラキノン等のアントラキノン類;アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類;エチル-4-ジメチルアミノベンゾエート、2-(ジメチルアミノ)エチルベンゾエート、p-ジメチル安息香酸エチルエステル等の安息香酸エステル類;1,2-オクタンジオン,1-[4-(フェニルチオ)フェニル]-,2-(O-ベンゾイルオキシム)]、エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシム)等のオキシムエステル類;ビス(η5-2,4-シクロペンタジエン-1-イル)-ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)フェニル)チタニウム、ビス(シクロペンタジエニル)-ビス[2,6-ジフルオロ-3-(2-(1-ピル-1-イル)エチル)フェニル]チタニウム等のチタノセン類;フェニルジスルフィド2-ニトロフルオレン、ブチロイン、アニソインエチルエーテル、アゾビスイソブチロニトリル、テトラメチルチウラムジスルフィド等を挙げることができる。 Specific examples of photopolymerization initiators include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, and bis-(2,6-dimethoxybenzoyl)-2,4,4-triphenylphosphine oxide. Bisacylphosphine oxides such as methylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, and bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide; monoacylphosphine oxides such as phenyl(2,4,6-trimethylbenzoyl)phosphinate ethyl, 1-hydroxy-cyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl hydroxyacetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc.; benzoins such as benzoin, benzil, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, etc.; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiphenyl ether, etc. benzophenones such as ethylaminobenzophenone; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- acetophenones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2- Anthraquinones such as amylanthraquinone and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-( Examples of such compounds include oxime esters such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and titanocenes such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyrrol-1-yl)ethyl)phenyl]titanium; phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, and tetramethylthiuram disulfide.
α-アミノアセトフェノン系光重合開始剤の市販品としては、IGM Resins社製のOmnirad 907、369、369E、379等が挙げられる。また、アシルフォスフィンオキサイド系光重合開始剤の市販品としては、IGM Resins社製のOmnirad 819等が挙げられる。オキシムエステル系光重合開始剤の市販品としては、BASFジャパン株式会社製のIrgacure OXE01、OXE02、株式会社ADEKA製N-1919、アデカアークルズ NCI-831、NCI-831E、常州強力電子新材料社製TR-PBG-304などが挙げられる。 Commercially available α-aminoacetophenone photopolymerization initiators include Omnirad 907, 369, 369E, and 379 manufactured by IGM Resins. Commercially available acylphosphine oxide photopolymerization initiators include Omnirad 819 manufactured by IGM Resins. Commercially available oxime ester photopolymerization initiators include Irgacure OXE01 and OXE02 manufactured by BASF Japan Ltd., N-1919 manufactured by ADEKA Corporation, Adeka Arcles NCI-831 and NCI-831E, and TR-PBG-304 manufactured by Changzhou Strong Electronic New Materials Co., Ltd.
その他、特開2004-359639号公報、特開2005-097141号公報、特開2005-220097号公報、特開2006-160634号公報、特開2008-094770号公報、特表2008-509967号公報、特表2009-040762号公報、特開2011-80036号公報記載のカルバゾールオキシムエステル化合物等を挙げることができる。 Other examples include carbazole oxime ester compounds described in JP-A-2004-359639, JP-A-2005-097141, JP-A-2005-220097, JP-A-2006-160634, JP-A-2008-094770, JP-T-2008-509967, JP-T-2009-040762, and JP-T-2011-80036.
光重合開始剤の配合量は、硬化性樹脂組成物全量あたり固形分換算で、好ましくは0.1~10質量%であり、より好ましくは1~7質量%である。光重合開始剤の配合量は、0.1質量%以上の場合、硬化性樹脂組成物の光硬化性が良好となり、耐薬品性等の塗膜特性も良好となる。一方、10質量%以下の場合、レジスト膜(硬化塗膜)表面での光吸収が良好となり、深部硬化性が低下しにくい。 The amount of the photopolymerization initiator is preferably 0.1 to 10% by mass, more preferably 1 to 7% by mass, calculated as the solid content based on the total amount of the curable resin composition. When the amount of the photopolymerization initiator is 0.1% by mass or more, the photocurability of the curable resin composition is good, and the coating properties such as chemical resistance are also good. On the other hand, when the amount is 10% by mass or less, the light absorption at the surface of the resist film (cured coating film) is good, and the deep curing property is less likely to decrease.
上記した光重合開始剤と併用して、光開始助剤または増感剤を用いてもよい。光開始助剤または増感剤としては、ベンゾイン化合物、アントラキノン化合物、チオキサントン化合物、ケタール化合物、ベンゾフェノン化合物、3級アミン化合物、およびキサントン化合物などを挙げることができる。特に、2,4-ジメチルチオキサントン、2,4-ジエチルチオキサントン、2-クロロチオキサントン、2-イソプロピルチオキサントン、4-イソプロピルチオキサントン等のチオキサントン化合物を用いることが好ましい。チオキサントン化合物が含まれることにより、深部硬化性を向上させることができる。これらの化合物は、光重合開始剤として用いることができる場合もあるが、光重合開始剤と併用して用いることが好ましい。また、光開始助剤または増感剤は1種類を単独で用いてもよく、2種以上を併用してもよい。 A photoinitiator assistant or sensitizer may be used in combination with the above-mentioned photopolymerization initiator. Examples of the photoinitiator assistant or sensitizer include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. In particular, it is preferable to use thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone. The inclusion of a thioxanthone compound can improve deep curing properties. These compounds may be used as photopolymerization initiators, but are preferably used in combination with a photopolymerization initiator. In addition, the photoinitiator assistant or sensitizer may be used alone or in combination of two or more types.
なお、これら光重合開始剤、光開始助剤、および増感剤は、特定の波長を吸収するため、場合によっては感度が低くなり、紫外線吸収剤として機能することがある。しかしながら、これらは樹脂組成物の感度を向上させることだけの目的に用いられるものではない。必要に応じて特定の波長の光を吸収させて、表面の光反応性を高め、レジストパターンのライン形状および開口を垂直、テーパー状、逆テーパー状に変化させるとともに、ライン幅や開口径の精度を向上させることができる。 These photopolymerization initiators, photoinitiator assistants, and sensitizers absorb specific wavelengths, and therefore in some cases may have low sensitivity and function as ultraviolet absorbers. However, they are not used solely for the purpose of improving the sensitivity of the resin composition. They can absorb light of specific wavelengths as necessary to increase the photoreactivity of the surface, change the line shape and openings of the resist pattern to vertical, tapered, or reverse tapered, and improve the precision of the line width and opening diameter.
((E)光重合性モノマー)
光重合性モノマーは、エチレン性不飽和二重結合を有するモノマーである。光重合性モノマーを含むことにより、硬化塗膜の耐溶剤性を向上させることができる。光重合性モノマーは、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
((E) Photopolymerizable Monomer)
The photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond. By including the photopolymerizable monomer, the solvent resistance of the cured coating film can be improved. The photopolymerizable monomer may be used alone or in combination of two or more kinds.
光重合性モノマーとしては、例えば、慣用公知のポリエステル(メタ)アクリレート、ポリエーテル(メタ)アクリレート、ウレタン(メタ)アクリレート、カーボネート(メタ)アクリレート、エポキシ(メタ)アクリレート等が挙げられる。具体的には、2-エチルヘキシルアクリレート、シクロヘキシルアクリレート等のアルキルアクリレート類;2-ヒドロキシエチルアクリレート、2-ヒドロキシプロピルアクリレート等のヒドロキシアルキルアクリレート類;エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール等のアルキレンオキサイド誘導体のモノまたはジアクリレート類;N,N-ジメチルアクリルアミド、N-メチロールアクリルアミド、N,N-ジメチルアミノプロピルアクリルアミドなどのアクリルアミド類;N,N-ジメチルアミノエチルアクリレート、N,N-ジメチルアミノプロピルアクリレート等のアミノアルキルアクリレート類;ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、ジトリメチロールプロパン、ジペンタエリスリトール、トリスヒドロキシエチルイソシアヌレート等の多価アルコールまたはこれらのアルキレンオキサイド付加物あるいはε-カプロラクトン付加物等の多価アクリレート類;フェノキシアクリレート、ビスフェノールAジアクリレート等のフェノール類またはこれらのアルキレンオキサイド付加物等の多価アクリレート類;グリセリンジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリグリシジルイソシアヌレート等のグリシジルエーテルのアクリレート類;前記に限らず、ポリエーテルポリオール、ポリカーボネートジオール、水酸基末端ポリブタジエン、ポリエステルポリオール等のポリオールを直接アクリレート化、もしくは、ジイソシアネートを介してウレタンアクリレート化したアクリレート類およびメラミンアクリレート、および前記アクリレートに対応する各メタクリレート類の少なくともいずれか1種から適宜選択して用いることができる。このような光重合性モノマーは、反応性希釈剤としても用いることができる。 Examples of photopolymerizable monomers include commonly used polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, carbonate (meth)acrylates, and epoxy (meth)acrylates. Specific examples include alkyl acrylates such as 2-ethylhexyl acrylate and cyclohexyl acrylate; hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; mono- or diacrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide, and N,N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and trishydroxyethyl isocyanurate. Polyhydric alcohols such as polyhydric alcohols, their alkylene oxide adducts, or their ε-caprolactone adducts; phenols such as phenoxy acrylate and bisphenol A diacrylate, and their alkylene oxide adducts; glycidyl ether acrylates such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; and acrylates obtained by directly acrylate polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, and polyester polyols, or by urethane acrylate via diisocyanates, melamine acrylates, and at least one of the methacrylates corresponding to the acrylates can be appropriately selected and used. Such photopolymerizable monomers can also be used as reactive diluents.
光重合性モノマーの配合量は、(A)重量平均分子量3000以下であるアルカリ可溶性感光性樹脂および(B)イミド骨格を含むアルカリ可溶性感光性樹脂の合計100質量部に対して、固形分換算で、好ましくは10質量部以上60質量部以下であり、より好ましくは15質量部以上55質量部以下であり、さらに好ましくは20質量部以上50質量部以下である。光重合性モノマーの配合量が10質量部以上であると、光硬化性が良好であり、活性エネルギー線照射後のアルカリ現像において、パターン形成がし易い。また、配合量が50質量部以下であると、ハレーションが生じにくく良好な解像性が得られ易い。 The amount of the photopolymerizable monomer is, in terms of solid content, preferably 10 parts by mass or more and 60 parts by mass or less, more preferably 15 parts by mass or more and 55 parts by mass or less, and even more preferably 20 parts by mass or more and 50 parts by mass or less, per 100 parts by mass of the total of (A) the alkali-soluble photosensitive resin having a weight-average molecular weight of 3000 or less and (B) the alkali-soluble photosensitive resin containing an imide skeleton. When the amount of the photopolymerizable monomer is 10 parts by mass or more, the photocurability is good, and pattern formation is easy in alkaline development after irradiation with active energy rays. Furthermore, when the amount is 50 parts by mass or less, halation is unlikely to occur and good resolution is easily obtained.
((F)無機フィラー)
無機フィラーとしては、従来公知のものを使用でき、シリカ、タルク、マイカ、酸化アルミニウム、酸化カルシウム、酸化マグネシウム、酸化亜鉛、炭酸カルシウム、炭酸マグネシウム、フライアッシュ、脱水汚泥、カオリン、クレー、水酸化カルシウム、水酸化アルミニウム、水酸化マグネシウム、ハイドロタルサイト、珪酸アルミニウム、珪酸マグネシウム、ケイ酸カルシウム、ウォラストナイト、チタン酸カリウム、硫酸マグネシウム、硫酸カルシウム、燐酸マグネシウム、セピオライト、ゾノライト、窒化ホウ素、ホウ酸アルミニウム、シリカバルーン、ガラスフレーク、ガラスバルーン、製鉄スラグ、銅、鉄、酸化鉄、センダスト、アルニコ磁石、各種フェライト等の磁性粉、セメント、ガラス粉末、ノイブルグ珪土、珪藻土、三酸化アンチモン、マグネシウムオキシサルフェイト、水和アルミニウム、水和石膏、ミョウバンおよび硫酸バリウム等が挙げられる。これら無機フィラーは1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
((F) Inorganic Filler)
As the inorganic filler, a conventionally known one can be used, and examples thereof include silica, talc, mica, aluminum oxide, calcium oxide, magnesium oxide, zinc oxide, calcium carbonate, magnesium carbonate, fly ash, dewatered sludge, kaolin, clay, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, hydrotalcite, aluminum silicate, magnesium silicate, calcium silicate, wollastonite, potassium titanate, magnesium sulfate, calcium sulfate, magnesium phosphate, sepiolite, zonolite, boron nitride, aluminum borate, silica balloons, glass flakes, glass balloons, ironmaking slag, copper, iron, iron oxide, sendust, alnico magnets, magnetic powders such as various ferrites, cement, glass powder, Neuburg diatomaceous earth, diatomaceous earth, antimony trioxide, magnesium oxysulfate, aluminum hydrate, hydrated gypsum, alum, and barium sulfate. These inorganic fillers may be used alone or in combination of two or more.
上記の無機フィラーの中でもシリカが好ましく、表面処理を施していないシリカがより好ましい。表面処理を施していないシリカは、表面処理が施されたシリカに比べて、シリカ表面の極性が高いため、シリカの親水性が向上し、現像時の残渣除去の効果が得られ易い。
なお、本発明においては、「表面処理を施していない」シリカとは、従来公知の表面処理方法で処理していないシリカを指す。従来公知の表面処理方法としては、硬化性反応基を有する表面処理剤で処理する方法が挙げられる。具体的には、硬化性反応基を有機基として有するカップリング剤等で処理する方法が挙げられる。このような表面処理を施した場合、シリカ表面の極性が低くなり、シリカの親水性が低下する恐れがある。
Among the above inorganic fillers, silica is preferred, and surface-untreated silica is more preferred. Surface-untreated silica has a higher polarity on the silica surface than surface-treated silica, which improves the hydrophilicity of the silica and makes it easier to remove residues during development.
In the present invention, "non-surface-treated" silica refers to silica that has not been treated by a conventionally known surface treatment method. Conventionally known surface treatment methods include a method of treating with a surface treatment agent having a curable reactive group. Specifically, a method of treating with a coupling agent having a curable reactive group as an organic group can be mentioned. When such a surface treatment is performed, the polarity of the silica surface is reduced, and the hydrophilicity of the silica may be reduced.
無機フィラーは、分散性等の観点から、平均粒径(D50)が好ましくは5nm以上500nm以下であり、より好ましくは7nm以上180nm以下であり、さらに好ましくは10nm以上100nm以下である。
なお、平均粒径は、レーザー回折散乱式粒度分布測定法を用いて得られる体積累積50%における粒径を意味する。また、シリカの平均粒径は、感光性樹脂組成物を調製(攪拌、混練)する前の無機フィラーを上記のようにして測定した値をいうものとする。
From the viewpoint of dispersibility, the inorganic filler preferably has an average particle size (D50) of 5 nm or more and 500 nm or less, more preferably 7 nm or more and 180 nm or less, and further preferably 10 nm or more and 100 nm or less.
The average particle size means a particle size at 50% cumulative volume obtained by a laser diffraction/scattering particle size distribution measurement method. The average particle size of silica means a value measured as described above for the inorganic filler before preparing (stirring and kneading) the photosensitive resin composition.
無機フィラーの配合量は、硬化性樹脂組成物全量あたり固形分換算で、好ましくは3質量%以上50質量%以下であり、より好ましくは10質量%以上35質量%以下である。無機フィラーの配合量が上記数値範囲内であれば、より解像性、塗膜の熱膨張率及び誘電特性が向上し易い。 The amount of inorganic filler is preferably 3% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 35% by mass or less, calculated as solid content based on the total amount of the curable resin composition. If the amount of inorganic filler is within the above numerical range, the resolution, the thermal expansion coefficient and the dielectric properties of the coating film are more likely to be improved.
本発明の硬化性樹脂組成物は、以下の任意成分を含んでもよい。 The curable resin composition of the present invention may contain the following optional components:
(硬化剤)
硬化剤としては、例えば、イミダゾール、2-メチルイミダゾール、2-エチルイミダゾール、2-エチル-4-メチルイミダゾール、2-フェニルイミダゾール、4-フェニルイミダゾール、1-シアノエチル-2-フェニルイミダゾール、1-(2-シアノエチル)-2-エチル-4-メチルイミダゾール等のイミダゾール誘導体;ジシアンジアミド、ベンジルジメチルアミン、4-(ジメチルアミノ)-N,N-ジメチルベンジルアミン、4-メトキシ-N,N-ジメチルベンジルアミン、4-メチル-N,N-ジメチルベンジルアミン等のアミン化合物、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド等のヒドラジン化合物;トリフェニルフォスフィン等のリン化合物等が挙げられる。また、市販されているものとしては、例えば四国化成工業株式会社製の2MZ-A、2MZ-OK、2PHZ、2P4BHZ、2P4MHZ(いずれもイミダゾール系化合物の商品名)、サンアプロ株式会社製のU-CAT 3513N(ジメチルアミン系化合物の商品名)、DBU、DBN、U-CAT SA 102(いずれも二環式アミジン化合物およびその塩)などが挙げられる。特に、これらに限られるものではなく、エポキシ樹脂やオキセタン化合物の硬化剤、もしくはエポキシ基およびオキセタニル基の少なくともいずれか1種とカルボキシル基の反応を促進するものであればよく、単独でまたは2種以上を混合して使用してもかまわない。
(Hardening agent)
Examples of the curing agent include imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available compounds include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd., and U-CAT 3513N (trade name of dimethylamine-based compounds), DBU, DBN, and U-CAT SA 102 (all bicyclic amidine compounds and salts thereof) manufactured by San-Apro Co., Ltd. In particular, the compound is not limited to these, and any compound that promotes the reaction of at least one of an epoxy resin or oxetane compound curing agent and an epoxy group and an oxetanyl group with a carboxyl group may be used alone or in combination of two or more kinds.
さらに、グアナミン、アセトグアナミン、ベンゾグアナミン、メラミン、2,4-ジアミノ-6-メタクリロイルオキシエチル-S-トリアジン、2-ビニル-2,4-ジアミノ-S-トリアジン、2-ビニル-4,6-ジアミノ-S-トリアジン・イソシアヌル酸付加物、2,4-ジアミノ-6-メタクリロイルオキシエチル-S-トリアジン・イソシアヌル酸付加物等のS-トリアジン誘導体を用いることもでき、好ましくはこれら密着性付与剤としても機能する化合物を硬化剤と併用する。硬化剤は、1種を単独で用いてもよく、2種以上を併用してもよい。 Furthermore, S-triazine derivatives such as guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, and 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct can also be used, and preferably these compounds that also function as adhesion-imparting agents are used in combination with the curing agent. The curing agent may be used alone or in combination of two or more types.
硬化剤の配合量は、硬化性樹脂組成物全量あたり固形分換算で、好ましくは0.1~8質量%であり、より好ましくは0.3~5質量%である。 The amount of the curing agent is preferably 0.1 to 8 mass %, more preferably 0.3 to 5 mass %, calculated as solid content based on the total amount of the curable resin composition.
(着色剤)
本発明の硬化性樹脂組成物には、着色剤を配合することができる。着色剤としては、特に限定されず、赤、青、緑、黄等の公知の着色剤を使用することができ、顔料、染料、色素のいずれでもよいが、環境負荷の低減や人体への影響が少ない観点からハロゲンを含有しない着色剤であることが好ましい。
(Coloring Agent)
A colorant can be blended in the curable resin composition of the present invention. The colorant is not particularly limited, and known colorants such as red, blue, green, and yellow can be used. Any of pigments, dyes, and coloring matters can be used, but from the viewpoint of reducing the environmental load and having little effect on the human body, it is preferable that the colorant does not contain halogen.
赤色着色剤としてはモノアゾ系、ジスアゾ系、アゾレーキ系、ベンズイミダゾロン系、ペリレン系、ジケトピロロピロール系、縮合アゾ系、アントラキノン系、キナクリドン系等があり、具体的には以下のようなカラ-インデックス(C.I.;ザ ソサイエティ オブ ダイヤーズ アンド カラリスツ(The Society of Dyersand Colourists)発行)番号が付されているものが挙げられる。 Red colorants include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone, and specific examples include those with the following Color Index (C.I.; published by The Society of Dyers and Colourists) numbers:
モノアゾ系赤色着色剤としては、Pigment Red 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114,146,147,151,170,184,187,188,193,210,245,253,258,266,267,268,269等が挙げられる。また、ジスアゾ系赤色着色剤としては、Pigment Red 37,38,41等が挙げられる。また、モノアゾレーキ系赤色着色剤としては、Pigment Red 48:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,52:2,53:1,53:2,57:1,58:4,63:1,63:2,64:1,68等が挙げられる。また、ベンズイミダゾロン系赤色着色剤としては、Pigment Red 171,175,176、185、208等が挙げられる。また、ぺリレン系赤色着色剤としては、Solvent Red 135,179,Pigment Red 123,149,166,178,179,190,194,224等が挙げられる。また、ジケトピロロピロール系赤色着色剤としては、Pigment Red 254,255,264,270,272等が挙げられる。また、縮合アゾ系赤色着色剤としては、Pigment Red 220,144,166,214,220,221,242等が挙げられる。また、アントラキノン系赤色着色剤としては、Pigment Red 168,177,216、Solvent Red 149,150,52,207等が挙げられる。また、キナクリドン系赤色着色剤としては、Pigment Red 122,202,206,207,209等が挙げられる。 Examples of monoazo red colorants include Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, and 269. Examples of disazo red colorants include Pigment Red 37, 38, and 41. Examples of monoazo lake-based red colorants include Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, and 68. Examples of benzimidazolone-based red colorants include Pigment Red 171, 175, 176, 185, and 208. Examples of perylene-based red colorants include Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, and 224. Examples of diketopyrrolopyrrole red colorants include Pigment Red 254, 255, 264, 270, and 272. Examples of condensed azo red colorants include Pigment Red 220, 144, 166, 214, 220, 221, and 242. Examples of anthraquinone red colorants include Pigment Red 168, 177, and 216, Solvent Red 149, 150, 52, and 207. Examples of quinacridone red colorants include Pigment Red 122, 202, 206, 207, and 209.
青色着色剤としてはフタロシアニン系、アントラキノン系があり、顔料系はピグメント(Pigment)に分類されている化合物が挙げられ、例えば、Pigment Blue 15,15:1,15:2,15:3,15:4,15:6,16,60。染料系としては、Solvent Blue 35,63,68,70,83,87,94,97,122,136,67,70等を使用することができる。上記以外にも、金属置換もしくは無置換のフタロシアニン化合物も使用することができる。 Blue colorants include phthalocyanine and anthraquinone types, and pigment types include compounds classified as pigments, such as Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, and 60. Dye types include Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, and 70. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.
黄色着色剤としてはモノアゾ系、ジスアゾ系、縮合アゾ系、ベンズイミダゾロン系、イソインドリノン系、アントラキノン系等が挙げられ、例えば、アントラキノン系黄色着色剤としては、Solvent Yellow 163,Pigment Yellow 24,108,193,147,199,202等が挙げられる。イソインドリノン系黄色着色剤としては、Pigment Yellow 110,109,139,179,185等が挙げられる。縮合アゾ系黄色着色剤としては、Pigment Yellow 93,94,95,128,155,166,180等が挙げられる。ベンズイミダゾロン系黄色着色剤としては、Pigment Yellow 120,151,154,156,175,181等が挙げられる。また、モノアゾ系黄色着色剤としては、Pigment Yellow 1,2,3,4,5,6,9,10,12,61,62,62:1,65,73,74,75,97,100,104,105,111,116,167,168,169,182,183等が挙げられる。また、ジスアゾ系黄色着色剤としては、Pigment Yellow 12,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174,176,188,198等が挙げられる。 Yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, etc. For example, anthraquinone yellow colorants include Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202, etc. Isoindolinone yellow colorants include Pigment Yellow 110, 109, 139, 179, 185, etc. Condensed azo yellow colorants include Pigment Yellow 93, 94, 95, 128, 155, 166, 180, etc. Examples of benzimidazolone yellow colorants include Pigment Yellow 120, 151, 154, 156, 175, and 181. Examples of monoazo yellow colorants include Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, and 183. Examples of disazo yellow colorants include Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, and 198.
その他、紫、オレンジ、茶色、黒等の着色剤を加えてもよい。具体的には、Pigment Black 1,6,7,8,9,10,11,12,13,18,20,25,26,28,29,30,31,32、Pigment Violet 19、23、29、32、36、38、42、Solvent Violet13,36、C.I.Pigment Orange 1,5,13,14,16,17,24,34,36,38,40,43,46,49,51,61,63,64,71,73、PigmentBrown 23,25,カーボンブラック等が挙げられる。 In addition, colorants such as purple, orange, brown, and black may be added. Specific examples include Pigment Black 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, Pigment Brown 23, 25, and carbon black.
着色剤の配合量は、硬化性樹脂組成物全量あたり固形分換算で、好ましくは0.1~2.0質量%であり、より好ましくは0.3~1.5質量%である。 The amount of colorant blended is preferably 0.1 to 2.0 mass %, more preferably 0.3 to 1.5 mass %, calculated as solid content based on the total amount of the curable resin composition.
(有機溶剤)
本発明の硬化性樹脂組成物には、組成物の調製や、基板やフィルムに塗布する際の粘度調整等の目的で、有機溶剤を含有させることができる。有機溶剤としては、メチルエチルケトン、シクロヘキサノン等のケトン類;トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類;セロソルブ、メチルセロソルブ、ブチルセロソルブ、カルビトール、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジエチルエーテル、ジエチレングリコールモノメチルエーテルアセテート、トリプロピレングリコールモノメチルエーテル等のグリコールエーテル類;酢酸エチル、酢酸ブチル、乳酸ブチル、セロソルブアセテート、ブチルセロソルブアセテート、ジエチレングリコールモノエチルエーテルアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、炭酸プロピレン等のエステル類;オクタン、デカン等の脂肪族炭化水素類;石油エーテル、石油ナフサ、ソルベントナフサ等の石油系溶剤など、公知慣用の有機溶剤が使用できる。これらの有機溶剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
(Organic solvent)
The curable resin composition of the present invention may contain an organic solvent for the purpose of adjusting the viscosity when preparing the composition or when applying it to a substrate or film. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, diethylene glycol monoethyl ether acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, petroleum naphtha, and solvent naphtha. These organic solvents may be used alone or in combination of two or more kinds.
有機溶剤の配合量は、特に限定されず、硬化性樹脂組成物を調製し易いように目的の粘度に応じて適宜設定することができる。 The amount of organic solvent to be added is not particularly limited, and can be set appropriately according to the desired viscosity so that the curable resin composition can be easily prepared.
(その他の添加成分)
本発明の硬化性樹脂組成物には、必要に応じてさらに、シアネート化合物、エラストマー、メルカプト化合物、ウレタン化触媒、チキソ化剤、密着促進剤、ブロック共重合体、連鎖移動剤、重合禁止剤、銅害防止剤、酸化防止剤、防錆剤、増粘剤、シリコーン系、フッ素系、高分子系等の消泡剤およびレベリング剤の少なくともいずれか1種、イミダゾール系、チアゾール系、トリアゾール系等のシランカップリング剤、フォスフィン酸塩、燐酸エステル誘導体、フォスファゼン化合物等のリン化合物等の難燃剤などの成分を配合することができる。これらは、電子材料の分野において公知の物を使用することができる。
(Other added ingredients)
The curable resin composition of the present invention may further contain, as necessary, components such as cyanate compounds, elastomers, mercapto compounds, urethanization catalysts, thixotropic agents, adhesion promoters, block copolymers, chain transfer agents, polymerization inhibitors, copper inhibitors, antioxidants, rust inhibitors, thickeners, at least one of silicone-based, fluorine-based, and polymer-based defoamers and leveling agents, imidazole-based, thiazole-based, and triazole-based silane coupling agents, and phosphorus compounds such as phosphinates, phosphate ester derivatives, and phosphazene compounds. These may be known in the field of electronic materials.
本発明の硬化性樹脂組成物は、ドライフィルム化して用いてもよい。 The curable resin composition of the present invention may be used in the form of a dry film.
[調製方法]
本発明の硬化性樹脂組成物の調製には、各成分を秤量、配合した後、攪拌機にて予備攪拌する。続いて、混練機にて各成分を分散させ、混練を行うことで調製することができる。
[Preparation method]
In preparing the curable resin composition of the present invention, each component is weighed, mixed, and then pre-mixed with a mixer, and then each component is dispersed and kneaded with a kneader to prepare the curable resin composition.
上記の混練機としては、例えばビーズミル、ボールミル、サンドミル、3本ロールミル、2本ロールミル等を挙げることができる。これらの中でも、分散性を向上させるためには、ビーズミルを用いることが好ましい。ビーズミルのビーズの種類や粒径等の分散条件は、目的とする粘度に応じて適宜設定することができる。 Examples of the kneading machine include a bead mill, a ball mill, a sand mill, a three-roll mill, and a two-roll mill. Among these, it is preferable to use a bead mill in order to improve dispersibility. The dispersion conditions, such as the type and particle size of the beads of the bead mill, can be appropriately set according to the desired viscosity.
[用途]
本発明による硬化性樹脂組成物は、プリント配線板の永久被膜としてパターン層を形成するために有用であり、さらにソルダーレジストやカバーレイ、層間絶縁層、再配線層等の形成に有用である。また、本発明の硬化性樹脂組成物は、薄膜でも膜強度に優れた硬化物を形成できることから、薄膜化が要求されるプリント配線板、例えばパッケージ基板(半導体パッケージに用いられるプリント配線板)におけるパターン層の形成にも好適に用いることができる。
[Application]
The curable resin composition according to the present invention is useful for forming a pattern layer as a permanent coating on a printed wiring board, and is further useful for forming a solder resist, a coverlay, an interlayer insulating layer, a rewiring layer, etc. In addition, since the curable resin composition according to the present invention can form a cured product having excellent film strength even in a thin film, it can also be suitably used for forming a pattern layer in a printed wiring board that requires a thin film, such as a package substrate (a printed wiring board used for a semiconductor package).
また、本発明の硬化性樹脂組成物は、硬化塗膜のパターン層を形成する用途だけでなく、パターン層を形成しない用途、例えばモールド用途(封止用途)に用いることができる。 The curable resin composition of the present invention can be used not only for forming a pattern layer of a cured coating film, but also for applications that do not form a pattern layer, such as molding applications (sealing applications).
[ドライフィルム]
本発明の硬化性樹脂組成物は、第一のフィルムと、この第一のフィルム上に形成された上記硬化性樹脂組成物の乾燥塗膜からなる樹脂層とを備えたドライフィルムの形態とすることもできる。ドライフィルム化に際しては、本発明の硬化性樹脂組成物を上記有機溶剤で希釈して適切な粘度に調整し、コンマコーター、ブレードコーター、リップコーター、ロッドコーター、スクイズコーター、リバースコーター、トランスファロールコーター、グラビアコーター、スプレーコーター等で第一のフィルム上に均一な厚さに塗布し、通常、50~130℃の温度で1~30分間乾燥して膜を得ることができる。塗布膜厚については特に制限はないが、一般に、乾燥後膜厚で、1~150μm、好ましくは5~60μmの範囲で適宜選択される。
[Dry film]
The curable resin composition of the present invention can also be in the form of a dry film comprising a first film and a resin layer consisting of a dried coating film of the curable resin composition formed on the first film. In forming the dry film, the curable resin composition of the present invention is diluted with the organic solvent to adjust the viscosity to an appropriate level, and is applied to a uniform thickness on the first film using a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, or the like, and is usually dried at a temperature of 50 to 130° C. for 1 to 30 minutes to obtain a film. There is no particular restriction on the coating film thickness, but the thickness after drying is generally appropriately selected within the range of 1 to 150 μm, preferably 5 to 60 μm.
第一のフィルムとしては、公知のものであれば特に制限なく使用することができ、例えば、ポリエチレンテレフタレートやポリエチレンナフタレート等のポリエステルフィルム、ポリイミドフィルム、ポリアミドイミドフィルム、ポリプロピレンフィルム、ポリスチレンフィルム等の熱可塑性樹脂からなるフィルムを好適に使用することができる。これらの中でも、耐熱性、機械的強度、取扱性等の観点から、ポリエステルフィルムが好ましい。また、これらフィルムの積層体を第一のフィルムとして使用することもできる。 As the first film, any known film can be used without particular limitation. For example, polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyimide films, polyamideimide films, polypropylene films, polystyrene films, and other films made of thermoplastic resins can be suitably used. Among these, polyester films are preferred from the viewpoints of heat resistance, mechanical strength, ease of handling, and the like. A laminate of these films can also be used as the first film.
また、上記したような熱可塑性樹脂フィルムは、機械的強度向上の観点から、一軸方向または二軸方向に延伸されたフィルムであることが好ましい。 In addition, from the viewpoint of improving mechanical strength, it is preferable that the thermoplastic resin film described above is a film that has been oriented uniaxially or biaxially.
第一のフィルムの厚さは、特に制限されるものではないが、例えば、10μm~150μmとすることができる。 The thickness of the first film is not particularly limited, but can be, for example, 10 μm to 150 μm.
第一のフィルム上に本発明の硬化性樹脂組成物の乾燥塗膜からなる樹脂層を形成した後、さらに、樹脂層の表面に塵が付着するのを防ぐなどの目的で、樹脂層の表面に剥離可能な第二のフィルムを積層することが好ましい。剥離可能な第二のフィルムとしては、例えば、ポリエチレンフィルム、ポリテトラフルオロエチレンフィルム、ポリプロピレンフィルム、表面処理した紙等を用いることができ、第二のフィルムを剥離するときに樹脂層と第一のフィルムとの接着力よりも樹脂層と第二のフィルムとの接着力がより小さいものであればよい。 After forming a resin layer consisting of a dried coating of the curable resin composition of the present invention on the first film, it is preferable to further laminate a peelable second film on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer. For example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, surface-treated paper, etc. can be used as the peelable second film, and it is sufficient that the adhesive strength between the resin layer and the second film is smaller than the adhesive strength between the resin layer and the first film when the second film is peeled off.
第二のフィルムの厚さは、特に限定されるものではないが、例えば、10μm~150μmとすることができる。 The thickness of the second film is not particularly limited, but can be, for example, 10 μm to 150 μm.
ドライフィルムを用いてプリント配線板上に硬化塗膜を作製するには、ドライフィルムから第二のフィルムを剥離し、ドライフィルムの露出した樹脂層を回路形成された基材に重ね、ラミネーター等を用いて貼り合わせ、回路形成された基材上に樹脂層を形成する。次いで、形成された樹脂層に対し、露光、現像、加熱硬化すれば、硬化塗膜を形成することができる。第二のフィルムは、露光前または露光後のいずれかで剥離すればよい。 To produce a cured coating film on a printed wiring board using a dry film, the second film is peeled off from the dry film, and the exposed resin layer of the dry film is placed on a substrate on which a circuit has been formed, and the two are laminated using a laminator or the like to form a resin layer on the substrate on which a circuit has been formed. The formed resin layer is then exposed to light, developed, and heat cured to form a cured coating film. The second film may be peeled off either before or after exposure.
[硬化物]
本発明の硬化物は、上記本発明の硬化性樹脂組成物、または、上記本発明のドライフィルムの樹脂層を硬化して得られるものである。硬化条件等の製造条件については[プリント配線板]にて後述する。本発明の硬化物は、プリント配線板や電子部品等に好適に用いることができる。
[Cured product]
The cured product of the present invention is obtained by curing the curable resin composition of the present invention or the resin layer of the dry film of the present invention. The manufacturing conditions such as curing conditions will be described later in [Printed wiring board]. The cured product of the present invention can be suitably used for printed wiring boards, electronic parts, etc.
[プリント配線板]
本発明のプリント配線板は、本発明の硬化性樹脂組成物またはドライフィルムの樹脂層から得られる硬化物を有するものである。本発明のプリント配線板の製造方法としては、例えば、本発明の硬化性樹脂組成物を、上記有機溶剤を用いて塗布方法に適した粘度に調整して、基材上に、ディップコート法、フローコート法、ロールコート法、バーコーター法、スクリーン印刷法、カーテンコート法等の方法により塗布した後、60~100℃の温度で15~90分間、組成物中に含まれる有機溶剤を揮発乾燥(仮乾燥)させることで、タックフリーの樹脂層を形成する。また、ドライフィルムの場合、ラミネーター等により樹脂層が基材と接触するように基材上に貼り合わせた後、第一のフィルムを剥がすことにより、基材上に樹脂層を形成する。
[Printed wiring board]
The printed wiring board of the present invention has a cured product obtained from the resin layer of the curable resin composition or dry film of the present invention. As a method for producing the printed wiring board of the present invention, for example, the curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method using the organic solvent, and applied to a substrate by a method such as dip coating, flow coating, roll coating, bar coater, screen printing, or curtain coating, and then the organic solvent contained in the composition is evaporated and dried (temporarily dried) at a temperature of 60 to 100° C. for 15 to 90 minutes to form a tack-free resin layer. In addition, in the case of a dry film, the resin layer is attached to the substrate by a laminator or the like so that the resin layer contacts the substrate, and then the first film is peeled off to form a resin layer on the substrate.
上記基材としては、あらかじめ銅等により回路形成されたプリント配線板やフレキシブルプリント配線板の他、紙フェノール、紙エポキシ、ガラス布エポキシ、ガラスポリイミド、ガラス布/不繊布エポキシ、ガラス布/紙エポキシ、合成繊維エポキシ、フッ素樹脂・ポリエチレン・ポリフェニレンエーテル、ポリフェニレンオキサイド・シアネート等を用いた高周波回路用銅張積層板等の材質を用いたもので、全てのグレード(FR-4等)の銅張積層板、その他、金属基板、ポリイミドフィルム、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレート(PEN)フィルム、ガラス基板、セラミック基板、ウエハ板等を挙げることができる。 The above-mentioned substrates include printed wiring boards and flexible printed wiring boards with circuits formed in advance using copper or the like, as well as materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven cloth epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, copper-clad laminates for high-frequency circuits using fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc., including copper-clad laminates of all grades (FR-4, etc.), as well as metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates, etc.
ドライフィルムの基材上への貼合は、真空ラミネーター等を用いて、加圧および加熱下で行うことが好ましい。このような真空ラミネーターを使用することにより、回路形成された基板を用いた場合に、回路基板表面に凹凸があっても、ドライフィルムが回路基板に密着するため、気泡の混入がなく、また、基板表面の凹部の穴埋め性も向上する。加圧条件は、0.1~2.0MPa程度であることが好ましく、また、加熱条件は、40~120℃であることが好ましい。 The dry film is preferably laminated onto the substrate under pressure and heat using a vacuum laminator or the like. By using such a vacuum laminator, when a circuit-formed substrate is used, the dry film adheres closely to the circuit substrate even if the substrate has an uneven surface, preventing the inclusion of air bubbles and improving the filling of recesses in the substrate surface. The pressure conditions are preferably about 0.1 to 2.0 MPa, and the heating conditions are preferably 40 to 120°C.
本発明の硬化性樹脂組成物を基材上に塗布した後に行う揮発乾燥は、熱風循環式乾燥炉、IR炉、ホットプレート、コンベクションオーブン等(蒸気による空気加熱方式の熱源を備えたものを用いて乾燥機内の熱風を向流接触せしめる方法およびノズルより支持体に吹き付ける方式)を用いて行うことができる。装置としては、熱風循環乾燥炉として、ヤマト科学株式会社製DF610等が挙げられる。 The volatilization drying carried out after the curable resin composition of the present invention is applied to a substrate can be carried out using a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, etc. (a method in which hot air in a dryer is brought into countercurrent contact using a heat source of an air heating method using steam, or a method in which hot air is blown onto a substrate from a nozzle). Examples of the apparatus include a hot air circulation drying oven such as DF610 manufactured by Yamato Scientific Co., Ltd.
基材上に樹脂層を形成後、所定のパターンを形成したフォトマスクを通して選択的に活性エネルギー線により露光し、未露光部を希アルカリ水溶液(例えば、0.3~3.0質量%炭酸ソーダ水溶液)により現像して硬化物のパターンを形成する。ドライフィルムの場合には、露光後、ドライフィルムから第一のフィルムを剥離して現像を行うことにより、基材上にパターニングされた硬化物を形成する。なお、特性を損なわない範囲であれば、露光前にドライフィルムから第一のフィルムを剥離して、露出した樹脂層を露光および現像してもよい。 After forming a resin layer on the substrate, it is selectively exposed to active energy rays through a photomask with a predetermined pattern formed thereon, and the unexposed areas are developed with a dilute alkaline aqueous solution (e.g., a 0.3 to 3.0% by mass aqueous solution of sodium carbonate) to form a pattern of the cured product. In the case of a dry film, after exposure, the first film is peeled off from the dry film and development is carried out to form a patterned cured product on the substrate. Note that, as long as the properties are not impaired, the first film may be peeled off from the dry film before exposure, and the exposed resin layer may be exposed and developed.
上記活性エネルギー線照射に用いられる露光機としては、高圧水銀灯ランプ、超高圧水銀灯ランプ、メタルハライドランプ、水銀ショートアークランプ等を搭載し、350~450nmの範囲で紫外線を照射する装置であればよく、さらに、直接描画装置(例えば、コンピューターからのCADデータにより直接レーザーで画像を描くレーザーダイレクトイメージング装置)も用いることができる。直描機のランプ光源またはレーザー光源としては、最大波長が350~450nmの範囲にあるものでよい。画像形成のための露光量は膜厚等によって異なるが、一般には10~1,000mJ/cm2、好ましくは20~800mJ/cm2の範囲内とすることができる。 The exposure machine used for the above-mentioned active energy ray irradiation may be a machine equipped with a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like, and capable of irradiating ultraviolet rays in the range of 350 to 450 nm, and further, a direct imaging machine (for example, a laser direct imaging machine that draws an image directly with a laser based on CAD data from a computer) may also be used. The lamp light source or laser light source of the direct imaging machine may have a maximum wavelength in the range of 350 to 450 nm. The exposure dose for forming an image varies depending on the film thickness, etc., but can generally be within the range of 10 to 1,000 mJ/cm 2 , preferably 20 to 800 mJ/cm 2 .
上記現像方法としては、ディッピング法、シャワー法、スプレー法、ブラシ法等によることができ、現像液としては、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、リン酸ナトリウム、ケイ酸ナトリウム、アンモニア、アミン類等のアルカリ水溶液が使用できる。 The above-mentioned developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and the developing solution can be an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc.
さらに、硬化物に活性エネルギー線を照射後に加熱硬化(例えば、100~220℃の温度で30~90分間)、もしくは加熱硬化後に活性エネルギー線を照射(例えば、1,000~2,000mJ/cm2)、または、加熱硬化のみで最終仕上げ硬化(本硬化) させることにより、密着性、硬度等の諸特性に優れた硬化塗膜を形成する。装置としては、高圧水銀ランプを用いたUVコンベアとして、株式会社オーク製作所製QRM-2082等が挙げられる。 Furthermore, the cured product is irradiated with active energy rays and then heat-cured (for example, at a temperature of 100 to 220°C for 30 to 90 minutes), or is irradiated with active energy rays after heat-curing (for example, 1,000 to 2,000 mJ/ cm2 ), or is heat-cured alone for final finish curing (main curing), thereby forming a cured coating film with excellent properties such as adhesion and hardness. Examples of the device include a UV conveyor using a high-pressure mercury lamp, such as QRM-2082 manufactured by Oak Manufacturing Co., Ltd.
上記内容は光硬化型熱硬化型の樹脂組成物による硬化塗膜の形成方法であるが、光硬化のみや熱硬化のみの場合は以下のとおり、製造することができる。
光硬化のみの場合、本発明の硬化性樹脂組成物を基材上にパターン印刷等で塗布した後に活性エネルギー線(例えば、1,000~2,000mJ/cm2)を照射して硬化させることにより、硬化塗膜を形成する。
一方、熱硬化のみの場合、本発明の硬化性樹脂組成物を基材上にパターン印刷等で塗布した後に加熱硬化(例えば、100~220℃の温度で30~90分間)させることにより、硬化塗膜を形成する。
The above is a method for forming a cured coating film using a photocurable or thermosetting resin composition, but in the case of only photocuring or only thermosetting, the coating film can be produced as follows.
In the case of photocuring only, the curable resin composition of the present invention is applied to a substrate by pattern printing or the like, and then cured by irradiation with active energy rays (for example, 1,000 to 2,000 mJ/cm 2 ) to form a cured coating film.
On the other hand, in the case of only thermal curing, the curable resin composition of the present invention is applied to a substrate by pattern printing or the like, and then heat-cured (for example, at a temperature of 100 to 220° C. for 30 to 90 minutes) to form a cured coating film.
以下、本発明を、実施例を用いてより詳細に説明するが、本発明は下記実施例に限定されるものではない。なお、以下において「部」および「%」とあるのは、特に断りのない限り全て質量基準である。 The present invention will be described in more detail below using examples, but the present invention is not limited to the following examples. Note that "parts" and "%" below are all based on mass unless otherwise specified.
(合成例1 アルカリ可溶性感光性樹脂1の合成)
まず、温度計、窒素導入装置兼アルキレンオキシド導入装置および攪拌装置を備えたオートクレーブに、ノボラック型クレゾール樹脂(昭和電工株式会社製のショウノールCRG951、OH当量:119.4)119.4部、水酸化カリウム1.19部およびトルエン119.4部を仕込み、攪拌しつつ系内を窒素置換し、加熱昇温した。次いで、プロピレンオキシド63.8部を徐々に滴下し、温度125~132℃、圧力0~4.8kg/cm2で16時間反応させた。次いで、系を室温まで冷却し、得られた反応溶液に89質量%リン酸1.56部を添加し混合して水酸化カリウムを中和して、不揮発分62.1%、水酸基価182.2g/eq.のノボラック型クレゾール樹脂のプロピレンオキシド反応溶液を得た。得られたノボラック型クレゾール樹脂には、フェノール性水酸基1当量当りアルキレンオキシドが平均1.08モル付加していた。得られたノボラック型クレゾール樹脂のアルキレンオキシド反応溶液293.0部、アクリル酸43.2部、メタンスルホン酸11.53部、メチルハイドロキノン0.18部およびトルエン252.9部を、攪拌機、温度計および空気吹き込み管を備えた反応器に仕込み、空気を10ml/分の速度で吹き込み、攪拌しながら、温度110℃で12時間反応させた。反応により生成した水は、トルエンとの共沸混合物として、12.6部の水が留出した。次いで、系を室温まで冷却し、得られた反応溶液を15%水酸化ナトリウム水溶液35.35部で中和し、水洗した。次いで、エバポレーターを用いてトルエンをジエチレングリコールモノエチルエーテルアセテート(カルビトールアセテート)118.1部で置換しつつ留去し、ノボラック型アクリレート樹脂溶液を得た。次いで、得られたノボラック型アクリレート樹脂溶液332.5部およびトリフェニルフォスフィン1.22部を、攪拌器、温度計および空気吹き込み管を備えた反応器に仕込み、空気を10ml/分の速度で吹き込み、攪拌しながら、テトラヒドロフタル酸無水物60.8部を徐々に添加して、温度95~101℃で6時間反応させ、次いで冷却して、固形物の酸価88mgKOH/g、重量平均分子量2550、固形分65.8%のアルカリ可溶性感光性樹脂1の溶液を得た。なお、実施例において、重量平均分子量の値は、ゲル浸透クロマトグラフィー(GPC)により測定した値である。
(Synthesis Example 1: Synthesis of Alkali-Soluble Photosensitive Resin 1)
First, 119.4 parts of novolac cresol resin (Showa Denko K.K.'s Shownol CRG951, OH equivalent: 119.4) were charged into an autoclave equipped with a thermometer, a nitrogen introduction device/alkylene oxide introduction device, and a stirrer, and the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 parts of propylene oxide were gradually dropped, and the reaction was carried out for 16 hours at a temperature of 125 to 132 ° C. and a pressure of 0 to 4.8 kg / cm 2. Next, the system was cooled to room temperature, and 1.56 parts of 89 mass % phosphoric acid was added to the obtained reaction solution and mixed to neutralize the potassium hydroxide, and a propylene oxide reaction solution of novolac cresol resin with a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / eq. was obtained. The novolak cresol resin obtained had an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group. 293.0 parts of the alkylene oxide reaction solution of the novolak cresol resin obtained, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone, and 252.9 parts of toluene were charged into a reactor equipped with a stirrer, a thermometer, and an air inlet tube, and the mixture was reacted at a temperature of 110° C. for 12 hours while stirring and blowing air at a rate of 10 ml/min. As for the water produced by the reaction, 12.6 parts of water were distilled as an azeotropic mixture with toluene. Next, the system was cooled to room temperature, and the reaction solution obtained was neutralized with 35.35 parts of 15% aqueous sodium hydroxide solution and washed with water. Next, toluene was distilled off using an evaporator while replacing it with 118.1 parts of diethylene glycol monoethyl ether acetate (carbitol acetate), to obtain a novolac-type acrylate resin solution. Next, 332.5 parts of the obtained novolac-type acrylate resin solution and 1.22 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer, and an air-inlet tube, and 60.8 parts of tetrahydrophthalic anhydride were gradually added while blowing air at a rate of 10 ml/min and stirring, and the mixture was reacted at a temperature of 95 to 101°C for 6 hours, and then cooled to obtain a solution of alkali-soluble photosensitive resin 1 having an acid value of 88 mgKOH/g, a weight average molecular weight of 2550, and a solid content of 65.8%. In the examples, the weight average molecular weight is a value measured by gel permeation chromatography (GPC).
(合成例2 アルカリ可溶性感光性樹脂2の合成)
冷却管、攪拌機を備えたフラスコに、ビスフェノールA 456部、水228部、37%ホルマリン649部を仕込み、40℃以下の温度を保ち、25%水酸化ナトリウム水溶液228部を添加した、添加終了後50℃で10時間反応した。反応終了後40℃まで冷却し、40℃以下を保ちながら37.5%リン酸水溶液でpH4まで中和した。その後静置し水層を分離した。分離後メチルイソブチルケトン300部を添加し均一に溶解した後、蒸留水500部で3回洗浄し、50℃以下の温度で減圧下、水、溶媒等を除去した。得られたポリメチロール化合物をメタノール550部に溶解し、ポリメチロール化合物のメタノール溶液1230部を得た。得られたポリメチロール化合物のメタノール溶液の一部を真空乾燥機中室温で乾燥したところ、固形分が55.2%であった。
得られたポリメチロール化合物のメタノール溶液500部、2,6-キシレノール440部を仕込み、50℃で均一に溶解した。均一に溶解した後50℃以下の温度で減圧下メタノールを除去した。その後シュウ酸8部を加え、100℃で10時間反応した。反応終了後180℃、50mmHgの減圧下で溜出分を除去し、ノボラック樹脂A 550部を得た。
更に、温度計、窒素導入装置兼アルキレンオキシド導入装置及び攪拌装置を備えたオートクレーブに、上記のノボラック樹脂Aを130部、50%水酸化ナトリウム水溶液2.6部、トルエン/メチルイソブチルケトン(質量比=2/1)100部を仕込み、攪拌しつつ系内を窒素置換し、次に加熱昇温し、150℃、8kg/cm2でエチレンオキシド45部を徐々に導入し反応させた。反応はゲージ圧0.0kg/cm2となるまで約4時間を続けた後、室温まで冷却した。この反応溶液に3.3部の36%塩酸水溶液を添加混合し、水酸化ナトリウムを中和した。この中和反応生成物をトルエンで希釈し、3回水洗し、エバポレーターにて脱溶剤して、水酸基価が175g/eq.であるノボラック樹脂Aのエチレンオキシド付加物を得た。これは、フェノール性水酸基1当量当りエチレンオキシドが平均1モル付加しているものであった。
このように得られたノボラック樹脂Aのエチレンオキシド付加物175部、アクリル酸50部、p-トルエンスルホン酸3.0部、ハイドロキノンモノメチルエーテル0.1部、トルエン130部を攪拌機、温度計、空気吹き込み管を備えた反応器に仕込み、空気を吹き込みながら攪拌して、115℃に昇温し、反応により生成した水をトルエンと共沸混合物として留去しながら、さらに4時間反応させたのち、室温まで冷却した。得られた反応溶液を5%NaCl水溶液を用いて水洗し、減圧留去にてトルエンを除去したのち、ジエチレングリコールモノエチルエーテルアセテートを加えて、固形分68%のアクリレート樹脂溶液を得た。
次に、攪拌器および還流冷却器の付いた4つ口フラスコに、得られたアクリレート樹脂溶液312部、ハイドロキノンモノメチルエーテル0.1部、トリフェニルフォスフィン0.3部を仕込み、この混合物を110℃に加熱し、テトラヒドロ無水フタル酸45部を加え、4時間反応させ、冷却後、固形分70%、固形分酸価65mgKOH/g、重量平均分子量11600のアルカリ可溶性感光性樹脂2の溶液を得た。
(Synthesis Example 2: Synthesis of Alkali-Soluble Photosensitive Resin 2)
In a flask equipped with a cooling tube and a stirrer, 456 parts of bisphenol A, 228 parts of water, and 649 parts of 37% formalin were charged, and the temperature was kept below 40°C, and 228 parts of a 25% aqueous sodium hydroxide solution was added. After the addition was completed, the mixture was reacted at 50°C for 10 hours. After the reaction was completed, the mixture was cooled to 40°C, and neutralized to pH 4 with a 37.5% aqueous phosphoric acid solution while keeping the temperature below 40°C. The mixture was then left to stand and the aqueous layer was separated. After the separation, 300 parts of methyl isobutyl ketone was added and dissolved uniformly, and the mixture was washed three times with 500 parts of distilled water, and water, solvent, etc. were removed under reduced pressure at a temperature below 50°C. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1230 parts of a methanol solution of the polymethylol compound. A part of the obtained methanol solution of the polymethylol compound was dried at room temperature in a vacuum dryer, and the solid content was 55.2%.
500 parts of the resulting methanol solution of the polymethylol compound and 440 parts of 2,6-xylenol were charged and uniformly dissolved at 50° C. After uniform dissolution, methanol was removed under reduced pressure at a temperature of 50° C. or less. Then, 8 parts of oxalic acid was added and reacted at 100° C. for 10 hours. After completion of the reaction, the distillate was removed under reduced pressure at 180° C. and 50 mmHg to obtain 550 parts of novolak resin A.
Further, 130 parts of the above novolak resin A, 2.6 parts of a 50% aqueous sodium hydroxide solution, and 100 parts of toluene/methyl isobutyl ketone (mass ratio = 2/1) were charged into an autoclave equipped with a thermometer, a nitrogen introduction device/alkylene oxide introduction device, and a stirrer, and the inside of the system was replaced with nitrogen while stirring, and then heated to increase the temperature, and 45 parts of ethylene oxide were gradually introduced at 150 ° C. and 8 kg/cm2 to react. The reaction was continued for about 4 hours until the gauge pressure reached 0.0 kg/ cm2 , and then cooled to room temperature. 3.3 parts of a 36% aqueous hydrochloric acid solution were added and mixed to this reaction solution to neutralize the sodium hydroxide. This neutralized reaction product was diluted with toluene, washed with water three times, and desolvated with an evaporator to obtain an ethylene oxide adduct of novolak resin A with a hydroxyl value of 175 g/eq. This was a product in which ethylene oxide was added on average 1 mole per equivalent of phenolic hydroxyl group.
175 parts of the ethylene oxide adduct of novolak resin A thus obtained, 50 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 parts of hydroquinone monomethyl ether, and 130 parts of toluene were charged into a reactor equipped with a stirrer, a thermometer, and an air-inlet tube, and the mixture was stirred while blowing in air, heated to 115° C., and reacted for another 4 hours while distilling off water produced by the reaction as an azeotropic mixture with toluene, and then cooled to room temperature. The resulting reaction solution was washed with a 5% aqueous NaCl solution, and the toluene was removed by distillation under reduced pressure, and diethylene glycol monoethyl ether acetate was added to obtain an acrylate resin solution with a solid content of 68%.
Next, 312 parts of the obtained acrylate resin solution, 0.1 parts of hydroquinone monomethyl ether, and 0.3 parts of triphenylphosphine were charged into a four-neck flask equipped with a stirrer and a reflux condenser, and this mixture was heated to 110° C., 45 parts of tetrahydrophthalic anhydride was added, and the mixture was reacted for 4 hours. After cooling, a solution of alkali-soluble photosensitive resin 2 having a solid content of 70%, an acid value of the solid content of 65 mgKOH/g, and a weight average molecular weight of 11,600 was obtained.
(合成例3 アルカリ可溶性感光性樹脂3の合成)
反応槽としての冷却管付きセパラブルフラスコに、プロピレングリコールモノメチルエーテルアセテート82.4部、イソプロパノール35.3部を仕込み、窒素置換した後、100℃に昇温した。他方、滴下槽1にN-フェニルマレイミドを40部、プロピレングリコールモノメチルエーテルアセテートを128部、イソプロパノールを32部混合したもの、滴下槽2にスチレンを13部、メタアクリル酸2-ヒドロキシエチルを20部、メタアクリル酸を27部、イソプロパノールを22.2部混合したもの、滴下槽3に重合開始剤としてパーブチルO(商品名;日油社製、t-ブチルパーオキシ-2-エチルヘキサノエート)10部をそれぞれ仕込んだ。反応温度を100℃に保ちながら、滴下槽1~3から3時間かけて滴下を行った。滴下終了後から更に100℃で30分、反応を継続した。その後、反応温度を115℃に昇温し、1.5時間反応を継続してラジカル重合性二重結合導入反応前の重合体溶液を得た。
次いで、この重合体溶液にサイクロマーM100を13.7部、プロピレングリコールモノメチルエーテルアセテートを31.2部、反応触媒としてトリフェニルフォスフィンを0.7部、重合禁止剤としてアンテージW-400を0.2部加え、窒素と酸素との混合ガス(酸素濃度7%)をバブリングしながら115℃で反応させてアルカリ可溶性感光性樹脂3の溶液を得た。
得られたアルカリ可溶性感光性樹脂3について各種物性を測定したところ、重量平均分子量は7400、真空下160℃にて加熱乾燥させて得られた固形分濃度は32.0%、固形分当たりの酸価は124mgKOH/gであった。
(Synthesis Example 3: Synthesis of Alkali-Soluble Photosensitive Resin 3)
In a separable flask equipped with a cooling tube as a reaction vessel, 82.4 parts of propylene glycol monomethyl ether acetate and 35.3 parts of isopropanol were charged, and after nitrogen replacement, the temperature was raised to 100°C. On the other hand, a mixture of 40 parts of N-phenylmaleimide, 128 parts of propylene glycol monomethyl ether acetate, and 32 parts of isopropanol was charged in the dropping vessel 1, a mixture of 13 parts of styrene, 20 parts of 2-hydroxyethyl methacrylate, 27 parts of methacrylic acid, and 22.2 parts of isopropanol was charged in the dropping vessel 2, and 10 parts of Perbutyl O (trade name; NOF Corporation, t-butylperoxy-2-ethylhexanoate) was charged as a polymerization initiator in the dropping vessel 3. While maintaining the reaction temperature at 100°C, dropping was performed from the dropping vessels 1 to 3 over a period of 3 hours. After the end of dropping, the reaction was continued at 100°C for another 30 minutes. Thereafter, the reaction temperature was raised to 115° C., and the reaction was continued for 1.5 hours to obtain a polymer solution prior to the reaction for introducing radically polymerizable double bonds.
Next, 13.7 parts of Cyclomer M100, 31.2 parts of propylene glycol monomethyl ether acetate, 0.7 parts of triphenylphosphine as a reaction catalyst, and 0.2 parts of Antage W-400 as a polymerization inhibitor were added to this polymer solution, and the mixture was reacted at 115° C. while bubbling a mixed gas of nitrogen and oxygen (oxygen concentration: 7%) to obtain a solution of alkali-soluble photosensitive resin 3.
Various physical properties of the obtained alkali-soluble photosensitive resin 3 were measured, and the weight average molecular weight was 7,400, the solid content concentration obtained by heating and drying at 160° C. in a vacuum was 32.0%, and the acid value per solid content was 124 mg KOH/g.
[実施例1~4、比較例1~3]
(硬化性樹脂組成物の調製)
各硬化性樹脂組成物について、下記表1に示す処方に従って各成分を配合し、攪拌機にて混合した。
[Examples 1 to 4, Comparative Examples 1 to 3]
(Preparation of Curable Resin Composition)
For each curable resin composition, the components were blended according to the recipe shown in Table 1 below and mixed with a stirrer.
表1中の配合量は、質量部(固形分換算量)を示す。
表1中の各成分の詳細は、以下の通りである。
※1:合成例1のアルカリ可溶性感光性樹脂1(重量平均分子量2550)
※2:合成例2のアルカリ可溶性感光性樹脂2(重量平均分子量11600)
※3:ZCR-1601H 日本化薬株式会社製(重量平均分子量4500)
※4:合成例3のアルカリ可溶性感光性樹脂3
※5:EMG-1015 DIC株式会社製(感光性無し)
※6:HP-7200L DIC株式会社製
※7:N-770 DIC株式会社製
※8:2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド
※9:ネオマー DA-600 三洋化成工業株式会社製
※10:AEROSIL 200 日本アエロジル株式会社製 (平均粒径12nm、表面処理なし)
※11:YA050C-HHL 株式会社アドマテックス製 (平均粒径50nm、ビニルシラン処理)
※12:YA050C-MJE 株式会社アドマテックス製 (平均粒径50nm、メタクリルシラン処理)
The blend amounts in Table 1 are shown in parts by weight (equivalent to solid content).
Details of each component in Table 1 are as follows.
*1: Alkali-soluble photosensitive resin 1 of Synthesis Example 1 (weight average molecular weight 2550)
*2: Alkali-soluble photosensitive resin 2 of Synthesis Example 2 (weight average molecular weight 11,600)
*3: ZCR-1601H manufactured by Nippon Kayaku Co., Ltd. (weight average molecular weight: 4500)
*4: Alkali-soluble photosensitive resin 3 of Synthesis Example 3
*5: EMG-1015 manufactured by DIC Corporation (non-photosensitive)
*6: HP-7200L manufactured by DIC Corporation *7: N-770 manufactured by DIC Corporation *8: 2,4,6-trimethylbenzoyldiphenylphosphine oxide *9: Neomer DA-600 manufactured by Sanyo Chemical Industries, Ltd. *10: AEROSIL 200 manufactured by Nippon Aerosil Co., Ltd. (average particle size 12 nm, no surface treatment)
*11: YA050C-HHL manufactured by Admatechs Co., Ltd. (average particle size 50 nm, vinyl silane treatment)
*12: YA050C-MJE, manufactured by Admatechs Co., Ltd. (average particle size 50 nm, methacrylsilane treatment)
(現像性の評価)
<評価基板の作製>
上記表1に示す実施例1~4および比較例1~3で得られた組成物を、第一のフィルム上に乾燥後の膜厚が10μmになるように塗布し、80℃で20分乾燥し、室温まで放冷した。銅貼り積層板上に90℃でラミネートし、1時間以上放置後、i線単線の投影露光機を用いて開口パターンにて露光を行った。一定時間放置後表面の第一のフィルムを剥離し、30℃の1質量%の炭酸ナトリウム水溶液をスプレー圧0.2MPaの条件で90秒間現像を行った。この基板を、UVコンベア炉にて積算露光量1000mJ/cm2で露光した後180℃で60分加熱して硬化した。得られた評価基板に対し走査電子顕微鏡を用いて開口径10μmのビアの底面の残渣を観察した。下記の基準に基づいて現像性を評価し、評価結果を表2に示した。
[評価基準]
◎:ビア底面に残渣がなかった。
〇:ビア底面の0%超50%未満が残渣で覆われていた。
△:ビア底面の50%以上90%未満が残渣で覆われていた。
×:ビア底面の90%以上が残渣で覆われていた。
(Evaluation of developability)
<Preparation of evaluation board>
The compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 shown in Table 1 above were applied onto the first film so that the film thickness after drying was 10 μm, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature. The film was laminated onto a copper-clad laminate at 90 ° C., left for 1 hour or more, and then exposed to an opening pattern using an i-line single-beam projection exposure machine. After leaving for a certain period of time, the first film on the surface was peeled off, and development was performed for 90 seconds under conditions of a spray pressure of 0.2 MPa with a 1 mass % sodium carbonate aqueous solution at 30 ° C. The substrate was exposed to an integrated exposure amount of 1000 mJ / cm 2 in a UV conveyor furnace, and then heated at 180 ° C. for 60 minutes to harden. The residue on the bottom of a via with an opening diameter of 10 μm was observed for the obtained evaluation substrate using a scanning electron microscope. The developability was evaluated based on the following criteria, and the evaluation results are shown in Table 2.
[Evaluation criteria]
⊚: No residue was found on the bottom of the via.
◯: More than 0% and less than 50% of the bottom surface of the via was covered with residue.
Δ: 50% or more and less than 90% of the bottom surface of the via was covered with residue.
x: 90% or more of the bottom surface of the via was covered with residue.
(解像性の評価)
上記(現像性の評価)試験と同様にして、硬化膜を有する基板を得た。得られた硬化物の開口径を走査型顕微鏡によって観測し、ハレーションやアンダーカットの発生が無いかを以下の基準に基づいて解像性を評価し、評価結果を表2に示した。
[評価基準]
〇:開口径10μmにて良好な開口径が得られた。
×:開口径10μmにて良好な開口径が得られなかった。
(Evaluation of Resolution)
A substrate having a cured film was obtained in the same manner as in the above (Evaluation of developability) test. The opening diameter of the obtained cured product was observed by a scanning microscope, and the resolution was evaluated based on the following criteria to determine whether or not halation or undercut occurred. The evaluation results are shown in Table 2.
[Evaluation criteria]
◯: A good opening diameter was obtained with an opening diameter of 10 μm.
×: A satisfactory opening diameter was not obtained with an opening diameter of 10 μm.
(耐溶剤性の評価)
上記表1に示す実施例1~4および比較例1~3で得られた組成物を、第一のフィルム上に乾燥後の膜厚が10μmになるように塗布し、80℃で20分乾燥し、室温まで放冷した。6インチのウエハ上に90℃でラミネートし、1時間以上放置後、i線単線の投影露光機を用いて全面露光を行った。一定時間放置後表面の第一のフィルムを剥離し、30℃の1質量%の炭酸ナトリウム水溶液をスプレー圧0.2MPaの条件で90秒間現像を行った。この基板を、UVコンベア炉にて積算露光量1000mJ/cm2で露光した後180℃で60分加熱して硬化した。得られた評価基板をアセトンに10分間浸漬後、光学顕微鏡を用いて表面のクラックの有無を観察した。下記の基準に基づいて現像性を評価し、評価結果を表2に示した。
[評価基準]
○:アセトン浸漬後にクラックは発生しなかった。
×:アセトン浸漬後にクラックが発生した。
(Evaluation of Solvent Resistance)
The compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 shown in Table 1 above were applied onto a first film so that the film thickness after drying was 10 μm, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature. The film was laminated onto a 6-inch wafer at 90 ° C., left for 1 hour or more, and then exposed to a full surface using an i-line single-beam projection exposure machine. After leaving for a certain period of time, the first film on the surface was peeled off, and development was performed for 90 seconds under conditions of a spray pressure of 0.2 MPa with a 1 mass % sodium carbonate aqueous solution at 30 ° C. After exposure to an accumulated exposure amount of 1000 mJ / cm 2 in a UV conveyor furnace, the substrate was heated at 180 ° C. for 60 minutes and cured. The obtained evaluation substrate was immersed in acetone for 10 minutes, and the presence or absence of cracks on the surface was observed using an optical microscope. The developability was evaluated based on the following criteria, and the evaluation results are shown in Table 2.
[Evaluation criteria]
◯: No cracks were generated after immersion in acetone.
×: Cracks occurred after immersion in acetone.
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