JP7383388B2 - Curable compositions, dry films, cured products, and electronic components - Google Patents
Curable compositions, dry films, cured products, and electronic components Download PDFInfo
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- JP7383388B2 JP7383388B2 JP2019060301A JP2019060301A JP7383388B2 JP 7383388 B2 JP7383388 B2 JP 7383388B2 JP 2019060301 A JP2019060301 A JP 2019060301A JP 2019060301 A JP2019060301 A JP 2019060301A JP 7383388 B2 JP7383388 B2 JP 7383388B2
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- 239000000203 mixture Substances 0.000 title claims description 104
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 76
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- 150000001875 compounds Chemical class 0.000 claims description 41
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- 239000000377 silicon dioxide Substances 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 26
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- 238000001035 drying Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 11
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- 239000002253 acid Substances 0.000 claims description 8
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
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- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- LXTZRIBXKVRLOA-UHFFFAOYSA-N padimate a Chemical compound CCCCCOC(=O)C1=CC=C(N(C)C)C=C1 LXTZRIBXKVRLOA-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WZESLRDFSNLECD-UHFFFAOYSA-N phenyl prop-2-eneperoxoate Chemical compound C=CC(=O)OOC1=CC=CC=C1 WZESLRDFSNLECD-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- CCDXIADKBDSBJU-UHFFFAOYSA-N phenylmethanetriol Chemical compound OC(O)(O)C1=CC=CC=C1 CCDXIADKBDSBJU-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- QCTJRYGLPAFRMS-UHFFFAOYSA-N prop-2-enoic acid;1,3,5-triazine-2,4,6-triamine Chemical compound OC(=O)C=C.NC1=NC(N)=NC(N)=N1 QCTJRYGLPAFRMS-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- LJFWQNJLLOFIJK-UHFFFAOYSA-N solvent violet 13 Chemical compound C1=CC(C)=CC=C1NC1=CC=C(O)C2=C1C(=O)C1=CC=CC=C1C2=O LJFWQNJLLOFIJK-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Epoxy Resins (AREA)
Description
本発明は、硬化性組成物、ドライフィルム、硬化物および電子部品に関し、特に、アルカリ現像可能な硬化性組成物、そのドライフィルム、その硬化物およびその硬化物を備える電子部品に関する。 The present invention relates to a curable composition, a dry film, a cured product, and an electronic component, and particularly relates to an alkali-developable curable composition, a dry film thereof, a cured product thereof, and an electronic component including the cured product.
従来より、民生用プリント基板や、産業用プリント配線板のソルダーレジストにおいて、高精度、高密度の観点から、紫外線照射後、現像することにより画像形成し、熱及び／又は光照射で仕上げ硬化（本硬化）する液状現像型ソルダーレジストが使用されており、液状現像型のソルダーレジストの中でも、環境問題への配慮から、現像液としてアルカリ水溶液を用いるアルカリ現像型のフォトソルダーレジストが主流になっている。 Conventionally, in order to achieve high precision and high density in solder resists for consumer printed circuit boards and industrial printed wiring boards, images are formed by irradiation with ultraviolet rays, development, and final curing (with heat and/or light irradiation). Among liquid developable solder resists, alkali developable photo solder resists that use an alkaline aqueous solution as a developer have become mainstream due to environmental concerns. There is.
一般に、基板上にフォトソルダーレジストを形成するために基板に塗布されるソルダーレジスト組成物には、ソルダーレジスト組成物の基板への濡れ性を高めるため、また、その塗膜のレベリング性（平坦性）を高めるために、シリコン系表面調整剤が添加される。 In general, the solder resist composition applied to the substrate to form a photo solder resist on the substrate has a number of ingredients to improve the wettability of the solder resist composition to the substrate, as well as to improve the leveling properties (flatness) of the coating film. ), a silicon-based surface conditioner is added.
基板上へのフォトソルダーレジストの形成後、基板上への部品の実装ははんだ付けにより行われるが、溶融はんだは基板に対する濡れ性が低いため、濡れ性向上（はんだ付け面の清浄化と酸化防止）のためにフラックスがソルダーレジスト面を含む基板面の全面に塗布される。 After the photo solder resist is formed on the board, components are mounted on the board by soldering, but since molten solder has low wettability to the board, it is necessary to improve wettability (cleaning the soldering surface and preventing oxidation). ), flux is applied to the entire surface of the board, including the solder resist surface.
しかし、シリコン系表面調整剤が基板上に形成されたソルダーレジスト中に含まれていると、フラックスが基板から弾かれてはんだ付け性が低下するという不具合が発生することが発明者らの検討によりわかってきた。 However, the inventors have found that if a silicon-based surface conditioner is included in the solder resist formed on the substrate, a problem occurs in which the flux is repelled from the substrate and the solderability deteriorates. I've come to understand.
一方、無機充填剤としてシリカがソルダーレジストの剛性強化及びソルダーレジスト組成物の硬化収縮抑制のためにソルダーレジスト組成物中に添加されることは良く知られている。 On the other hand, it is well known that silica is added as an inorganic filler to solder resist compositions in order to strengthen the rigidity of the solder resist and suppress curing shrinkage of the solder resist composition.
特許文献１には、その実施例に、上記従来技術のソルダーレジスト組成物として、シリコン系表面調整剤を含有するアルカリ現像型光硬化性・熱硬化性ソルダーレジスト組成物が開示され、比較例２として、無機粉末として表面改質処理を施していない溶融球状シリカを含有するアルカリ現像型光硬化性・熱硬化性ソルダーレジスト組成物が開示されている。 Patent Document 1 discloses an alkali-developable photo-curable/thermo-curable solder resist composition containing a silicon-based surface conditioner as the conventional solder resist composition described above in its Examples, and Comparative Example 2 discloses an alkali-developable photo-curable/thermo-curable solder resist composition containing fused spherical silica which has not been surface-modified as an inorganic powder.
特許文献１の実施例に係るシリコン系表面調整剤を含有するアルカリ現像型光硬化性・熱硬化性ソルダーレジスト組成物によれば、基板に対するソルダーレジスト組成物の濡れ性は向上するものの、形成されたソルダーレジストがフラックスを弾くため、はんだ付け性が低下してしまう。 According to the alkaline-developable photocurable/thermocurable solder resist composition containing the silicon-based surface conditioner according to the example of Patent Document 1, although the wettability of the solder resist composition to the substrate is improved, the solder resist composition is not formed. The solder resist repels flux, resulting in poor solderability.
また、特許文献１の比較例２にかかるアルカリ現像型光硬化性・熱硬化性ソルダーレジスト組成物によれば、添加されたシリカは表面改質処理が施されておらず親水性であるため、そのままでは凝集・沈殿の問題が生じる虞があり、例えば表面を疎水性に改質し、凝集・沈殿の問題を解消する必要がある。また、比較例２にかかるアルカリ現像型光硬化性・熱硬化性ソルダーレジスト組成物はシリコン系表面調整剤が添加されていないため、ソルダーレジスト組成物の基板に対する濡れ性も改善されていない。 Furthermore, according to the alkali-developable photocurable/thermocurable solder resist composition according to Comparative Example 2 of Patent Document 1, the added silica has not been subjected to surface modification treatment and is hydrophilic. If left as is, there is a risk of agglomeration/precipitation problems, and it is necessary to solve the agglomeration/precipitation problems by, for example, modifying the surface to make it hydrophobic. Furthermore, since the alkali-developable photocurable/thermocurable solder resist composition according to Comparative Example 2 does not contain a silicone surface conditioner, the wettability of the solder resist composition to the substrate is not improved.
本発明は、上記課題に鑑みてなされたものであり、その目的は、親水性シリカ、シリコン系表面調整剤を含有しつつ、はんだ付け性が良好でシリカの凝集・沈殿の問題が解消された硬化性組成物、ドライフィルム、硬化物及び電子部品を提供することにある。 The present invention was made in view of the above problems, and its purpose is to provide a product that contains hydrophilic silica and a silicon-based surface conditioner, has good solderability, and eliminates the problems of silica aggregation and precipitation. Our objective is to provide curable compositions, dry films, cured products, and electronic components.
本発明者らは、上記目的達成に向け鋭意検討を行った。その結果、意外なことに、シリコーン化合物、親水性シリカ及び有機揺変剤を配合させた際に、銅張基板とソルダーレジスト組成物の濡れ性を維持しつつ、親水性シリカの凝集・沈殿の問題、及びシリコーン化合物に起因するフラックスの弾きの問題が解消されたことを見出し、本発明を完成するに至った。 The present inventors have conducted extensive studies toward achieving the above objective. As a result, we surprisingly found that when a silicone compound, hydrophilic silica, and organic thixotropic agent were blended, the wettability of the copper-clad substrate and the solder resist composition was maintained while the aggregation and precipitation of the hydrophilic silica was prevented. The present inventors have discovered that the problem of flux repellency caused by silicone compounds has been solved, and have completed the present invention.
すなわち、本発明の上記目的は、
（Ａ）アルカリ可溶性樹脂と、
（Ｂ）光重合開始剤と、
（Ｃ）エポキシ樹脂と、
（Ｄ）シリコーン化合物と、
（Ｅ）親水性シリカと、
（Ｆ）有機揺変剤と、
を含むことを特徴とする硬化性組成物により達成されることが見出された。
That is, the above object of the present invention is to
(A) an alkali-soluble resin;
(B) a photopolymerization initiator;
(C) an epoxy resin;
(D) a silicone compound;
(E) hydrophilic silica;
(F) an organic thixotropic agent;
It has been found that this can be achieved by a curable composition comprising:
本発明の硬化性組成物は、さらに（Ｅ）親水性シリカの粒径メジアン径Ｄ５０が、０．２μｍ以上２．０μｍ以下であることが好ましい。 In the curable composition of the present invention, it is further preferable that (E) the hydrophilic silica has a median particle diameter D50 of 0.2 μm or more and 2.0 μm or less.
また、（Ｆ）有機揺変剤の量が、（Ｅ）親水性シリカ１００質量部に対して０．０１質量部以上１５質量部以下であり、且つ（Ｄ）シリコーン化合物２質量部に対して０．０５質量部以上であることがさらに好ましい。 Further, the amount of (F) the organic thixotropic agent is 0.01 parts by mass or more and 15 parts by mass or less with respect to (E) 100 parts by mass of the hydrophilic silica, and (D) with respect to 2 parts by mass of the silicone compound. More preferably, the amount is 0.05 parts by mass or more.
そのうえ、（Ｇ）酸化防止剤をさらに含むことが好ましい。 Moreover, it is preferable to further include (G) an antioxidant.
また、本発明の上記目的は、本発明の硬化性組成物を、キャリアフィルム上に塗布、乾燥させて得られることを特徴とするドライフィルム、
本発明の硬化性組成物を、基材上に塗布、乾燥させて得られる乾燥塗膜、または、前記硬化性組成物を、キャリアフィルム上に塗布、乾燥させて得られるドライフィルムが基材にラミネートされてなる塗膜を、硬化させて得られることを特徴とする硬化物、及び
この硬化物を備えることを特徴とする電子部品
によっても達成することができる。
Further, the above object of the present invention is a dry film obtained by applying the curable composition of the present invention onto a carrier film and drying it.
A dry coating film obtained by coating and drying the curable composition of the present invention on a substrate, or a dry film obtained by coating and drying the curable composition on a carrier film is applied to the substrate. This can also be achieved by a cured product obtained by curing a laminated coating film, and an electronic component equipped with this cured product.
本発明によれば、硬化性組成物内での親水性シリカの凝集・沈殿の問題が解消され、基材に硬化性組成物が塗布された場合に、（Ｄ）シリコーン化合物によって基材への濡れ性が維持され、同時に、得られた硬化物に対するフラックスのぬれ性が向上することから、硬化物がソルダーレジストとして使用された場合に、はんだ付け性の向上効果が得られる。 According to the present invention, the problems of agglomeration and precipitation of hydrophilic silica within the curable composition are solved, and when the curable composition is applied to the substrate, the silicone compound (D) Since the wettability is maintained and, at the same time, the wettability of the flux to the obtained cured product is improved, when the cured product is used as a solder resist, the effect of improving solderability can be obtained.
＜硬化性組成物＞
本発明の硬化性組成物は、
（Ａ）アルカリ可溶性樹脂と、
（Ｂ）光重合開始剤と、
（Ｃ）エポキシ樹脂と、
（Ｄ）シリコーン化合物と、
（Ｅ）親水性シリカと、
（Ｆ）有機揺変剤と、
を含む。
<Curable composition>
The curable composition of the present invention is
(A) an alkali-soluble resin;
(B) a photopolymerization initiator;
(C) an epoxy resin;
(D) a silicone compound;
(E) hydrophilic silica;
(F) an organic thixotropic agent;
including.
［（Ａ）アルカリ可溶性樹脂］
アルカリ可溶性樹脂は、硬化性組成物のアルカリ現像液への溶解、すなわち、アルカリでの現像を可能とする樹脂である。
[(A) Alkali-soluble resin]
The alkali-soluble resin is a resin that enables the curable composition to be dissolved in an alkaline developer, that is, to be developed with an alkali.
アルカリ可溶性樹脂としては、カルボキシル基含有樹脂またはフェノール樹脂を用いることが好ましい。特に、カルボキシル基含有樹脂を用いると現像性の面からより好ましい。 As the alkali-soluble resin, it is preferable to use a carboxyl group-containing resin or a phenol resin. In particular, it is more preferable to use a carboxyl group-containing resin from the viewpoint of developability.
カルボキシル基含有樹脂としては、分子中にカルボキシル基を有し、さらにエチレン性不飽和基を有さない（非感光性の）、又はこれを有する（感光性の）従来公知の各種カルボキシル基含有樹脂を使用することができる。 The carboxyl group-containing resin includes various conventionally known carboxyl group-containing resins that have a carboxyl group in the molecule and do not have an ethylenically unsaturated group (non-photosensitive) or have this (photosensitive). can be used.
本発明において、エチレン性不飽和基とは、エチレン性不飽和結合を有する置換基であって、例えば、ビニル基、（メタ）アクリロイル基が挙げられ、反応性の観点から、（メタ）アクリロイル基であることが好ましい。ここで、（メタ）アクリロイル基とは、アクリロイル基及びメタアクリロイル基を総称する用語である。 In the present invention, an ethylenically unsaturated group is a substituent having an ethylenically unsaturated bond, such as a vinyl group or a (meth)acryloyl group. It is preferable that Here, the (meth)acryloyl group is a term that collectively refers to acryloyl groups and methacryloyl groups.
エチレン性不飽和基を有さない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。 Specific examples of carboxyl group-containing resins that do not have ethylenically unsaturated groups include the following compounds (which may be oligomers or polymers).
（１）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を含有する、ジアルコール化合物、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、ビスフェノールＡ系アルキレンオキシド付加体ジオール、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。 (1) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, cycloaliphatic diisocyanates, and aromatic diisocyanates, and dialcohol compounds and polycarbonate polyols containing carboxyl groups such as dimethylolpropionic acid and dimethylolbutanoic acid; A carboxyl group-containing urethane resin produced by polyaddition reaction of diol compounds such as polyether polyols, polyester polyols, polyolefin polyols, bisphenol A-based alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.
（２）ジイソシアネートと、カルボキシル基含有ジアルコ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。 (2) A carboxyl group-containing urethane resin produced by a polyaddition reaction between a diisocyanate and a carboxyl group-containing dialcohol compound.
（３）（メタ）アクリル酸等の不飽和カルボン酸と、スチレン、α－メチルスチレン、低級アルキル（メタ）アクリレート、イソブチレン等の不飽和基含有化合物との共重合により得られるカルボキシル基含有樹脂。 (3) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, or isobutylene.
（４）２官能エポキシ樹脂または２官能オキセタン樹脂にアジピン酸、フタル酸、ヘキサヒドロフタル酸等のジカルボン酸を反応させ、生じた水酸基に無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸等の２塩基酸無水物を付加させたカルボキシル基含有ポリエステル樹脂。 (4) A dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid, etc. is reacted with a bifunctional epoxy resin or a bifunctional oxetane resin, and the resulting hydroxyl group is reacted with a dicarboxylic acid such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. Carboxyl group-containing polyester resin to which dibasic acid anhydride has been added.
（５）エポキシ樹脂またはオキセタン樹脂を開環させ、生成した水酸基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樹脂。 (5) A carboxyl group-containing resin obtained by ring-opening an epoxy resin or oxetane resin and reacting the generated hydroxyl group with a polybasic acid anhydride.
（６）１分子中に複数のフェノール性水酸基を有する化合物、すなわちポリフェノール化合物を、エチレンオキシド、プロピレンオキシド等のアルキレンオキシドと反応させて得られるポリアルコール樹脂等の反応生成物に、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樹脂。 (6) A polybasic acid anhydride is added to a reaction product such as a polyalcohol resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule, that is, a polyphenol compound, with an alkylene oxide such as ethylene oxide or propylene oxide. A carboxyl group-containing resin obtained by reacting.
また、エチレン性不飽和基を有する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、カルボキシル基含有樹脂におけるエチレン性不飽和結合は、アクリル酸もしくはメタクリル酸またはそれらの誘導体由来であることが好ましい。 Further, specific examples of the carboxyl group-containing resin having an ethylenically unsaturated group include the following compounds (which may be either oligomers or polymers). Note that the ethylenically unsaturated bond in the carboxyl group-containing resin is preferably derived from acrylic acid, methacrylic acid, or a derivative thereof.
（７）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を含有する、ジアルコール化合物、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系アルキレンオキシド付加体ジオール、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感光性ウレタン樹脂。 (7) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, cycloaliphatic diisocyanates, and aromatic diisocyanates, and dialcohol compounds and polycarbonate polyols containing carboxyl groups such as dimethylolpropionic acid and dimethylolbutanoic acid; Containing carboxyl groups by polyaddition reaction of diol compounds such as polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups. Photosensitive urethane resin.
（８）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官能エポキシ樹脂の（メタ）アクリレートもしくはその部分酸無水物変性物と、カルボキシル基含有ジアルコ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。 (8) Diisocyanate and bifunctional epoxy resins such as bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bixylenol epoxy resin, and biphenol epoxy resin ( A carboxyl group-containing photosensitive urethane resin produced by a polyaddition reaction between meth)acrylate or its partially modified acid anhydride and a carboxyl group-containing dialcohol compound.
（９）上述の（７）または（８）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。 (9) During the synthesis of the resin of (7) or (8) above, a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as hydroxyalkyl (meth)acrylate, is added to the terminal (Meth)acrylated carboxyl group-containing photosensitive urethane resin.
（１０）上述の（８）または（９）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。 (10) During the synthesis of the resin of (8) or (9) above, one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. A carboxyl group-containing photosensitive urethane resin that has been terminally (meth)acrylated by adding a compound having the following.
（１１）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。 (11) A carboxyl group-containing photosensitive resin obtained by reacting a difunctional or higher polyfunctional (solid) epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride to the hydroxyl group present in the side chain.
（１２）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。 (12) A carboxyl product obtained by reacting (meth)acrylic acid with a polyfunctional epoxy resin in which the hydroxyl groups of a bifunctional (solid) epoxy resin are further epoxidized with epichlorohydrin, and adding a dibasic acid anhydride to the resulting hydroxyl groups. Group-containing photosensitive resin.
（１３）２官能オキセタン樹脂にアジピン酸、フタル酸、ヘキサヒドロフタル酸等のジカルボン酸を反応させ、生じた１級の水酸基に無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸等の２塩基酸無水物を付加させたカルボキシル基含有ポリエステル感光性樹脂。 (13) Difunctional oxetane resin is reacted with a dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid, etc., and the resulting primary hydroxyl group is converted into a dibase such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. Carboxyl group-containing polyester photosensitive resin with acid anhydride added.
（１４）１分子中に複数のフェノール性水酸基を有する化合物、すなわちポリフェノール化合物を、エチレンオキシド、プロピレンオキシド等のアルキレンオキシドと反応させて得られるポリアルコール樹脂等の反応生成物に、（メタ）アクリル酸等の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、更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。 (14) A reaction product such as a polyalcohol resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule, that is, a polyphenol compound, with an alkylene oxide such as ethylene oxide or propylene oxide, is added to (meth)acrylic acid. A carboxyl group-containing photosensitive resin obtained by reacting an unsaturated group-containing monocarboxylic acid such as, and further reacting the resulting reaction product with a polybasic acid anhydride.
（１５）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。 (15) Obtained by reacting a reaction product 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 with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.
（１６）上述の（７）～（１５）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。 (16) A carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins (7) to (15) above.
これら感光性カルボキシル基含有樹脂は、（７）～（１６）として述べた以外のものも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。特にカルボキシル基含有樹脂の中で芳香環を有している樹脂が好ましい。 As these photosensitive carboxyl group-containing resins, resins other than those mentioned in (7) to (16) can also be used, and one type may be used alone or a plurality of types may be used in combination. Among carboxyl group-containing resins, resins having an aromatic ring are particularly preferred.
上述のカルボキシル基含有樹脂は、感光性、非感光性問わず、以下のことが言える。すなわち、バックボーン・ポリマーの側鎖に多数のカルボキシル基を有するため、希アルカリ水溶液による現像が可能になる。 The following can be said about the carboxyl group-containing resin described above, regardless of whether it is photosensitive or non-photosensitive. That is, since the backbone polymer has a large number of carboxyl groups in its side chains, it can be developed with a dilute aqueous alkaline solution.
また、カルボキシル基含有樹脂の酸価は、４０～２００ｍｇＫＯＨ／ｇの範囲が適当であり、より好ましくは４５～１２０ｍｇＫＯＨ／ｇの範囲である。カルボキシル基含有樹脂の酸価がこのような範囲内であれば、アルカリ現像が容易となり、現像液による露光部の溶解が抑制され、必要以上にラインが痩せることなく、現像液による溶解剥離のない正常なパターンの描画が可能となる。 Further, the acid value of the carboxyl group-containing resin is suitably in the range of 40 to 200 mgKOH/g, more preferably in the range of 45 to 120 mgKOH/g. If the acid value of the carboxyl group-containing resin is within this range, alkaline development will be easy, the dissolution of the exposed area by the developer will be suppressed, the line will not become thinner than necessary, and there will be no dissolution and peeling due to the developer. It becomes possible to draw a normal pattern.
また、上述のカルボキシル基含有樹脂の重量平均分子量は、樹脂骨格により異なるが、一般的に２，０００以上１５０，０００以下、さらには５，０００以上１００，０００以下の範囲にあるものが好ましい。重量平均分子量がこのような範囲内であれば、タックフリー性能に優れ、露光後の塗膜の耐湿性が良好であり、解像度や現像性、貯蔵安定性に優れる。
このようなカルボキシル基含有樹脂の配合量は、硬化性組成物（固形分）中に、２０質量％以上８０質量％以下、好ましくは３０質量％以上７０質量％以下の範囲が適当である。カルボキシル基含有樹脂の配合量がこのような範囲内であれば、塗膜強度が低下せず、増粘や、作業性の低下が起こらない。
Further, the weight average molecular weight of the carboxyl group-containing resin described above varies depending on the resin skeleton, but it is generally preferably in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is within this range, the tack-free performance is excellent, the moisture resistance of the coating film after exposure is good, and the resolution, developability, and storage stability are excellent.
The amount of such carboxyl group-containing resin in the curable composition (solid content) is suitably in the range of 20% by mass or more and 80% by mass or less, preferably 30% by mass or more and 70% by mass or less. If the amount of the carboxyl group-containing resin is within this range, the strength of the coating film will not decrease, and neither thickening nor workability will occur.
また、本発明においては、（Ａ）アルカリ可溶性樹脂として、感光性カルボキシル基含有樹脂、および、感光性を有しないカルボキシル基含有樹脂のいずれか一方を用いることも、これらを混合して用いることも可能である。 Furthermore, in the present invention, as the alkali-soluble resin (A), either a photosensitive carboxyl group-containing resin or a non-photosensitive carboxyl group-containing resin may be used, or a mixture of these may be used. It is possible.
フェノール樹脂としては、フェノール性水酸基を有する化合物、例えば、ビフェニル骨格若しくはフェニレン骨格またはその両方の骨格を有する化合物、または、フェノール性水酸基含有化合物、例えば、フェノール、オルソクレゾール、パラクレゾール、メタクレゾール、２，３－キシレノール、２，４－キシレノール、２，５－キシレノール、２，６－キシレノール、３，４－キシレノール、３，５－キシレノール、カテコール、レゾルシノール、ハイドロキノン、メチルハイドロキノン、２，６－ジメチルハイドロキノン、トリメチルハイドロキノン、ピロガロール、フロログルシノール等を用いて合成した、様々な骨格を有するフェノール樹脂を用いてもよい。 The phenolic resin includes a compound having a phenolic hydroxyl group, such as a compound having a biphenyl skeleton, a phenylene skeleton, or both skeletons, or a phenolic hydroxyl group-containing compound, such as phenol, orthocresol, para-cresol, meta-cresol, 2 , 3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone Phenol resins having various skeletons synthesized using trimethylhydroquinone, pyrogallol, phloroglucinol, etc. may also be used.
例えば、フェノールノボラック樹脂、アルキルフェノールボラック樹脂、ビスフェノールＡノボラック樹脂、ジシクロペンタジエン型フェノール樹脂、Ｘｙｌｏｋ型フェノール樹脂、テルペン変性フェノール樹脂、ポリビニルフェノール類、ビスフェノールＦ、ビスフェノールＳ型フェノール樹脂、ポリ－ｐ－ヒドロキシスチレン、ナフトールとアルデヒド類の縮合物、ジヒドロキシナフタレンとアルデヒド類との縮合物など公知慣用のフェノール樹脂を用いることができる。 For example, phenol novolac resin, alkylphenol volac resin, bisphenol A novolac resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene-modified phenol resin, polyvinyl phenols, bisphenol F, bisphenol S type phenol resin, poly-p- Known and commonly used phenol resins such as hydroxystyrene, condensates of naphthol and aldehydes, and condensates of dihydroxynaphthalene and aldehydes can be used.
これらは、単独でまたは２種以上を組み合わせて使用することができる。 These can be used alone or in combination of two or more.
かかるフェノール樹脂の市販品としては、ＨＦ－１Ｍ（明和化成社製）、フェノライトＴＤ－２０９０、フェノライトＴＤ－２１３１（ＤＩＣ社製）、ベスモールＣＺ－２５６－Ａ（ＤＩＣ社製）、シヨウノールＢＲＧ－５５５、シヨウノールＢＲＧ－５５６（アイカ工業社製）、ＣＧＲ－９５１（丸善石油社製）、または、ポリビニルフェノールのＣＳＴ７０、ＣＳＴ９０、Ｓ－１Ｐ、Ｓ－２Ｐ（丸善石油社製）等を挙げることができる。これらのフェノール樹脂は、単独で、あるいは２種類以上を適宜組合せて用いることができる。 Commercially available products of such phenolic resins include HF-1M (manufactured by Meiwa Kasei Co., Ltd.), Phenolyte TD-2090, Phenolyte TD-2131 (manufactured by DIC Corporation), Besmol CZ-256-A (manufactured by DIC Corporation), and Shionol BRG. -555, Shionol BRG-556 (manufactured by Aica Kogyo Co., Ltd.), CGR-951 (manufactured by Maruzen Oil Co., Ltd.), or polyvinylphenol CST70, CST90, S-1P, S-2P (manufactured by Maruzen Oil Co., Ltd.), etc. Can be done. These phenol resins can be used alone or in an appropriate combination of two or more.
［（Ｂ）光重合開始剤］
（Ｂ）光重合開始剤は、エネルギー線の照射により、エチレン性不飽和基のラジカル重合を開始させるために添加される。
[(B) Photopolymerization initiator]
(B) A photopolymerization initiator is added to initiate radical polymerization of ethylenically unsaturated groups by irradiation with energy rays.
（Ｂ）光重合開始剤は、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインとベンゾインアルキルエーテル類；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、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等のアセトフェノン類；２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノプロパン－１－オン、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－モルフォリニル）フェニル］－１－ブタノン等のアミノアルキルフェノン類；２－メチルアントラキノン、２－エチルアントラキノン、２－ターシャリーブチルアントラキノン、１－クロロアントラキノン等のアントラキノン類；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；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；（２，６－ジメトキシベンゾイル）－２，４，４－ペンチルホ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、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、エチル－２，４，６－トリメチルベンゾイルフェニルフォスフィネイト等のフォスフィンオキサイド類；１，２－オクタンジオン，１－［４－（フェニルチオ）－，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；各種パーオキサイド類、チタノセン系開始剤などが挙げられる。これらは、Ｎ，Ｎ－ジメチルアミノ安息香酸エチルエステル、Ｎ，Ｎ－ジメチルアミノ安息香酸イソアミルエステル、ペンチル－４－ジメチルアミノベンゾエート、トリエチルアミン、トリエタノールアミン等の三級アミン類のような光増感剤等と併用してもよい。これらの光重合開始剤は単独で、または２種以上を組み合わせて用いることができる。 (B) Photopolymerization initiators include, for example, benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2- Acetophenones such as diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4- Aminoalkylphenones such as (4-morpholinyl)phenyl]-1-butanone; Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone; 2,4-dimethylthioxanthone , 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as 4,4'-bis(diethylamino)benzophenone; (2,6-dimethoxybenzoyl)-2,4,4-pentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, Phosphine oxides such as ethyl-2,4,6-trimethylbenzoylphenylphosphinate; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone, Oxime esters such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime); various peroxides, titanocene initiators, etc. can be mentioned. These include photosensitizers such as tertiary amines such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine. It may be used in combination with other agents. These photopolymerization initiators can be used alone or in combination of two or more.
（Ｂ）光重合開始剤の配合量は、本発明の硬化性組成物中、（Ａ）アルカリ可溶性樹脂１００質量部（固形分）に対して０．０１質量部以上３０質量部以下の範囲で、好ましくは０．５質量部以上２０質量部以下の範囲で配合される。 (B) The amount of the photopolymerization initiator is in the range of 0.01 parts by mass or more and 30 parts by mass or less based on 100 parts by mass (solid content) of the (A) alkali-soluble resin in the curable composition of the present invention. , preferably in a range of 0.5 parts by mass or more and 20 parts by mass or less.
［（Ｃ）エポキシ樹脂］
（Ｃ）エポキシ樹脂は、本発明の硬化性組成物を熱硬化させるために添加される化合物である。
[(C) Epoxy resin]
(C) Epoxy resin is a compound added to heat cure the curable composition of the present invention.
（Ｃ）エポキシ樹脂は、１分子中に少なくとも２つのエポキシ基を有する公知慣用の多官能エポキシ樹脂が使用できる。（Ｃ）エポキシ樹脂としては、例えば、三菱ケミカル社製のｊＥＲ８２８、ｊＥＲ８３４、ｊＥＲ１００１、ｊＥＲ１００４、ＤＩＣ社製のＥＰＩＣＬＯＮ８４０、ＥＰＩＣＬＯＮ８５０、ＥＰＩＣＬＯＮ８５０－Ｓ、ＥＰＩＣＬＯＮ１０５０、ＥＰＩＣＬＯＮ２０５５、東都化成社製のエポトートＹＤ－０１１、ＹＤ－０１３、ＹＤ－１２７、ＹＤ－１２８、ダウケミカル社製のＤ．Ｅ．Ｒ．３１７、Ｄ．Ｅ．Ｒ．３３１、Ｄ．Ｅ．Ｒ．６６１、Ｄ．Ｅ．Ｒ．６６４、住友化学工業社製のスミ－エポキシＥＳＡ－０１１、ＥＳＡ－０１４、ＥＬＡ－１１５、ＥＬＡ－１２８等（何れも商品名）のビスフェノールＡ型エポキシ樹脂；三菱ケミカル社製のｊＥＲ ＹＬ９０３、ＤＩＣ社製のＥＰＩＣＬＯＮ１５２、ＥＰＩＣＬＯＮ１６５、東都化成社製のエポトートＹＤＢ－４００、ＹＤＢ－５００、ダウケミカル社製のＤ．Ｅ．Ｒ．５４２、住友化学工業社製のスミ－エポキシＥＳＢ－４００、ＥＳＢ－７００等（何れも商品名）のブロム化エポキシ樹脂；三菱ケミカル社製のｊＥＲ１５２、ｊＥＲ１５４、ダウケミカル社製のＤ．Ｅ．Ｎ．４３１、Ｄ．Ｅ．Ｎ．４３８、ＤＩＣ社製のＥＰＩＣＬＯＮ Ｎ－７３０、ＥＰＩＣＬＯＮ Ｎ－７７０、ＥＰＩＣＬＯＮ Ｎ－８６５、東都化成社製のエポトートＹＤＣＮ－７０１、ＹＤＣＮ－７０４、日本化薬社製のＥＰＰＮ－２０１、ＥＯＣＮ－１０２５、ＥＯＣＮ－１０２０、ＥＯＣＮ－１０４Ｓ、ＲＥ－３０６、ＮＣ－３０００、住友化学工業社製のスミ－エポキシＥＳＣＮ－１９５Ｘ、ＥＳＣＮ－２２０、新日鐵化学社製のＹＤＣＮ－７００－２、ＹＤＣＮ－７００－３、ＹＤＣＮ－７００－５，ＹＤＣＮ－７００－７、ＹＤＣＮ－７００－１０、ＹＤＣＮ－７０４ ＹＤＣＮ－７０４Ａ、ＤＩＣ社製のＥＰＩＣＬＯＮ Ｎ－６８０、ＥＰＩＣＬＯＮ Ｎ－６９０、ＥＰＩＣＬＯＮ Ｎ－６９５（いずれも商品名）等のノボラック型エポキシ樹脂；ＤＩＣ社製のＥＰＩＣＬＯＮ８３０、三菱ケミカル社製ｊＥＲ８０７、東都化成社製のエポトートＹＤＦ－１７０、ＹＤＦ－１７５、ＹＤＦ－２００４等（何れも商品名）のビスフェノールＦ型エポキシ樹脂；東都化成社製のエポトートＳＴ－２００４、ＳＴ－２００７、ＳＴ－３０００（商品名）、三菱ケミカル社製のＹＸ８０３４等の水添ビスフェノールＡ型エポキシ樹脂；三菱ケミカル社製のｊＥＲ６０４、東都化成社製のエポトートＹＨ－４３４、住友化学工業社製のスミ－エポキシＥＬＭ－１２０等（何れも商品名）のグリシジルアミン型エポキシ樹脂；ヒダントイン型エポキシ樹脂；ダイセル化学工業社製のセロキサイド２０２１等（何れも商品名）の脂環式エポキシ樹脂；三菱ケミカル社製のＹＬ－９３３、日本化薬社製のＥＰＰＮ－５０１、ＥＰＰＮ－５０２等（何れも商品名）のトリヒドロキシフェニルメタン型エポキシ樹脂；三菱ケミカル社製のＹＬ－６０５６、ＹＸ－４０００、ＹＬ－６１２１（何れも商品名）等のビキシレノール型もしくはビフェノール型エポキシ樹脂又はそれらの混合物；日本化薬社製ＥＢＰＳ－２００、ＡＤＥＫＡ社製ＥＰＸ－３０、ＤＩＣ社製のＥＸＡ－１５１４（商品名）等のビスフェノールＳ型エポキシ樹脂；三菱ケミカル社製のｊＥＲ１５７Ｓ（商品名）等のビスフェノールＡノボラック型エポキシ樹脂；三菱ケミカル社製のｊＥＲ ＹＬ－９３１等（何れも商品名）のテトラフェニロールエタン型エポキシ樹脂；日本油脂社製ブレンマーＤＧＴ等のジグリシジルフタレート樹脂；日産化学工業社製のＴＥＰＩＣ等（何れも商品名）の複素環式エポキシ樹脂；東都化成社製ＺＸ－１０６３等のテトラグリシジルキシレノイルエタン樹脂；新日鐵化学社製ＥＳＮ－１９０、ＥＳＮ－３６０、ＤＩＣ社製ＨＰ－４０３２、ＥＸＡ－４７５０、ＥＸＡ－４７００等のナフタレン基含有エポキシ樹脂；ＤＩＣ社製ＨＰ－７２００、ＨＰ－７２００Ｈ等のジシクロペンタジエン骨格を有するエポキシ樹脂；日本油脂社製ＣＰ－５０Ｓ、ＣＰ－５０Ｍ等のグリシジルメタアクリレート共重合系エポキシ樹脂；さらにシクロヘキシルマレイミドとグリシジルメタアクリレートの共重合エポキシ樹脂；ＣＴＢＮ変性エポキシ樹脂（例えば東都化成社製のＹＲ－１０２、ＹＲ－４５０等）等が挙げられるが、これらに限られるものではない。 As the epoxy resin (C), a known and commonly used polyfunctional epoxy resin having at least two epoxy groups in one molecule can be used. (C) Epoxy resins include, for example, jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, EPICLON840, EPICLON850, EPICLON850-S, EPICLON1050, and EPICLON2055 manufactured by DIC Corporation. , Epotote YD-011 manufactured by Toto Kasei Co., Ltd., YD -013, YD-127, YD-128, D. E. R. 317, D. E. R. 331, D. E. R. 661, D. E. R. 664, bisphenol A type epoxy resin such as Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128 (all trade names) manufactured by Sumitomo Chemical; jER YL903 manufactured by Mitsubishi Chemical, DIC EPICLON152 and EPICLON165 manufactured by Toto Kasei Co., Ltd., Epotote YDB-400 and YDB-500 manufactured by Toto Kasei Co., Ltd., and D. E. R. 542, brominated epoxy resins such as Sumi-Epoxy ESB-400 and ESB-700 (all trade names) manufactured by Sumitomo Chemical; jER152 and jER154 manufactured by Mitsubishi Chemical, and D. E. N. 431, D. E. N. 438, EPICLON N-730, EPICLON N-770, EPICLON N-865 manufactured by DIC, EPOTOTO YDCN-701, YDCN-704 manufactured by Toto Kasei, EPPN-201, EOCN-1025, EOCN manufactured by Nippon Kayaku Co., Ltd. -1020, EOCN-104S, RE-306, NC-3000, Sumi-Epoxy ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Co., Ltd., YDCN-700-2, YDCN-700-3 manufactured by Nippon Steel Chemical Co., Ltd. , YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704 YDCN-704A, EPICLON N-680, EPICLON N-690, EPICLON N-695 manufactured by DIC (all product names) Bisphenol F-type epoxy resins such as EPICLON830 manufactured by DIC, jER807 manufactured by Mitsubishi Chemical, Epotote YDF-170, YDF-175, YDF-2004 manufactured by Toto Kasei (all trade names); Hydrogenated bisphenol A type epoxy resins such as Epotote ST-2004, ST-2007, ST-3000 (product name) manufactured by Toto Kasei Co., Ltd. and YX8034 manufactured by Mitsubishi Chemical Corporation; Glycidylamine-type epoxy resins such as Epototo YH-434 and Sumitomo Chemical Co., Ltd.'s Sum-Epoxy ELM-120 (all trade names); Hydantoin-type epoxy resins; Celoxide 2021 (all trade names) made by Daicel Chemical Industries, Ltd. ) alicyclic epoxy resin; YL-933 manufactured by Mitsubishi Chemical; trihydroxyphenylmethane type epoxy resin such as EPPN-501, EPPN-502 manufactured by Nippon Kayaku Co., Ltd. (all trade names); manufactured by Mitsubishi Chemical Bixylenol type or biphenol type epoxy resins such as YL-6056, YX-4000, YL-6121 (all trade names) or mixtures thereof; Nippon Kayaku Co., Ltd. EBPS-200, ADEKA Co., Ltd. EPX-30, DIC Bisphenol S type epoxy resin such as EXA-1514 (trade name) manufactured by Mitsubishi Chemical Corporation; Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; jER YL-931 etc. manufactured by Mitsubishi Chemical Corporation (both Tetraphenyloethane type epoxy resin (trade name); Diglycidyl phthalate resin such as Blenmar DGT manufactured by Nihon Yushi; Heterocyclic epoxy resin such as TEPIC (all trade names) manufactured by Nissan Chemical Industries, Ltd.; manufactured by Toto Kasei Co., Ltd. Tetraglycidylxylenoylethane resins such as ZX-1063; naphthalene group-containing epoxy resins such as ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. and HP-4032, EXA-4750 and EXA-4700 manufactured by DIC Corporation; DIC Epoxy resins with a dicyclopentadiene skeleton such as HP-7200 and HP-7200H made by Nihon Yushi; glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M made by Nihon Yushi; Copolymerized epoxy resins include, but are not limited to, CTBN-modified epoxy resins (for example, YR-102 and YR-450 manufactured by Toto Kasei Co., Ltd.).
（Ｃ）エポキシ樹脂を配合する場合は、（Ａ）アルカリ可溶性樹脂のカルボン酸当量に対して、０．８エポキシ当量以上２．０エポキシ当量以下となる量で配合される。ここで、カルボン酸当量とは、カルボキシル基１ｍｏｌ量を得るのに必要な（Ａ）アルカリ可溶性樹脂の重量を表し、単位はｇ／ｍｏｌである。また、エポキシ当量とは、エポキシ基１ｍｏｌ量を得るのに必要な（Ｃ）エポキシ樹脂の重量を表し、単位はｇ／ｍｏｌである。（Ｃ）エポキシ樹脂の質量が、（Ａ）アルカリ可溶性樹脂のカルボン酸当量に対して０．８エポキシ当量以上２．０エポキシ当量以下である。エポキシ当量が、このような範囲内にあると耐熱性や電気特性、クラック耐性に優れた硬化物を得ることが出来る。 When (C) an epoxy resin is blended, it is blended in an amount of 0.8 to 2.0 epoxy equivalents relative to the carboxylic acid equivalent of the alkali-soluble resin (A). Here, the carboxylic acid equivalent represents the weight of the alkali-soluble resin (A) required to obtain 1 mol of carboxyl group, and the unit is g/mol. Moreover, the epoxy equivalent represents the weight of the (C) epoxy resin necessary to obtain 1 mol of epoxy groups, and the unit is g/mol. The mass of the epoxy resin (C) is 0.8 to 2.0 epoxy equivalents relative to the carboxylic acid equivalent of the alkali-soluble resin (A). When the epoxy equivalent is within this range, a cured product with excellent heat resistance, electrical properties, and crack resistance can be obtained.
［（Ｄ）シリコーン化合物］
（Ｄ）シリコーン化合物は、銅張基板（基材）に対する本発明の硬化性組成物のぬれ性を向上させ、そのはじきを抑え、レベリング性を向上させるために配合される。
[(D) Silicone compound]
(D) The silicone compound is blended to improve the wettability of the curable composition of the present invention to the copper-clad substrate (substrate), suppress its repellency, and improve leveling properties.
（Ｄ）シリコーン化合物は、ポリジメチルシロキサン又はポリジメチルシロキサンを基本構造とする誘導体であって、ポリジメチルシロキサン、ポリエーテル変性ポリジメチルシロキサン、ポリエステル変性ポリジメチルシロキサン、ポリエステル変性ポリメチルアルキルシロキサン、ポリエーテル変性ポリメチルアルキルシロキサン、アラルキル変性ポリメチルアルキルシロキサン、ポリエーテル変性シロキサン、ポリエステル変性水酸基含有ポリジメチルシロキサンなどが挙げられる。 (D) The silicone compound is polydimethylsiloxane or a derivative having a basic structure of polydimethylsiloxane, and includes polydimethylsiloxane, polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, polyester-modified polymethylalkylsiloxane, and polyether-modified polydimethylsiloxane. Examples include modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyether-modified siloxane, and polyester-modified hydroxyl group-containing polydimethylsiloxane.
（Ｄ）シリコーン化合物の市販品としては、ＢＹＫ（登録商標）－３００、ＢＹＫ（登録商標）－３０２、ＢＹＫ（登録商標）－３０６、ＢＹＫ（登録商標）－３０７、ＢＹＫ（登録商標）－３１０、ＢＹＫ（登録商標）－３１５Ｎ、ＢＹＫ（登録商標）－３２０、ＢＹＫ（登録商標）－３２２、ＢＹＫ（登録商標）－３２３、ＢＹＫ（登録商標）－３２５、ＢＹＫ（登録商標）－３３０、ＢＹＫ（登録商標）－３３１、ＢＹＫ（登録商標）－３３３、ＢＹＫ（登録商標）－３４２、ＢＹＫ（登録商標）－３４５、ＢＹＫ（登録商標）－３４６、ＢＹＫ（登録商標）－３４７、ＢＹＫ（登録商標）－３４８、ＢＹＫ（登録商標）－３４９、ＢＹＫ（登録商標）－３７０、ＢＹＫ（登録商標）－３７７、ＢＹＫ（登録商標）－３７８、ＢＹＫ（登録商標）－３４５５（以上、ビックケミー・ジャパン社製）が挙げられる。 (D) Commercially available silicone compounds include BYK (registered trademark) -300, BYK (registered trademark) -302, BYK (registered trademark) -306, BYK (registered trademark) -307, BYK (registered trademark) -310. , BYK (registered trademark) -315N, BYK (registered trademark) -320, BYK (registered trademark) -322, BYK (registered trademark) -323, BYK (registered trademark) -325, BYK (registered trademark) -330, BYK (registered trademark) -331, BYK (registered trademark) -333, BYK (registered trademark) -342, BYK (registered trademark) -345, BYK (registered trademark) -346, BYK (registered trademark) -347, BYK (registered trademark) Trademark) -348, BYK (registered trademark) -349, BYK (registered trademark) -370, BYK (registered trademark) -377, BYK (registered trademark) -378, BYK (registered trademark) -3455 (the above, BYK (registered trademark) (manufactured by the company).
（Ｄ）シリコーン化合物は、本発明の硬化性組成物中、（Ａ）アルカリ可溶性樹脂１００質量部（固形分）に対して０．１質量部以上１０質量部以下の範囲で、好ましくは１質量部以上５質量部以下の範囲で配合される。（Ｄ）シリコーン化合物が０．１質量部以上１０質量部以下の範囲であることで、硬化性組成物の銅張基板（基材）に対するぬれ性が確保され、レベリング性が良好となるとともに、硬化物に対するフラックスのぬれ性も良好なものとなる。 (D) The silicone compound is contained in the curable composition of the present invention in an amount of 0.1 parts by mass or more and 10 parts by mass or less, preferably 1 part by mass, based on 100 parts by mass (solid content) of the alkali-soluble resin (A). It is blended in a range of 5 parts by mass or more and 5 parts by mass or less. (D) Since the silicone compound is in the range of 0.1 parts by mass or more and 10 parts by mass or less, the wettability of the curable composition to the copper-clad substrate (base material) is ensured, and the leveling property is improved, The flux also has good wettability with respect to the cured product.
［（Ｅ）親水性シリカ］
（Ｅ）親水性シリカは、本発明の硬化性組成物の硬化収縮抑制のため、及び得られた硬化物の剛性強化のために添加される。
[(E) Hydrophilic silica]
(E) Hydrophilic silica is added to suppress curing shrinkage of the curable composition of the present invention and to strengthen the rigidity of the obtained cured product.
本発明において、（Ｅ）親水性シリカとは、その親水性表面に疎水性有機基を付加する表面処理が施されていない未処理のシリカのことをいい、溶融シリカ、球状シリカ、無定形シリカ、結晶性シリカ等が挙げられる。 In the present invention, (E) hydrophilic silica refers to untreated silica that has not been surface-treated to add a hydrophobic organic group to its hydrophilic surface, and includes fused silica, spherical silica, amorphous silica, etc. , crystalline silica, and the like.
なお、疎水性有機基を付加する表面処理とは、例えば、エチレン性不飽和基（光硬化性反応基）、アルキル基等の疎水性有機基を有するカップリング剤等で（未処理の）親水性シリカの表面を処理することをいい、かかる表面処理が施されたシリカは上記（Ｅ）親水性シリカには含まれない。 Note that surface treatment to add a hydrophobic organic group refers to, for example, a coupling agent having a hydrophobic organic group such as an ethylenically unsaturated group (photocurable reactive group) or an alkyl group to add an (untreated) hydrophilic group. This refers to treating the surface of hydrophilic silica, and silica that has been subjected to such surface treatment is not included in the above (E) hydrophilic silica.
市販品としては、ＦＢ―１５Ｄ、ＦＢ―１０５、ＦＢ―１０５Ｘ、ＦＢ―５ＳＤＸ、ＳＦＰ―２０Ｍ、ＳＦＰ―１３０ＭＣ（以上、電気化学工業社製）、エクセシリカ（登録商標）（株式会社トクヤマ製）、ＳＲ―ＮＰ（エムテック化学社製）等が挙げられる。 Commercially available products include FB-15D, FB-105, FB-105X, FB-5SDX, SFP-20M, SFP-130MC (manufactured by Denki Kagaku Kogyo Co., Ltd.), Excelsilica (registered trademark) (manufactured by Tokuyama Corporation), Examples include SR-NP (manufactured by Mtec Chemical Co., Ltd.).
（Ｅ）親水性シリカは、プリント配線板の硬化膜を形成する用途では、メジアン径（Ｄ５０）が３０μｍ以下であり、ＩＣパッケージ基板に硬化膜を形成する用途では５μｍ以下であり、メジアン径（Ｄ５０）が０．２μｍ以上２μｍ以下の範囲であると硬化性組成物中での分散性の観点から好ましい。なお、メジアン径（Ｄ５０）の測定方法は以下のとおりである。 (E) Hydrophilic silica has a median diameter (D50) of 30 μm or less when used to form a cured film on a printed wiring board, and a median diameter (D50) of 5 μm or less when used to form a cured film on an IC package substrate. D50) is preferably in the range of 0.2 μm or more and 2 μm or less from the viewpoint of dispersibility in the curable composition. The method for measuring the median diameter (D50) is as follows.
＜メジアン径（Ｄ５０）の測定方法＞
容量１００ｍｌのビーカーにエタノール３０ｍｌとシリカ粉末１ｇを入れて、卓上型超音波洗浄機内で3分間攪拌後、レーザー回折／散乱式粒度分布計（マイクロトラック・ベル社製）マイクロトラックＭＴ－３３００を使用し、エタノール溶媒にて体積基準メジアン径（Ｄ５０）を測定した。
<Measurement method of median diameter (D50)>
Put 30 ml of ethanol and 1 g of silica powder in a 100 ml beaker, stir for 3 minutes in a tabletop ultrasonic cleaner, and then use a laser diffraction/scattering particle size distribution analyzer (Microtrac MT-3300, manufactured by Microtrac Bell). Then, the volume-based median diameter (D50) was measured using an ethanol solvent.
また、（Ｅ）親水性シリカは、本発明の硬化性組成物中、（Ａ）アルカリ可溶性樹脂１００質量部（固形分）に対して１０質量部以上２００質量部以下の範囲で、好ましくは２０質量部以上１８０質量部以下の範囲で配合される。（Ｅ）親水性シリカが１０質量部以上２００質量部以下の範囲であることで、硬化収縮抑制及び硬化物の剛性強化の効果を得つつ、分散性も良好なものとなる。 Furthermore, (E) hydrophilic silica is present in the curable composition of the present invention in an amount of 10 parts by mass or more and 200 parts by mass or less, preferably 20 parts by mass or less, based on 100 parts by mass (solid content) of the alkali-soluble resin (A). It is blended in a range of not less than 180 parts by mass. (E) When the amount of hydrophilic silica is in the range of 10 parts by mass or more and 200 parts by mass or less, good dispersibility can be achieved while suppressing curing shrinkage and increasing the rigidity of the cured product.
［（Ｆ）有機揺変剤］
（Ｆ）有機揺変剤は、本発明の硬化性組成物中での（Ｅ）親水性シリカの凝集・沈殿抑制のため、及び本発明で初めて明らかになったように、本発明の硬化性組成物の硬化物に対するフラックスのぬれ性向上のために添加される。
[(F) Organic thixotropic agent]
(F) The organic thixotropic agent is used to suppress the aggregation and precipitation of (E) hydrophilic silica in the curable composition of the present invention, and as revealed for the first time in the present invention, the curable composition of the present invention It is added to improve the wettability of the flux to the cured product of the composition.
本発明の硬化性組成物中で用いることができる（Ｆ）有機揺変剤としては、植物油脂肪酸とアミンより合成される脂肪酸アミド類（アマイドワックス系）；脂肪酸エステル類、ポリエーテル類、硫酸化油、高級アルコールサルフェートなどの界面活性剤系；ポリカルボン酸エステル類；ポリカルボン酸アミド類；尿素変性化合物が含まれるが、ひまし油ワックスと呼ばれる水素添加ひまし油系のもの、及びポリエチレンを酸化処理し、極性基を導入したワックスである酸化ポリエチレン系のものは含まれない。 Examples of organic thixotropic agents (F) that can be used in the curable composition of the present invention include fatty acid amides (amide wax type) synthesized from vegetable oil fatty acids and amines; fatty acid esters, polyethers, sulfated These include surfactant systems such as oils and higher alcohol sulfates; polycarboxylic acid esters; polycarboxylic acid amides; Oxidized polyethylene waxes, which are waxes with polar groups introduced, are not included.
（Ｆ）有機揺変剤の市販品としては、ＢＹＫ（登録商標）－Ｒ６０６、ＢＹＫ（登録商標）－４０５、ＢＹＫ（登録商標）－Ｒ６０５、ＢＹＫ（登録商標）－Ｒ６０７、ＢＹＫ（登録商標）－４１０、ＢＹＫ（登録商標）－４１１、ＢＹＫ（登録商標）－４１５、ＢＹＫ（登録商標）－４３０、ＢＹＫ（登録商標）－４３１、ＢＹＫ（登録商標）－７４１０ＥＴ、ＢＹＫ（登録商標）－７４１１ＥＳ（以上、ビックケミー・ジャパン社製）、ターレン１４５０、ターレン２０００、ターレン２２００Ａ、ターレン７２００ー２０、ターレン８２００－２０、ターレン８３００－２０、ターレン８７００－２０、ターレンＢＡ－６００、フローノンＳＨ－２９０、フローノンＳＨ－２９５Ｓ、フローノンＳＨ－３５０、フローノンＨＲ－２、フローノンＨＲ－４ＡＦ（以上、共栄社化学社製）が挙げられる。 (F) Commercially available organic thixotropic agents include BYK (registered trademark) -R606, BYK (registered trademark) -405, BYK (registered trademark) -R605, BYK (registered trademark) -R607, BYK (registered trademark) -410, BYK (registered trademark) -411, BYK (registered trademark) -415, BYK (registered trademark) -430, BYK (registered trademark) -431, BYK (registered trademark) -7410ET, BYK (registered trademark) -7411ES (manufactured by BIC Chemie Japan), Talen 1450, Talen 2000, Talen 2200A, Talen 7200-20, Talen 8200-20, Talen 8300-20, Talen 8700-20, Talen BA-600, Flonon SH-290, Flonon Examples include SH-295S, Fluonon SH-350, Fluonon HR-2, and Fluonon HR-4AF (manufactured by Kyoeisha Chemical Co., Ltd.).
（Ｆ）有機揺変剤は、本発明の硬化性組成物中、（Ｅ）親水性シリカ１００質量部（固形分）に対して０．０１質量部以上１５質量部以下であり、好ましくは０．０５質量部以上１０質量部以下である。 (F) The organic thixotropic agent is present in the curable composition of the present invention in an amount of 0.01 parts by mass or more and 15 parts by mass or less, preferably 0.01 parts by mass or more and 15 parts by mass or less, based on 100 parts by mass (solid content) of the (E) hydrophilic silica. The amount is .05 parts by mass or more and 10 parts by mass or less.
また、（Ｆ）有機揺変剤は、本発明の硬化性組成物中、（Ｄ）シリコーン化合物２質量部に対して０．０５質量部以上であり、好ましくは０．１質量部以上である。 Furthermore, (F) the organic thixotropic agent is present in an amount of 0.05 parts by mass or more, preferably 0.1 parts by mass or more, based on 2 parts by mass of the (D) silicone compound in the curable composition of the present invention. .
上記範囲内であることで、（Ｅ）親水性シリカが良好に分散し、且つ硬化性組成物の硬化物に対するフラックスのぬれ性も良好なものとなる。 Within the above range, (E) hydrophilic silica is well dispersed, and the flux has good wettability with respect to the cured product of the curable composition.
［（Ｇ）酸化防止剤］
本発明の硬化性組成物は、（Ｇ）酸化防止剤が添加されていることが好ましい。（Ｇ）酸化防止剤は、銅張基板（基材）の銅の酸化を抑制することで基材と硬化性組成物の密着性を向上させる。
[(G) Antioxidant]
The curable composition of the present invention preferably contains (G) an antioxidant. (G) The antioxidant improves the adhesion between the base material and the curable composition by suppressing the oxidation of copper in the copper-clad substrate (base material).
（Ｇ）酸化防止剤としては、３－（Ｎ－サリチロイル）アミノ－１，２，４－トリアゾール等のヒンダードフェノール化合物、２－メルカプトベンツイミダゾールの亜鉛塩等の硫黄系酸化防止剤、トリフェニルホスファイト等のリン系酸化防止剤、ジ－ｔｅｒｔ－ブチルジフェニルアミン等の芳香族アミン系酸化防止剤、メラミン、ベンゾトリアゾール、トリルトリアゾール等のヘテロ原子として窒素を含む複素乾式化合物（硫黄系酸化防止剤を除く）等が挙げられる。なかでも、メラミンが好ましい。 (G) Antioxidants include hindered phenol compounds such as 3-(N-salicyloyl)amino-1,2,4-triazole, sulfur-based antioxidants such as zinc salt of 2-mercaptobenzimidazole, triphenyl Phosphorous antioxidants such as phosphites, aromatic amine antioxidants such as di-tert-butyldiphenylamine, complex dry compounds containing nitrogen as a heteroatom (sulfur-based antioxidants) such as melamine, benzotriazole, tolyltriazole, etc. ), etc. Among them, melamine is preferred.
（Ｇ）酸化防止剤の配合量は、本発明の硬化性組成物中、（Ａ）アルカリ可溶性樹脂１００質量部（固形分）に対して０．１質量部以上５質量部以下であり、０．５質量部以上２質量部以下であることが好ましい。 The blending amount of (G) antioxidant is 0.1 parts by mass or more and 5 parts by mass or less based on 100 parts by mass (solid content) of (A) alkali-soluble resin in the curable composition of the present invention, and 0. The content is preferably .5 parts by mass or more and 2 parts by mass or less.
［他の成分］
さらに、本発明の硬化性組成物には、光重合性多官能モノマーを添加することが好ましい。光重合性多官能モノマーは、１分子中に２個以上のエチレン性不飽和基を有する化合物であって、（（Ａ）アルカリ可溶性樹脂にエチレン性不飽和基が含まれる場合には、）活性エネルギー線照射による（Ａ）アルカリ可溶性樹脂の光硬化を助け、硬化性組成物を光硬化させるために用いられる。
[Other ingredients]
Furthermore, it is preferable to add a photopolymerizable polyfunctional monomer to the curable composition of the present invention. A photopolymerizable polyfunctional monomer is a compound having two or more ethylenically unsaturated groups in one molecule, and (if the alkali-soluble resin (A) contains an ethylenically unsaturated group) It is used to assist in the photocuring of the alkali-soluble resin (A) by energy ray irradiation and to photocure the curable composition.
光重合性多官能モノマーとして用いられる化合物としては、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）アクリレートなどが挙げられる。具体的には、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などの多価アルコール又はこれらのエチレオキサイド付加物、プロピレンオキサイド付加物、もしくはε－カプロラクトン付加物など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、及びこれらのフェノール類のエチレンオキサイド付加物もしくはプロピレンオキサイド付加物など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、グリセリントリ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などのグリシジルエーテルの多価アクリレート類；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など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及びメラミンアクリレート、及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何れか一種などが挙げられる。 Examples of compounds used as photopolymerizable polyfunctional monomers include commonly known polyester (meth)acrylate, polyether (meth)acrylate, urethane (meth)acrylate, carbonate (meth)acrylate, and epoxy (meth)acrylate. Can be mentioned. Specifically, polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or their ethylene oxide adducts, propylene oxide adducts, ε-caprolactone adducts, etc. Polyvalent acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide or propylene oxide adducts of these phenols; Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether Polyhydric acrylates of glycidyl ethers such as glycidyl ether and triglycidyl isocyanurate; not limited to the above, polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, and polyester polyols can be directly acrylated, or urethane can be produced through diisocyanates. Examples include at least one of acrylated acrylates, melamine acrylate, and methacrylates corresponding to the acrylates.
光重合性多官能モノマーは、本発明の硬化性組成物中、（Ａ）アルカリ可溶性樹脂１００質量部（固形分）に対して３質量部以上３０質量部以下の範囲で、好ましくは１０質量部以上２０質量部以下の範囲で配合される。 The photopolymerizable polyfunctional monomer is present in the curable composition of the present invention in an amount of 3 parts by mass or more and 30 parts by mass or less, preferably 10 parts by mass, based on 100 parts by mass (solid content) of the alkali-soluble resin (A). It is blended in a range of 20 parts by mass or less.
本発明の硬化性組成物は、さらにジシアンジアミド、三フッ化ホウ素－アミン触媒、有機酸ヒドラジッドなどの硬化触媒を含むことが好ましい。硬化触媒は、本発明の硬化性組成物中、（Ａ）アルカリ可溶性樹脂１００質量部（固形分）に対して５質量部以下、好ましくは０．１質量部以上２質量部以下の範囲の量で添加される。 The curable composition of the present invention preferably further contains a curing catalyst such as dicyandiamide, boron trifluoride-amine catalyst, or organic acid hydrazide. The curing catalyst is present in the curable composition of the present invention in an amount of 5 parts by mass or less, preferably 0.1 parts by mass or more and 2 parts by mass or less, based on 100 parts by mass (solid content) of the alkali-soluble resin (A). It is added in
さらに、本発明の硬化性組成物には、着色を目的として、着色顔料や染料等を添加しても良い。着色顔料や染料等としては、カラ－インデックスで表される公知慣用のものが使用可能である。例えば、Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５、１５:１、１５:２、１５:３、１５:４、１５:６、１６、６０、Ｓｏｌｖｅｎｔ Ｂｌｕｅ ３５、６３、６８、７０、８３、８７、９４、９７、１２２、１３６、６７、７０、ＰｉｇｍｅｎｔＧｒｅｅｎ ７、 ３６、３、５、２０、２８、Ｓｏｌｖｅｎｔ Ｙｅｌｌｏｗ １６３、Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ ２４、１０８、１９３、１４７、１９９、２０２、１１０、１０９、１３９ １７９ １８５ ９３、９４、９５、１２８、１５５、１６６、１８０、１２０、１５１、１５４、１５６、１７５、１８１、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、１２、１３、１４、１６、１７、５５、６３、８１、８３、８７、１２６、１２７、１５２、１７０、１７２、１７４、１７６、１８８、 １９８、Ｐｉｇｍｅｎｔ Ｏｒａｎｇｅ １、５、１３、１４、１６、１７、２４、３４、３６、３８、４０、４３、４６、４９、５１、６１、６３、６４、７１、７３、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、３７、３８、４１、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、１７１、１７５、１７６、１８５、２０８、１２３、１４９、１６６、１７８、１７９、１９０、１９４、２２４、２５４、２５５、２６４、２７０、２７２、２２０、１４４、１６６、２１４、２２０、２２１、２４２、１６８、１７７、２１６、１２２、２０２、２０６、２０７、２０９、Ｓｏｌｖｅｎｔ Ｒｅｄ １３５、１７９、１４９、１５０、５２、２０７、Ｐｉｇｍｅｎｔ Ｖｉｏｌｅｔ １９、２３、２９、３２、３６、３８、４２、Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ １３、３６、Ｐｉｇｍｅｎｔ Ｂｒｏｗｎ ２３、２５、ＰｉｇｍｅｎｔＢｌａｃｋ １、７等が挙げられる。これら着色顔料・染料等は、硬化性組成物１００質量部に対して、０．０１質量部以上５質量部以下の範囲の量で、好ましくは０．１質量部以上３質量部以下の範囲の量で添加することができる。 Furthermore, coloring pigments, dyes, etc. may be added to the curable composition of the present invention for the purpose of coloring. As coloring pigments, dyes, etc., known and commonly used ones represented by color index can be used. For example, Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70, Pigment Green 7, 36, 3, 5, 20, 28, Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202, 110, 109, 139 179 185 93, 94 ,95, 128, 155, 166, 180, 120, 151, 154, 156, 175, 181, 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, 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, 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, 37, 38, 41, 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, 171, 175, 176, 185, 208, 123, 149, 166, 178, 179, 190, 194, 224, 254, 255, 264, 270, 272, 220, 144, 166, 214, 220, 221, 242, 168, 177, 177, 216, 122, 202, 206, 209, Solvent Red 135, 179, 149, 150, 150, 207, Pigment VIOLET 19, 23, 29, 36, 38, 42, Solvent Violet 13, 36, Pigment Brown 23, 25, Pigment Black 1, 7, etc. These coloring pigments, dyes, etc. are used in amounts ranging from 0.01 parts by mass to 5 parts by mass, preferably from 0.1 parts by mass to 3 parts by mass, based on 100 parts by mass of the curable composition. Can be added in amounts.
さらに、必要に応じて、ハイドロキノン、ハイドロキノンモノメチルエーテル、ｔ－ブチルカテコール、ピロガロール、フェノチアジンなどの公知慣用の重合禁止剤、光重合増感剤、光安定剤、分散剤、難燃剤、難燃助剤などのような公知慣用の添加剤類を配合することができる。 Furthermore, if necessary, known and commonly used polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, and phenothiazine, photopolymerization sensitizers, light stabilizers, dispersants, flame retardants, and flame retardant aids. Known and commonly used additives such as the following may be blended.
また、本発明の硬化性組成物は、粘度調整のために用いられる有機溶剤を含有してもよい。有機溶剤としては、例えば、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（ＤＰＭ）、ジプロピレングリコールジエチルエーテル、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、カルビトールアセテート、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を使用することができる。これらの有機溶剤は、単独で、または、２種類以上を組み合わせて用いることができる。 Further, the curable composition of the present invention may contain an organic solvent used for adjusting viscosity. Examples of organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, and propylene glycol. Glycol ethers such as monomethyl ether, dipropylene glycol monomethyl ether (DPM), dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbyl Esters such as tall acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha. can do. These organic solvents can be used alone or in combination of two or more.
＜本発明の硬化性組成物のドライフィルム、および硬化物＞
本発明の硬化性組成物は、キャリアフィルム（支持体）上に塗布、乾燥させて得られるドライフィルムの形態とすることができる。ドライフィルム化に際しては、本発明の硬化性組成物を上記有機溶剤により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キャリア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、乾燥塗膜とすることができる。塗布膜厚については特に制限はないが、一般に、乾燥後の膜厚で０．１～１００μｍ、好適には０．５～５０μｍの範囲で適宜選択される。
<Dry film and cured product of curable composition of the present invention>
The curable composition of the present invention can be in the form of a dry film obtained by coating and drying on a carrier film (support). When forming a dry film, the curable composition of the present invention is diluted with the above-mentioned organic solvent to adjust the viscosity to an appropriate level, and the curable composition of the present invention is adjusted to an appropriate viscosity using a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, A dry coating film can be obtained by applying it to a uniform thickness on a carrier film using a gravure coater, spray coater, etc., and drying it for 1 to 30 minutes, usually at a temperature of 50 to 130°C. There are no particular restrictions on the coating film thickness, but it is generally appropriately selected within the range of 0.1 to 100 μm, preferably 0.5 to 50 μm after drying.
キャリアフィルムとしては、プラスチックフィルムが用いられ、ポリエチレンテレ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プラスチックフィルムを用いることが好ましい。キャリアフィルムの厚さについては特に制限はないが、一般に、０．１～１５０μｍの範囲で適宜選択される。 As the carrier film, a plastic film is used, and it is preferable to use a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film. There are no particular restrictions on the thickness of the carrier film, but it is generally appropriately selected within the range of 0.1 to 150 μm.
この場合、キャリアフィルム上に塗膜を成膜した後、塗膜の表面に塵が付着するのを防ぐなどの目的で、塗膜の表面にさらに、剥離可能なカバーフィルムを積層することが好ましい。剥離可能なカバーフィルムとしては、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、カバーフィルムを剥離する際に、塗膜とカバーフィルムとの接着力が、塗膜とキャリアフィルムとの接着力よりも小さいものであればよい。 In this case, after forming the coating film on the carrier film, it is preferable to further laminate a removable cover film on the surface of the coating film for the purpose of preventing dust from adhering to the surface of the coating film. . As the removable cover film, for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc. can be used, and when the cover film is peeled off, the adhesive strength between the coating film and the cover film is smaller than the adhesive force between the coating film and the carrier film.
また、本発明の硬化性組成物につき上記有機溶剤を用いて塗布方法に適した粘度に調整した後、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、ダイコーター法等の方法により塗布して、約５０℃～９０℃の温度で組成物中に含まれる有機溶剤を揮発乾燥（仮乾燥）させることにより、タックフリーの乾燥塗膜を形成することができる。また、本発明の硬化性組成物をキャリアフィルム上に塗布し、乾燥させてフィルムとして巻き取ったドライフィルムの場合、これを、ラミネーター等により硬化性組成物の塗膜が基材と接触するように基材上に貼り合わせた後、キャリアフィルムを剥がすことにより、基材上に塗膜の層を形成することができる。 Further, the curable composition of the present invention may be applied to a substrate by dip coating, flow coating, roll coating, bar coating, or screen printing after adjusting the viscosity to be suitable for the coating method using the above-mentioned organic solvent. The organic solvent contained in the composition is volatilized and dried (temporary drying) at a temperature of approximately 50°C to 90°C, resulting in a tack-free dry coating. A film can be formed. In addition, in the case of a dry film in which the curable composition of the present invention is applied onto a carrier film, dried, and wound up as a film, the curable composition is coated with a laminator or the like so that the coating film of the curable composition comes into contact with the base material. A coating layer can be formed on the base material by peeling off the carrier film after laminating the film onto the base material.
これらの塗膜を、例えば、活性エネルギー線照射により光硬化させるか、または、１００℃～２５０℃の温度に加熱して熱硬化させることにより、硬化物を得ることができる。 A cured product can be obtained by photo-curing these coating films, for example, by irradiating them with active energy rays, or thermally curing them by heating them to a temperature of 100° C. to 250° C.
上記基材としては、予め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＋フェノール樹脂、紙＋エポキシ樹脂、紙＋ガラス布＋エポキシ樹脂、ガラス不織布＋エポキシ樹脂、ガラス織布＋エポキシ樹脂、ガラス繊維＋ポリイミド樹脂等の銅張積層板を挙げることができる。 In addition to printed wiring boards with circuits formed in advance and flexible printed wiring boards, the above-mentioned base materials include paper + phenol resin, paper + epoxy resin, paper + glass cloth + epoxy resin, glass nonwoven fabric + epoxy resin, glass woven cloth + Examples include copper-clad laminates made of epoxy resin, glass fiber + polyimide resin, and the like.
本発明の硬化性組成物を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など、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させる方法、および、ノズルより支持体に吹き付ける方法を用いて行うことができる。 The volatilization drying performed after applying the curable composition of the present invention is carried out using a dryer equipped with an air heating type heat source using steam, such as a hot air circulation drying oven, IR oven, hot plate, or convection oven. This can be carried out by using a method of bringing them into countercurrent contact with each other, or a method of spraying onto a support from a nozzle.
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データにより直接活性エネルギー線を照射し画像を描くダイレクトイメージング装置）も用いることができる。直描機の光源としては、最大波長が３５０～４１０ｎｍの範囲にある光を用いているものであればよい。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２０～１０００ｍＪ／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 active energy ray irradiation may be a device equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc., and irradiates ultraviolet rays in the range of 350 to 450 nm. , a direct drawing device (for example, a direct imaging device that draws an image by directly irradiating active energy rays based on CAD data from a computer) can also be used. The light source of the direct drawing machine may be one that uses light having a maximum wavelength in the range of 350 to 410 nm. The exposure amount for image formation varies depending on the film thickness, etc., but can generally be in the range of 20 to 1000 mJ/cm 2 , preferably 20 to 800 mJ/cm 2 .
また、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、アミン類などのアルカリ水溶液が使用できる。 In addition, the developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and the developing solution is potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, etc. Alkaline aqueous solutions such as , ammonia, and amines can be used.
このように、本発明の硬化性組成物から得られたドライフィルム、硬化物によれば、耐熱性、剛性、基材への密着性、絶縁性に優れることから種々の用途に適用可能であり、適用対象に特に制限はない。例えば、プリント配線板のエッチングレジスト、ソルダーレジスト、マーキングレジストの作成等に用いることができ、中でも、はんだ付け性が向上していることから、高い耐熱性が要求されるソルダーレジストとして好適に用いることができる。 As described above, the dry film and cured product obtained from the curable composition of the present invention have excellent heat resistance, rigidity, adhesion to substrates, and insulation properties, and can be applied to various uses. , there are no particular restrictions on the applicable targets. For example, it can be used to create etching resists, solder resists, marking resists, etc. for printed wiring boards, and in particular, it is suitable for use as solder resists that require high heat resistance because of its improved solderability. Can be done.
＜硬化性組成物の硬化物を絶縁性硬化被膜として用いた電子部品＞
上記基材上にパターン印刷した硬化性組成物の硬化物がソルダーレジストとして用いられる場合、部品の実装のためのはんだ付け工程で加熱される。はんだ付けは、手はんだ付け、フローはんだ付け、リフローはんだ付け等のいずれで行われてもよいが、例えば、リフローはんだ付けの場合には、１００℃～１４０℃で１～４時間の予熱と、その後、２４０～２８０℃で５～２０秒程度の加熱を複数回（例えば、２～４回）繰り返してはんだを加熱・溶融させるリフロー工程に供され、冷却後、必要により部品が実装されて電子部品が完成する。
<Electronic components using cured product of curable composition as insulating cured film>
When the cured product of the curable composition pattern-printed on the base material is used as a solder resist, it is heated in the soldering process for mounting components. Soldering may be performed by hand soldering, flow soldering, reflow soldering, etc., but for example, in the case of reflow soldering, preheating at 100 ° C to 140 ° C for 1 to 4 hours, After that, it is subjected to a reflow process in which the solder is heated and melted by repeating heating at 240 to 280 degrees Celsius for about 5 to 20 seconds multiple times (for example, 2 to 4 times), and after cooling, parts are mounted as necessary and electronic The parts are completed.
以下、実施例を示して本発明について具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、以下において特に断りのない限り、「部」は質量部を意味するものとする。 EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited only to these Examples. In addition, unless otherwise specified below, "parts" shall mean parts by mass.
（アルカリ可溶性樹脂の合成）
［合成例１］
ビスフェノールＦ型エポキシ樹脂（エポキシ当量９５０ｇ／ｅｑ、軟化点８５℃）３８０部とエピクロルヒドリン９２５部をジメチルスルホキシド４６２．５部に溶解させた後、攪拌下７０℃で９８．５％ＮａＯＨ６０．９部を１００分かけて添加した。添加後さらに７０℃で３時間反応を行った。反応終了後、水２５０部を加え水洗を行った。油水分離後、油層よりジメチルスルホキシドの大半および過剰の未反応エピクロルヒドリンを減圧下に蒸留回収し、残留した副製塩とジメチルスルホキシドを含む反応生成物をメチルイソブチルケトン７５０部に溶解させ、更に３０％ＮａＯＨ１０部を加え、７０℃で１時間反応させた。反応終了後、水２００部で２回水洗を行った。油水分離後、油層よりメチルイソブチルケトンを蒸留回収して、エポキシ当量３１０ｇ／ｅｑ、軟化点６９℃のエポキシ樹脂（ａ）を得た。得られたエポキシ樹脂（ａ）は、エポキシ当量から計算すると、前記出発物質ビスフェノールＦ型エポキシ樹脂におけるアルコール性水酸基６．２個のうち約５個がエポキシ化されたものであった。このエポキシ樹脂（ａ）３１０部およびカルビトールアセテート２８２部をフラスコに仕込み、９０℃に加熱・攪拌し、溶解した。得られた溶液を一旦６０℃まで冷却し、アクリル酸７２部（１モル）、メチルハイドロキノン０．５部、トリフェニルホスフィン２部を加え、１００℃に加熱し、約６０時間反応させ、酸価が０．２ｍｇＫＯＨ／ｇの反応物を得た。これにテトラヒドロ無水フタル酸１４０部（０．９２モル）を加え、９０℃に加熱し、反応を行い、感光性のカルボキシル基含有樹脂ワニス（Ａ－１）を得た。得られたカルボキシル基含有樹脂ワニス（Ａ－１）の固形分濃度は６２．５％、固形分酸価（ｍｇＫＯＨ／ｇ）は１００であった。
(Synthesis of alkali-soluble resin)
[Synthesis example 1]
After dissolving 380 parts of bisphenol F type epoxy resin (epoxy equivalent: 950 g/eq, softening point: 85°C) and 925 parts of epichlorohydrin in 462.5 parts of dimethyl sulfoxide, 60.9 parts of 98.5% NaOH was added at 70°C with stirring. It was added over 100 minutes. After the addition, the reaction was further carried out at 70°C for 3 hours. After the reaction was completed, 250 parts of water was added to wash with water. After oil and water separation, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin were distilled and recovered from the oil layer under reduced pressure, and the reaction product containing the remaining by-product salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone, and further dissolved in 30% NaOH10. of the mixture was added, and the mixture was reacted at 70°C for 1 hour. After the reaction was completed, washing was performed twice with 200 parts of water. After oil and water separation, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain an epoxy resin (a) having an epoxy equivalent of 310 g/eq and a softening point of 69°C. In the obtained epoxy resin (a), as calculated from the epoxy equivalent, about 5 out of 6.2 alcoholic hydroxyl groups in the starting bisphenol F type epoxy resin were epoxidized. 310 parts of this epoxy resin (a) and 282 parts of carbitol acetate were placed in a flask, heated to 90°C and stirred to dissolve. The obtained solution was once cooled to 60°C, 72 parts (1 mol) of acrylic acid, 0.5 part of methylhydroquinone, and 2 parts of triphenylphosphine were added, heated to 100°C, and reacted for about 60 hours to increase the acid value. A reactant containing 0.2 mgKOH/g was obtained. To this was added 140 parts (0.92 mol) of tetrahydrophthalic anhydride, and the mixture was heated to 90°C to carry out a reaction to obtain a photosensitive carboxyl group-containing resin varnish (A-1). The solid content concentration of the obtained carboxyl group-containing resin varnish (A-1) was 62.5%, and the solid content acid value (mgKOH/g) was 100.
［合成例２］
クレゾールノボラック型エポキシ樹脂（大日本インキ化学工業（株）製、登録商標“エピクロン”Ｎ－６９５、エポキシ当量：２２０）２２０部を撹拌機及び還流冷却器の付いた四つ口フラスコに入れ、カルビトールアセテート２１４部を加え、加熱溶解した。次に、重合禁止剤としてハイドロキノン０．１部と、反応触媒としてジメチルベンジルアミン２．０部を加えた。この混合物を９５～１０５℃に加熱し、アクリル酸７２部を徐々に滴下し、１６時間反応させた。この反応生成物を８０～９０℃まで冷却し、テトラヒドロフタル酸無水物１０６部を加え、８時間反応させ、冷却後、取り出した。
このようにして得られたエチレン性不飽和結合及びカルボキシル基を併せ持つ感光性樹脂は、不揮発分６５％、固形物の酸価８５ｍｇＫＯＨ／ｇ、重量平均分子量Ｍｗ約３，５００であった。以下、この樹脂溶液をワニス（Ａ－２）と称す。
なお、得られた樹脂の重量平均分子量の測定は、（株）島津製作所製ポンプＬＣ－８０４、ＫＦ－８０３、ＫＦ－８０２を三本つないだ高速液体クロマトグラフィーにより測定した。
[Synthesis example 2]
220 parts of cresol novolak type epoxy resin (manufactured by Dainippon Ink and Chemicals Co., Ltd., registered trademark "Epiclon" N-695, epoxy equivalent: 220) was placed in a four-necked flask equipped with a stirrer and a reflux condenser, and 214 parts of tall acetate was added and dissolved by heating. Next, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of dimethylbenzylamine as a reaction catalyst were added. This mixture was heated to 95-105°C, 72 parts of acrylic acid was gradually added dropwise, and the mixture was allowed to react for 16 hours. This reaction product was cooled to 80 to 90°C, 106 parts of tetrahydrophthalic anhydride was added, and the reaction product was allowed to react for 8 hours. After cooling, it was taken out.
The thus obtained photosensitive resin having both an ethylenically unsaturated bond and a carboxyl group had a nonvolatile content of 65%, an acid value of solid matter of 85 mgKOH/g, and a weight average molecular weight Mw of about 3,500. Hereinafter, this resin solution will be referred to as varnish (A-2).
The weight average molecular weight of the obtained resin was measured by high performance liquid chromatography using three pumps LC-804, KF-803, and KF-802 manufactured by Shimadzu Corporation.
＜１．実施例１～９および比較例１～３の硬化性組成物の調製＞
合成例の樹脂溶液及び表１に示す各材料をそれぞれ配合、撹拌機にて予備混合し、次いで３本ロールミルにより混練して硬化性組成物を調製した。表１中、（Ａ－１）～（Ａ－３）については、溶媒を含むそれぞれの樹脂溶液の質量部を示す。
<1. Preparation of curable compositions of Examples 1 to 9 and Comparative Examples 1 to 3>
The resin solution of the synthesis example and each material shown in Table 1 were blended, premixed using a stirrer, and then kneaded using a three-roll mill to prepare a curable composition. In Table 1, (A-1) to (A-3) indicate parts by mass of each resin solution containing a solvent.
上記各組成物について以下に示す特性試験を行った。その結果を表１に示す。 The following characteristic tests were conducted on each of the above compositions. The results are shown in Table 1.
＜２．基材に対する硬化性組成物のはじき・レベリング性の評価＞
化学研磨処理により表面を粗化した銅張基板（基材）上にスクリーン版（テトロン１００メッシュ）を用いて＜１．実施例１～９および比較例１～３の硬化性組成物の調製＞で調整された各硬化性組成物を銅張基板の全面に膜厚１０μｍとなるように印刷した。
<2. Evaluation of repellency and leveling properties of curable composition on substrate>
<1. Preparation of Curable Compositions of Examples 1 to 9 and Comparative Examples 1 to 3> Each of the curable compositions prepared in the above were printed on the entire surface of a copper-clad substrate to a film thickness of 10 μm.
印刷直後の塗膜を目視にて観察し、硬化性組成物のはじきの有無及びレベリング状態（平滑性）を確認した。次いで、印刷基板を８０℃、３０分で乾燥し、室温に戻してから乾燥後の塗膜状態を同様に目視して確認した。（なお、本実施例では目視で確認しているが、目視での判定が困難な場合には、表面粗さ測定機（サーフコーダ：株式会社小坂研究所製）や形状測定レーザーマイクロスコープ（ＶＫ－Ｘ－１００／ＫＥＹＥＮＣＥ社製）を用いて表面粗さを観察してもよい。）
評価基準は以下のとおりである。
The coating film immediately after printing was visually observed to confirm the presence or absence of repellency of the curable composition and the leveling state (smoothness). Next, the printed substrate was dried at 80° C. for 30 minutes, returned to room temperature, and the condition of the coating film after drying was similarly visually confirmed. (In this example, confirmation was performed visually, but if visual judgment is difficult, use a surface roughness measuring device (Surfcoder: manufactured by Kosaka Laboratory Co., Ltd.) or a shape measuring laser microscope (VK -X-100/manufactured by KEYENCE) may be used to observe the surface roughness.)
The evaluation criteria are as follows.
○：はじき無く、メッシュ跡が無い
△：はじき有り、且つメッシュ跡が無い、あるいは、はじき無し、且つメッシュ跡有り
×：はじき有り、且つメッシュ跡有り
○: No repelling and no mesh marks △: Repelling and no mesh marks, or no repelling and mesh marks ×: Repelling and mesh marks
＜３．フラックスはじきの評価＞
スクリーン版（テトロン１００メッシュ）を用いて＜１．実施例１～４および比較例１～４の硬化性組成物の調製＞で調整された各硬化性組成物を、化学研磨処理により表面を粗化した外形１５０×９５ｍｍ、厚さ１．６ｍｍのＦＲ－４、３５μｍ厚銅張積層板の全面に膜厚１０μｍとなるように印刷した。
<3. Flux repellent evaluation>
Using a screen plate (Tetron 100 mesh) <1. Preparation of curable compositions of Examples 1 to 4 and Comparative Examples 1 to 4> Each of the curable compositions prepared in Example 1 to 4 and Comparative Examples 1 to 4 was prepared in a mold with an outer diameter of 150 x 95 mm and a thickness of 1.6 mm, the surface of which was roughened by chemical polishing. Printing was performed on the entire surface of a FR-4, 35 μm thick copper clad laminate to a film thickness of 10 μm.
８０℃、３０分で乾燥後、パターン形成のため９５×１５０ｍｍの大きさの露光マスクを用いて６００ｍＪ／ｃｍ２で露光し、アルカリ現像(１％Ｎａ２Ｏ３ａｑ、３０℃、６０秒現像)を行い、１５０℃／６０分で熱硬化後、１０００ｍＪ／ｃｍ２のポストＵＶ処理を行った。 After drying at 80°C for 30 minutes, it was exposed to light at 600 mJ/cm 2 using an exposure mask with a size of 95 x 150 mm to form a pattern, followed by alkaline development (1% Na 2 O 3 aq, 30°C, 60 seconds development). ), and after heat curing at 150° C./60 minutes, post-UV treatment at 1000 mJ/cm 2 was performed.
硬化性組成物の硬化物が固定されたＦＲ－４基板（基材）に無電解Ｓｎめっき処理（Ｓｎ：１．１μｍ／塚田理研工業（株））を施し、リフロー工程（２６５℃）を１回から３回まで繰り返し実施し、無電解Ｓｎめっき処理後リフロー工程前、リフロー工程１回後、リフロー工程２回後、リフロー工程３回後の各段階で、硬化性組成物の硬化物が固定されたＦＲ－４基板に対してぬれ張力試験を実施した。 The FR-4 substrate (base material) on which the cured product of the curable composition was fixed was subjected to electroless Sn plating treatment (Sn: 1.1 μm/Tsukada Riken Kogyo Co., Ltd.), and then subjected to a reflow process (265°C) for 1 time. The cured product of the curable composition is fixed at each stage after electroless Sn plating, before the reflow process, after 1 reflow process, after 2 reflow processes, and after 3 times. A wet tension test was conducted on the FR-4 substrate.
ぬれ張力試験は、ＪＩＳ Ｋ６７６８に基づいて行い、ぬれ張力試験用混合液としては、無電解Ｓｎめっき処理後リフロー工程前は“ぬれ張力試験用混合液ＮＯ．６０．０”を、リフロー工程１回後は“ぬれ張力試験用混合液ＮＯ．３８．０”を、リフロー工程２回後は“ぬれ張力試験用混合液ＮＯ．３６．０”を、リフロー工程３回後は“ぬれ張力試験用混合液ＮＯ．３４．０”を、それぞれ用いた。いずれのぬれ張力試験用混合液も富士フィルム和光純薬社製である。なお、各混合液のＮＯ．は、その混合液の表面張力（単位：ｍＮ／ｍ）を示す。 The wet tension test was conducted based on JIS K6768, and the mixed solution for the wet tension test was "mixed solution for wet tension test No. 60.0" after the electroless Sn plating treatment and before the reflow process, and once in the reflow process. After that, use "wet tension test mixture NO. 38.0", after 2 reflow processes use "wet tension test mixture NO. 36.0", and after 3 reflow processes use "wet tension test mixture NO. 36.0". Liquid No. 34.0'' was used in each case. Both liquid mixtures for wetting tension tests are manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. In addition, the NO. of each mixed liquid. represents the surface tension (unit: mN/m) of the mixed liquid.
ぬれ張力試験は、具体的には、ぬれ張力試験用混合液の付いた綿棒で基板をなぞり、２秒後の液膜の状態を観察した。そして、液膜が破れを生じないで、２秒以上塗布されたときの状態を保っている場合をぬれていると判断した。 Specifically, in the wetting tension test, the substrate was traced with a cotton swab coated with the mixed solution for wetting tension testing, and the state of the liquid film was observed after 2 seconds. The liquid film was determined to be wet when it remained in the state it was in when it was applied for 2 seconds or more without causing any breakage.
なお、ぬれ張力試験用混合液の数値が高いほどフラックスはじきが良いことから、ぬれ張力試験は、フラックスはじきを評価する試験となっている。 Note that the higher the numerical value of the mixed liquid for wet tension test, the better the flux repellency, so the wet tension test is a test for evaluating flux repulsion.
表１において、評価基準は以下のとおりである。 In Table 1, the evaluation criteria are as follows.
○：無電解Ｓｎめっき処理後リフロー工程前～リフロー工程３回後までの全ての段階において、ぬれている（はじきがない）と判断される。 ○: Determined to be wet (no repellency) at all stages from before the reflow process to after the third reflow process after electroless Sn plating treatment.
×：無電解Ｓｎめっき処理後リフロー工程前～リフロー工程３回後までのうち、１回でもぬれていない（はじきがある）と判断されている場合がある。 ×: After the electroless Sn plating process, it may be determined that there is no wetness (there is repellency) even once from before the reflow process to after the reflow process three times.
*1：サイクロマーＰ（ＡＣＡ）Ｚ２５０（固形分４５ｗｔ％の不飽和基含有カルボキシル基含有共重合樹脂溶液、ダイセル化学社製）
*2：２，４，６－トリメチルベンゾイルジフェニルホスフィンオキシド（Ｏｍｎｉｒａｄ ＴＰＯ Ｈ：ＩＧＭ Ｒｅｓｉｎｓ Ｂ．Ｖ．社製）
*3：２－ジメチルアミノ－２－（４－メチル－ベンジル）－１－（４－モルホリン－４－イル－フェニル）－ブタン－１－オン（Ｏｍｎｉｒａｄ ３７９：ＩＧＭ Ｒｅｓｉｎｓ Ｂ．Ｖ．社製）
*4：ビスフェノールＡ型エポキシ樹脂（ＪＥＲ（登録商標）－８３４：三菱ケミカル社製）
*5：イソシアヌル酸トリグリシジル（ＴＥＰＩＣ－ＨＰ：日産化学工業社製）
*6：ポリエステル変性ポリジメチルシロキサン（ＢＹＫ（登録商標）－３１３：ビックケミー・ジャパン社製）
*7：ポリエーテル変性ポリジメチルシロキサン（ＢＹＫ（登録商標）－３００：ビックケミー・ジャパン社製）
*8：球状シリカ（Ｄ５０＝０．６μｍ）（ＳＦＰ－１３０ＭＣ：電気化学工業社製）
*9：球状シリカ（Ｄ５０＝０．４μｍ）（ＳＦＰ－２０Ｍ：電気化学工業社製）
*10：ポリヒドロキシカルボン酸エステル（ＢＹＫ（登録商標）－Ｒ ６０６：ビックケミー・ジャパン社製）
*11：メラミン（メラミン：日産化学工業社製）
*12：メタクリルシラン処理を表面に施した球状シリカ（１．５μｍＳＭ－Ｃ４：アドマテックス社製）
*13：ジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ：日本化薬社製）
*14：ジシアンジアミド（Ｃ０４５４：東京化成工業社製）
*15：青色顔料（ファーストゲンブルー５３８０：ＤＩＣ社製）、表１では固形分の質量部を示す。
*16：黄色顔料（Ｃｒｏｍｏｐｈｔａｌ（登録商標） Ｙｅｌｌｏｗ Ｓ１５１５：ＢＡＳＦ社製）、表１では固形分の質量部を示す。
*17：ジプロピレングリコールメチルエーテル（ダワノール（Ｄｏｗａｎｏｌ）（登録商標）ＤＰＭ：ダウ・ケミカル日本社製）
*1: Cyclomer P (ACA) Z250 (solid content 45 wt% unsaturated group-containing carboxyl group-containing copolymer resin solution, manufactured by Daicel Chemical Co., Ltd.)
*2: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Omnirad TPO H: manufactured by IGM Resins B.V.)
*3: 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (Omnirad 379: manufactured by IGM Resins B.V.)
*4: Bisphenol A type epoxy resin (JER (registered trademark)-834: manufactured by Mitsubishi Chemical Corporation)
*5: Triglycidyl isocyanurate (TEPIC-HP: manufactured by Nissan Chemical Industries, Ltd.)
*6: Polyester modified polydimethylsiloxane (BYK (registered trademark)-313: manufactured by BYK Chemie Japan Co., Ltd.)
*7: Polyether modified polydimethylsiloxane (BYK (registered trademark)-300: manufactured by BYK Chemie Japan Co., Ltd.)
*8: Spherical silica (D50=0.6μm) (SFP-130MC: manufactured by Denki Kagaku Kogyo Co., Ltd.)
*9: Spherical silica (D50=0.4μm) (SFP-20M: manufactured by Denki Kagaku Kogyo Co., Ltd.)
*10: Polyhydroxycarboxylic acid ester (BYK (registered trademark)-R 606: manufactured by BYK Chemie Japan)
*11: Melamine (Melamine: manufactured by Nissan Chemical Industries, Ltd.)
*12: Spherical silica with methacrylic silane treatment on the surface (1.5 μm SM-C4: manufactured by Admatex)
*13: Dipentaerythritol hexaacrylate (DPHA: manufactured by Nippon Kayaku Co., Ltd.)
*14: Dicyandiamide (C0454: manufactured by Tokyo Chemical Industry Co., Ltd.)
*15: Blue pigment (First Gen Blue 5380: manufactured by DIC Corporation), Table 1 shows the solid content in parts by mass.
*16: Yellow pigment (Cromophtal (registered trademark) Yellow S1515: manufactured by BASF), Table 1 shows parts by mass of solid content.
*17: Dipropylene glycol methyl ether (Dowanol (registered trademark) DPM: manufactured by Dow Chemical Japan Co., Ltd.)
表１の実施例に示すように、（Ｄ）シリコーン化合物、（Ｅ）親水性シリカ及び（Ｆ）有機揺変剤が配合されるとき、銅張基板（基材）に対する本発明の硬化性組成物のぬれ性が維持され、レベリング性も良好なものとなり、（Ｅ）親水性シリカの凝集・沈殿も生じなかった。また、本発明の硬化性組成物の硬化物が固定された基材上にぬれ張力試験用混合液を塗布した場合にも、当該硬化物上でのぬれ張力試験用混合液のはじきがなく、当該硬化物に対するぬれ張力試験用混合液のぬれ性が維持されていた。 As shown in the examples in Table 1, when (D) a silicone compound, (E) a hydrophilic silica, and (F) an organic thixotropic agent are blended, the curable composition of the present invention for a copper-clad substrate (base material) The wettability of the material was maintained, the leveling property was also good, and (E) no aggregation or precipitation of hydrophilic silica occurred. Furthermore, even when the mixed liquid for wet tension testing is applied onto a substrate on which a cured product of the curable composition of the present invention is fixed, the mixed liquid for wet tension testing does not repel on the cured product. The wettability of the mixed liquid for wetting tension test on the cured product was maintained.
一方、シリカの表面に疎水性処理が施されている比較例１では、（Ｆ）有機揺変剤が配合されていたとしても硬化性組成物の硬化物が固定された基材に対するぬれ張力試験用混合液のぬれ性が低下しており、はんだ付け性が低下するものと考えられた。また、（Ｆ）有機揺変剤を含まない比較例２では、（Ｄ）シリコーン化合物及び（Ｅ）親水性シリカが配合されていても硬化性組成物の硬化物が固定された基材に対するぬれ張力試験用混合液のぬれ性が低下しており、はんだ付け性が低下するものと考えられた。さらに、（Ｄ）シリコーン化合物が含まれていない比較例３では、銅張基板（基材）に対する硬化性組成物のぬれ性が不十分であるか、あるいはレベリング性が悪化していた。 On the other hand, in Comparative Example 1 in which the surface of silica was subjected to hydrophobic treatment, even if (F) an organic thixotropic agent was blended, a wet tension test was performed on a substrate to which a cured product of the curable composition was fixed. It was thought that the wettability of the liquid mixture for soldering had decreased, and that the solderability had decreased. In addition, in Comparative Example 2 which does not contain (F) an organic thixotropic agent, even though (D) a silicone compound and (E) a hydrophilic silica are blended, the cured product of the curable composition does not wet the substrate on which it is fixed. The wettability of the mixed solution for tension testing was reduced, and it was thought that the solderability was reduced. Furthermore, in Comparative Example 3 in which the silicone compound (D) was not included, the wettability of the curable composition to the copper-clad substrate (base material) was insufficient, or the leveling property was deteriorated.
Claims (7)
（Ｂ）光重合開始剤と、
（Ｃ）エポキシ樹脂と、
（Ｄ）シリコーン化合物と、
（Ｅ）親水性シリカと、
（Ｆ）有機揺変剤と、
を含み、
（Ｆ）有機揺変剤がポリヒドロキシカルボン酸エステルであり、
（Ｄ）シリコーン化合物が、シリコーン系表面調整剤としてのポリジメチルシロキサン又はポリジメチルシロキサンを基本構造とする誘導体であることを特徴とする硬化性組成物。 (A) an alkali-soluble resin;
(B) a photopolymerization initiator;
(C) an epoxy resin;
(D) a silicone compound;
(E) hydrophilic silica;
(F) an organic thixotropic agent;
including;
(F) the organic thixotropic agent is a polyhydroxycarboxylic acid ester,
(D) A curable composition characterized in that the silicone compound is polydimethylsiloxane or a derivative having polydimethylsiloxane as a basic structure as a silicone-based surface conditioner.
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| JP2005195943A (en) | 2004-01-08 | 2005-07-21 | Taiyo Ink Mfg Ltd | Alkali developable photosensitive resin composition and printed wiring board using the same |
| JP2005241977A (en) | 2004-02-26 | 2005-09-08 | Taiyo Ink Mfg Ltd | Photosetting/thermosetting resin composition and printed wiring board using the same |
| JP2013156506A (en) | 2012-01-31 | 2013-08-15 | Taiyo Ink Mfg Ltd | Photosensitive resin composition and printed wiring board |
| JP2018173609A (en) | 2017-03-31 | 2018-11-08 | 太陽インキ製造株式会社 | Curable resin composition, dry film, cured product, and printed wiring board |
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| JP2009194222A (en) * | 2008-02-15 | 2009-08-27 | Denki Kagaku Kogyo Kk | White alkali-developable photocurable and thermosetting solder resist composition, and metal-base circuit substrate using the same |
| JP6171573B2 (en) * | 2013-05-29 | 2017-08-02 | 東洋インキＳｃホールディングス株式会社 | Photosensitive resin composition and cured film |
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| JP2005195943A (en) | 2004-01-08 | 2005-07-21 | Taiyo Ink Mfg Ltd | Alkali developable photosensitive resin composition and printed wiring board using the same |
| JP2005241977A (en) | 2004-02-26 | 2005-09-08 | Taiyo Ink Mfg Ltd | Photosetting/thermosetting resin composition and printed wiring board using the same |
| JP2013156506A (en) | 2012-01-31 | 2013-08-15 | Taiyo Ink Mfg Ltd | Photosensitive resin composition and printed wiring board |
| JP2018173609A (en) | 2017-03-31 | 2018-11-08 | 太陽インキ製造株式会社 | Curable resin composition, dry film, cured product, and printed wiring board |
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