TWI825246B - Hardening compositions, dry films, hardened materials and electronic parts - Google Patents
Hardening compositions, dry films, hardened materials and electronic parts Download PDFInfo
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- TWI825246B TWI825246B TW108146092A TW108146092A TWI825246B TW I825246 B TWI825246 B TW I825246B TW 108146092 A TW108146092 A TW 108146092A TW 108146092 A TW108146092 A TW 108146092A TW I825246 B TWI825246 B TW I825246B
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- 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)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Materials For Photolithography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
本發明提供含有親水性二氧化矽、聚矽氧系表面調整劑,並且焊接性良好且消除了二氧化矽凝集・沉澱問題之硬化性組成物、乾膜、硬化物及電子零件。 本發明之硬化性組成物包含(A)鹼可溶性樹脂,(B)光聚合起始劑,(C)環氧樹脂,(D)聚矽氧化合物,(E)親水性二氧化矽,及(F)有機搖變劑。藉此,消除了硬化性組成物內之親水性二氧化矽凝集、沉澱的問題,於基材上塗佈硬化性組成物時,藉由(D)聚矽氧化合物維持對基材之溼潤性,同時提高助焊劑對於所得硬化物之溼潤性,因此將硬化物作為防焊劑使用時,可獲得焊接性之提高效果。 The present invention provides curable compositions, dry films, cured products, and electronic parts that contain hydrophilic silica and polysiloxane-based surface conditioners, have good weldability, and eliminate problems of silica aggregation and precipitation. The curable composition of the present invention includes (A) alkali-soluble resin, (B) photopolymerization initiator, (C) epoxy resin, (D) polysiloxy compound, (E) hydrophilic silica, and ( F) Organic thixotropic agent. This eliminates the problem of aggregation and precipitation of hydrophilic silica in the curable composition. When the curable composition is coated on the substrate, the (D) polysiloxane compound maintains the wettability to the substrate. , and at the same time improves the wettability of the flux to the obtained hardened product, so when the hardened product is used as a solder resist, the weldability improvement effect can be obtained.
Description
本發明有關硬化性組成物、乾膜、硬化物及電子零件,尤其有關鹼可顯像之硬化性組成物、其乾膜、其硬化物及具備其硬化物之電子零件。The present invention relates to curable compositions, dry films, cured materials, and electronic components, and in particular to alkali-developable curable compositions, dry films thereof, cured materials thereof, and electronic components having cured materials thereof.
過去以來,民生用印刷基板或產業用印刷配線板之防焊劑中,基於高精度、高密度之觀點,係使用於紫外線照射後,藉由顯像而形成圖像,藉由熱及/或光照射而加工硬化(正式硬化)之液狀顯像型防焊劑中,液狀顯像型防焊劑中,基於對環境問題之顧慮,主流係使用鹼水溶液作為顯像液之鹼顯像型光防焊劑。In the past, from the viewpoint of high precision and high density, solder resists for consumer printed circuit boards or industrial printed wiring boards were used to form images through development after ultraviolet irradiation, using heat and/or light. Among the liquid developing type solder resists that are work-hardened (formally hardened) by irradiation, among the liquid developing type solder resists, due to concerns about environmental issues, the mainstream is the alkali developing type photoresist that uses an alkali aqueous solution as the developer. Flux.
一般,用以於基板上形成光防焊劑而塗佈於基板之防焊劑組成物中,為了提高防焊劑組成物對基板之溼潤性,且為了提高其塗膜之調平性(平坦性),而添加聚矽氧系表面調整劑。Generally, a solder resist composition is used to form a photo-solder resist on a substrate and is coated on the substrate. In order to improve the wettability of the solder resist composition to the substrate and to improve the leveling (flatness) of the coating film, And add polysiloxane surface conditioner.
於基板上形成光防焊劑後,藉由焊接進行零件對基板之安裝,但由於熔融焊料對基板之溼潤性低,故為了提高溼潤性(焊接面之乾淨化與抗氧化)而於包含防焊劑面之基板面全面塗佈助焊劑。After the photo-solder resist is formed on the substrate, the parts are mounted on the substrate by soldering. However, since the wettability of the molten solder to the substrate is low, the solder resist is included in order to improve the wettability (cleaning and anti-oxidation of the soldering surface). The entire surface of the substrate is coated with flux.
因此,藉由本發明人等之檢討,了解若於基板上形成之防焊劑中包含聚矽氧系表面調整劑,則會發生助焊劑不沾著於基板而使焊接性降低之缺點。Therefore, through examination by the present inventors, it was found that if the solder resist formed on the substrate contains a polysiloxane-based surface conditioner, the flux will not adhere to the substrate and the solderability will be reduced.
另一方面,已充分知悉為了強化防焊劑之剛性及抑制防焊劑組成物之硬化收縮而於防焊劑組成物中添加作為無機填充劑之二氧化矽。On the other hand, it is well known that silicon dioxide as an inorganic filler is added to the solder resist composition in order to enhance the rigidity of the solder resist and suppress the hardening shrinkage of the solder resist composition.
專利文獻1中,其實施例中,作為上述先前技術之防焊劑組成物,揭示有含有聚矽氧系表面調整劑之鹼顯像型光硬化性、熱硬化性防焊劑組成物,作為比較例2,則揭示含有未實施表面改質處理之熔融球狀二氧化矽作為無機粉末之鹼顯像型光硬化性、熱硬化性防焊劑組成物。 [先前技術文獻] [專利文獻]Patent Document 1 discloses, as a comparative example, an alkali-developing photo-curable and thermosetting solder resist composition containing a polysiloxane-based surface conditioner as a solder resist composition of the above-mentioned prior art in its Examples. 2, discloses an alkali-developable photo-curable and thermo-curable solder resist composition containing molten spherical silica without surface modification treatment as an inorganic powder. [Prior technical literature] [Patent Document]
[專利文獻1] 日本特開2009-194222號公報[Patent Document 1] Japanese Patent Application Publication No. 2009-194222
[發明欲解決之課題][Problem to be solved by the invention]
依據專利文獻1之實施例的含有聚矽氧系表面調整劑之鹼顯像型光硬化性、熱硬化性防焊劑組成物,雖提高防焊劑組成物對基板之溼潤性,但由於所形成之防焊劑會使助焊劑不沾著,故會使焊接性降低。According to the embodiment of Patent Document 1, the alkali-developing photo-curable and thermosetting solder resist composition containing a polysiloxane-based surface conditioner improves the wettability of the solder resist composition to the substrate, but due to the The solder resist will prevent the flux from sticking, so it will reduce the solderability.
又,依據專利文獻1之比較例2之鹼顯像型光硬化性、熱硬化性防焊劑組成物,由於所添加之二氧化矽並未實施表面改質處理而為親水性,因此有發生就此凝集、沉澱之問題之虞,而例如必須將表面改質為疏水性,而消除凝集、沉澱問題。又,比較例2之鹼顯像型光硬化性、熱硬化性防焊劑組成物,由於未添加聚矽氧系表面調整劑,因此亦無法改善防焊劑組成物對基板之溼潤性。Furthermore, according to the alkali-developable photocurable and thermosetting solder resist composition of Comparative Example 2 of Patent Document 1, the added silicon dioxide has not been subjected to surface modification treatment and is hydrophilic. Therefore, this may occur. There is a risk of aggregation and precipitation problems. For example, the surface must be modified to be hydrophobic to eliminate aggregation and precipitation problems. In addition, since the alkali-developing photocurable and thermosetting solder resist composition of Comparative Example 2 does not add a polysiloxane-based surface conditioner, the wettability of the solder resist composition to the substrate cannot be improved.
本發明係鑒於上述課題而完成者,其目的在於提供含有親水性二氧化矽、聚矽氧系表面調整劑,並且焊接性良好且消除了二氧化矽凝集、沉澱問題之硬化性組成物、乾膜、硬化物及電子零件。 [用以解決課題之手段]The present invention was made in view of the above-mentioned problems, and its object is to provide a curable composition, a dry composition containing hydrophilic silica and a polysiloxane-based surface conditioner, which has good weldability and eliminates the problems of silica aggregation and precipitation. Films, hardened materials and electronic parts. [Means used to solve problems]
本發明人等為了達成上述目的而進行積極檢討。其結果意外地發現調配聚矽氧化合物、親水性二氧化矽及有機搖變劑時,可維持貼銅基板與防焊劑組成物之溼潤性,且消除了親水性二氧化矽之凝集、沉澱問題及起因於聚矽氧化合物之助焊劑不沾著之問題,因而完成本發明。In order to achieve the above-mentioned object, the present inventors conducted active examination. As a result, it was unexpectedly found that when polysiloxane, hydrophilic silica and organic thixotrope are formulated, the wettability of the copper-clad substrate and solder resist composition can be maintained, and the problems of aggregation and precipitation of hydrophilic silica can be eliminated. And the problem of flux non-adhesion caused by polysiloxane compounds led to the completion of the present invention.
亦即,發現本發明之上述目的可藉由下述硬化組成物而達成,該硬化性組成物之特徵係包含: (A)鹼可溶性樹脂, (B)光聚合起始劑, (C)環氧樹脂, (D)聚矽氧化合物, (E)親水性二氧化矽,及 (F)有機搖變劑。That is, it is found that the above object of the present invention can be achieved by the following curable composition. The characteristics of the curable composition include: (A) Alkali-soluble resin, (B) Photopolymerization initiator, (C) Epoxy resin, (D)Polysilicone compound, (E) Hydrophilic silica, and (F) Organic thixotropic agent.
本發明之硬化性組成物進而較佳(E)親水性二氧化矽之中位直徑D50為0.2μm以上2.0μm以下。In the curable composition of the present invention, it is further preferred that (E) the median diameter D50 of the hydrophilic silica is 0.2 μm or more and 2.0 μm or less.
又,較佳(F)有機搖變劑之量,相對於(E)親水性二氧化矽100質量份,為0.01質量份以上15質量份以下,且相對於(D)聚矽氧化合物2質量份,為0.05質量份以上。Furthermore, the preferred amount of (F) organic thixotrope is 0.01 to 15 parts by mass relative to 100 parts by mass of (E) hydrophilic silica, and 2 mass parts to (D) polysiloxy compound. parts, more than 0.05 parts by mass.
而且,較佳進而包含(G)抗氧化劑。Moreover, it is preferable to further contain (G) antioxidant.
又,本發明之上述目的可藉由乾膜、硬化物及電子零件而達成,該乾膜之特徵係將本發明之硬化性組成物塗佈於載體膜上並乾燥而獲得, 該硬化物之特徵係將本發明之硬化性組成物塗佈於基材上並乾燥所得之乾燥塗膜硬化而獲得,或將前述硬化性組成物塗佈於載體膜上並乾燥所得之乾膜層合於基材上而成之塗膜硬化而獲得,及 該電子零件之特徵係具備該硬化物。 [發明效果]In addition, the above object of the present invention can be achieved by a dry film, a cured product and an electronic component. The dry film is characterized by being obtained by coating the curable composition of the present invention on a carrier film and drying it. The characteristics of the cured product are obtained by applying the curable composition of the present invention on a base material and drying the resulting dry coating film, or by coating the aforementioned curable composition on a carrier film and drying the resulting dry film. Obtained by hardening the coating film laminated on the substrate, and The electronic component is characterized by having the hardened material. [Effects of the invention]
依據本發明,可消除硬化性組成物內之親水性二氧化矽之凝集、沉澱問題,於將硬化性組成物塗佈於基材時,可藉由(D)聚矽氧化合物維持對基材之溼潤性,同時可提高助焊劑對於所得硬化物之溼潤性,故將硬化物作為防焊劑使用時,獲得焊接性提高效果。According to the present invention, the problem of aggregation and precipitation of hydrophilic silica in the curable composition can be eliminated. When the curable composition is coated on the substrate, the (D) polysiloxane compound can maintain contact with the substrate. The wettability of the flux can also improve the wettability of the hardened product. Therefore, when the hardened product is used as a solder resist, the solderability improvement effect is obtained.
<硬化性組成物><Cureable composition>
本發明之硬化性組成物包含: (A)鹼可溶性樹脂, (B)光聚合起始劑, (C)環氧樹脂, (D)聚矽氧化合物, (E)親水性二氧化矽,及 (F)有機搖變劑。The curable composition of the present invention contains: (A) Alkali-soluble resin, (B) Photopolymerization initiator, (C) Epoxy resin, (D)Polysilicone compound, (E) Hydrophilic silica, and (F) Organic thixotropic agent.
[(A)鹼可溶性樹脂] 鹼可溶性樹脂係可使硬化性組成物溶解於鹼顯像液,亦即可藉鹼顯像之樹脂。[(A) Alkali-soluble resin] Alkali-soluble resin is a resin that can dissolve the curable composition in an alkali developing solution, that is, it can be developed by alkali.
作為鹼可溶性樹脂,較佳使用含羧基之樹脂或酚樹脂。尤其使用含羧基之樹脂時就顯像性方面而言較佳。As the alkali-soluble resin, a carboxyl group-containing resin or a phenol resin is preferably used. In particular, the use of a carboxyl group-containing resin is preferable in terms of developability.
作為含羧基之樹脂可使用分子中具有羧基,進而不具有乙烯性不飽和基(非感光性)或具有乙烯性不飽和基(感光性)之以往習知之各種含羧基之樹脂。As the carboxyl group-containing resin, various conventionally known carboxyl group-containing resins may be used that have a carboxyl group in the molecule and do not have an ethylenically unsaturated group (non-photosensitive) or have an ethylenically unsaturated group (photosensitive).
本發明中,所謂乙烯性不飽和基為具有乙烯性不飽和鍵之取代基,舉例為係如乙烯基、(甲基)丙烯醯基,基於反應性之觀點,較佳為(甲基)丙烯醯基。此處,所謂(甲基)丙烯醯基係丙烯醯基及甲基丙烯醯基總稱之用語。In the present invention, the so-called ethylenically unsaturated group is a substituent having an ethylenically unsaturated bond. Examples thereof include vinyl and (meth)acrylyl. From the viewpoint of reactivity, (meth)acryl is preferred. Jiji. Here, (meth)acrylyl group is a general term for acrylyl group and methacrylyl group.
作為不具有乙烯性不飽和基之含羧基之樹脂具體力可舉例如下之化合物(寡聚物及聚合物之任一者)。Specific examples of the carboxyl group-containing resin having no ethylenically unsaturated group include the following compounds (any of oligomers and polymers).
(1) 藉由使脂肪族二異氰酸酯、分支脂肪族二異氰酸酯、脂環式二異氰酸酯、芳香族二異氰酸酯等之二異氰酸酯、與二羥甲基丙酸、二羥甲基丁酸等之含羧基之二醇化合物、聚碳酸酯系多元醇、聚醚系多元醇、聚酯系多元醇、聚烯烴系多元醇、雙酚A系環氧烷加成物二醇、具有酚性羥基及醇性羥基之化合物等之二醇化合物之聚加成反應所得之含羧基之胺基甲酸酯樹脂。(1) By combining diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, etc., and dimethylol propionic acid, dimethylol butyric acid, etc. containing carboxyl groups Diol compounds, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, bisphenol A alkylene oxide adduct diols, with phenolic hydroxyl and alcohol properties Carboxyl group-containing urethane resin obtained by polyaddition reaction of glycol compounds such as hydroxyl compounds.
(2) 藉由二異氰酸酯與含羧基之二醇化合物之聚加成反應所得之含羧基之胺基甲酸酯樹脂。(2) Carboxyl group-containing urethane resin obtained by the polyaddition reaction of diisocyanate and carboxyl group-containing diol compound.
(3) 藉由使(甲基)丙烯酸等之不飽和羧酸與苯乙烯、α-甲基苯乙烯、(甲基)丙烯酸低級烷酯、異丁烯等之含不飽和基之化合物之共聚合而得之含羧基之樹脂。(3) By copolymerizing unsaturated carboxylic acids such as (meth)acrylic acid and unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene, etc. Resins containing carboxyl groups are obtained.
(4) 使2官能環氧樹脂或2官能氧雜環丁烷樹脂與己二酸、鄰苯二甲酸、六氫鄰苯二甲酸等之二羧酸反應,對產生之羥基加成鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐等之二元酸酐而成之含羧基之聚酯樹脂。(4) React bifunctional epoxy resin or bifunctional oxetane resin with dicarboxylic acids such as adipic acid, phthalic acid, hexahydrophthalic acid, and add phthalic acid to the generated hydroxyl group. Carboxyl-containing polyester resin made from dibasic acid anhydrides such as formic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.
(5)使環氧樹脂或氧雜環丁烷樹脂開環,對生成之羥基反應多元酸酐而得之含羧基之樹脂。(5) A carboxyl group-containing resin obtained by ring-opening an epoxy resin or an oxetane resin and reacting a polybasic acid anhydride with the generated hydroxyl group.
(6) 對使1分子中具有複數酚性羥基之化合物亦即多酚化合物與環氧乙烷、環氧丙烷等之環氧烷反應而得之多元醇數之等之反應生成物與多元酸酐反應而得之含羧基之樹脂。(6) Reaction products and polybasic acid anhydrides equal to the number of polyhydric alcohols obtained by reacting a polyphenolic compound with a plurality of phenolic hydroxyl groups in one molecule and an alkylene oxide such as ethylene oxide or propylene oxide. Carboxyl-containing resin obtained by reaction.
又,作為具有乙烯性不飽和基之含羧基之樹脂具體例,可舉例如以下之化合物(寡聚物及聚合物之任一者)。又,含羧基之樹脂中之乙烯性不飽和鍵較佳為丙烯酸或甲基丙烯酸或源自該等之衍生物。Specific examples of the carboxyl group-containing resin having an ethylenically unsaturated group include the following compounds (any of oligomers and polymers). Furthermore, the ethylenically unsaturated bond in the carboxyl group-containing resin is preferably acrylic acid or methacrylic acid or a derivative thereof.
(7) 於脂肪族二異氰酸酯、分支脂肪族二異氰酸酯、脂環式二異氰酸酯、芳香族二異氰酸酯等之二異氰酸酯與二羥甲基丙酸、二羥甲基丁酸等之含羧基之二醇化合物、聚碳酸酯系多元醇、聚醚系多元醇、聚酯系多元醇、聚烯烴系多元醇、丙烯酸系多元醇、雙酚A系環氧烷加成物二醇、具有酚性羥基及醇性羥基之化合物等之二醇化合物之聚加成反應所得之含羧基之感光性胺基甲酸酯樹脂。(7) Diols containing carboxyl groups such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, etc. and dimethylol propionic acid, dimethylol butyric acid, etc. Compounds, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, phenolic hydroxyl groups and Photosensitive urethane resin containing carboxyl groups obtained by the polyaddition reaction of diol compounds such as alcoholic hydroxyl compounds.
(8) 使二異氰酸酯與雙酚A型環氧樹脂、氫化雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、聯二甲酚型環氧樹脂、聯酚型環氧樹脂等之2官能環氧樹脂之(甲基)丙烯酸酯或其部分酸酐改質物、含羧基之二醇化合物之聚加成反應所得之含羧基之感光性聚胺基甲酸酯樹脂。(8) Mix diisocyanate with bisphenol A-type epoxy resin, hydrogenated bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bixylenol-type epoxy resin, Photosensitive polyurethane containing carboxyl groups obtained by the polyaddition reaction of (meth)acrylate or partial acid anhydride modifications of bifunctional epoxy resins such as phenolic epoxy resins and carboxyl group-containing glycol compounds resin.
(9) 於上述(7)或(8)之樹脂之合成中,添加(甲基)丙烯酸羥基烷酯等之分子中具有1個羥基與1個以上(甲基)丙烯醯基之化合物,進行末端(甲基)丙烯酸化之含羧基之感光性胺基甲酸酯樹脂。(9) In the synthesis of the resin in the above (7) or (8), a compound having one hydroxyl group and one or more (meth)acrylyl groups in the molecule, such as hydroxyalkyl (meth)acrylate, is added. Photosensitive urethane resin containing carboxyl groups with terminal (meth)acrylation.
(10) 上述(8)或(9)之樹脂合成中,添加異佛酮二異氰酸酯與季戊四醇三丙烯酸酯之等莫耳反應物等之分子內具有1個異氰酸酯基與1個以上(甲基)丙烯醯基之化合物之末端(甲基)丙烯酸化之含羧基之感光性胺基甲酸酯樹脂。(10) In the resin synthesis of the above (8) or (9), molar reactants such as isophorone diisocyanate and pentaerythritol triacrylate are added which have one isocyanate group and more than one (methyl) group in the molecule It is a carboxyl-containing photosensitive urethane resin with terminal (meth)acrylation of acrylic compounds.
(11) 使2官能或其以上之多官能(固形)環氧樹脂與(甲基)丙烯酸反應,而於側鏈存在之羥基加成二元酸酐之含羧基之感光性樹脂。(11) A carboxyl group-containing photosensitive resin in which a bifunctional or higher polyfunctional (solid) epoxy resin is reacted with (meth)acrylic acid to add a dibasic acid anhydride to the hydroxyl group present in the side chain.
(12)使2官能(固形)環氧樹脂之羥基進而以表氯醇環氧化之多官能環氧樹脂與(甲基)丙烯酸反應,而於產生之羥基加成二元酸酐之含羧基之感光性樹脂。(12) The hydroxyl group of a bifunctional (solid) epoxy resin is reacted with a polyfunctional epoxy resin epoxidized with epichlorohydrin and (meth)acrylic acid, and the carboxyl group-containing dibasic acid anhydride is added to the generated hydroxyl group. Sex resin.
(13) 使2官能氧雜環丁烷樹脂與己二酸、鄰苯二甲酸、六氫鄰苯二甲酸等之二羧酸反應,對產生之1級羥基加成鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐等之二元酸酐之含羧基之聚酯感光性樹脂。(13) React bifunctional oxetane resin with dicarboxylic acids such as adipic acid, phthalic acid, and hexahydrophthalic acid, and add phthalic anhydride and tetrahydrophthalic anhydride to the resulting primary hydroxyl group. Polyester photosensitive resin containing carboxyl groups of dibasic acid anhydrides such as hydrogen phthalic anhydride and hexahydrophthalic anhydride.
(14) 使1分子中具有複數酚性羥基之化合物亦即多酚化合物與環氧乙烷、環氧丙烷等之環氧烷反應所得之多元醇樹脂等之反應生成物與(甲基)丙烯酸等之含不飽和基之單羧酸反應,所得之反應生成物與多元酸酐反應而得之含羧基之感光性樹脂。(14) Reaction products of polyol resins, etc. obtained by reacting polyphenol compounds, which are compounds having plural phenolic hydroxyl groups in one molecule, and alkylene oxides such as ethylene oxide and propylene oxide, and (meth)acrylic acid The carboxyl group-containing photosensitive resin is obtained by reacting monocarboxylic acids containing unsaturated groups, and the reaction product obtained reacts with polybasic acid anhydrides.
(15) 使1分子中具有複數酚性羥基之化合物與碳酸伸乙酯、碳酸伸丙酯等之環狀碳酸酯化合物反應所得之反應生成物與含不飽和基之單羧酸反應,所得之反應生成物與多元酸酐反應而得之含羧基之感光性樹脂。(15) The reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethyl carbonate or propyl carbonate is reacted with a monocarboxylic acid containing an unsaturated group. A carboxyl-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.
(16) 於前述(7)~(15)之樹脂進而加成1分子內具有1個環氧基與1個以上(甲基)丙烯醯基之化合物而成之含羧基之感光性樹脂。(16) A carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth)acrylyl groups per molecule to the resins of the above (7) to (15).
該等感光性含羧基之樹脂亦可使用作為(7)~(16)敘述以外者,可單獨使用1種,亦可混合複數種使用。尤其於含羧基之樹脂中較佳為具有芳香環之樹脂。These photosensitive carboxyl group-containing resins can also be used other than those described in (7) to (16). One type can be used alone, or a plurality of types can be mixed and used. In particular, resins having an aromatic ring are preferred among resins containing carboxyl groups.
上述含羧基之樹脂無論是感光性、非感光性,均可說以下之情況。亦即,由於於主鏈・聚合物之側鏈具有多數羧基,因此可藉由稀鹼水溶液顯像。The following can be said for the above-mentioned carboxyl group-containing resin regardless of whether it is photosensitive or non-photosensitive. That is, since it has many carboxyl groups in the main chain and side chains of the polymer, it can be developed with a dilute alkali aqueous solution.
含羧基之樹脂的酸價較好為40~200mgKOH/g 之範圍,更好為45~120mgKOH/g之範圍。含羧基之樹脂的酸價為此等範圍內時,鹼顯像變容易,可抑制顯像液對曝光部之溶解,不會使線過於變細,不會陰顯像液而溶解剝離可描繪正常圖型。The acid value of the carboxyl group-containing resin is preferably in the range of 40 to 200 mgKOH/g, more preferably in the range of 45 to 120 mgKOH/g. When the acid value of the carboxyl-containing resin is within this range, alkali development becomes easier, the dissolution of the exposed part by the developing solution can be suppressed, the lines will not be too thin, and the developing solution will not dissolve and peel, and normal drawings can be achieved. graphics.
又,上述之含羧基之樹脂的重量平均分子量係隨樹脂骨架而異,但較佳為2,000以上150,000以下,更佳為5,000以上100,000以下之範圍。重量平均分子量若為此等範圍內,則無觸黏性能良好,曝光後之塗膜耐濕性良好,顯像性或解像性、儲存安定性優異。 此等含羧基之樹脂的調配量,於硬化性組成物(固形分)中,為20質量%以上80質量%以下,較佳30質量%以上70質量%以下之範圍為適當。含羧基之樹脂的調配量若為此等範圍內,塗膜強度不會降低,不會引起增黏或作業性降低。In addition, the weight average molecular weight of the above-mentioned carboxyl group-containing resin varies depending on the resin skeleton, but is preferably in the range of 2,000 to 150,000, and more preferably 5,000 to 100,000. If the weight average molecular weight is within this range, the non-tackiness properties will be good, the moisture resistance of the coating film after exposure will be good, and the developability, resolution, and storage stability will be excellent. The compounding amount of these carboxyl group-containing resins in the curable composition (solid content) is in the range of 20 mass% or more and 80 mass% or less, preferably 30 mass% or more and 70 mass% or less. If the compounding amount of the carboxyl group-containing resin is within this range, the coating film strength will not be reduced, and the viscosity will not be increased or the workability will be reduced.
又,本發明中,作為(A)鹼可溶性樹脂,可使用感光性含羧基之樹脂及不具有感光性之含羧基之樹脂之任一者,亦可混合該等而使用。Furthermore, in the present invention, as (A) the alkali-soluble resin, either a photosensitive carboxyl group-containing resin or a non-photosensitive carboxyl group-containing resin can be used, or these can be mixed and used.
作為酚樹脂為具有酚性羥基之化合物,舉例為例如具有聯苯骨架或伸苯基骨架或其兩者骨架之化合物,或使用含酚性羥基之化合物例如苯酚、鄰甲酚、對甲酚、間甲酚、2,3-二甲酚、2,4-二甲酚、2,5-二甲酚、2,6-二甲酚、3,4-二甲酚、3,5-二甲酚、兒茶酚、間苯二酚、對苯二酚、甲基對苯二酚、2,6-二甲基對苯二酚、三甲基對苯二酚、焦棓酚(pyrogallol)、間苯三酚等合成而成之具有各種骨架之酚樹脂。The phenol resin is a compound having a phenolic hydroxyl group, for example, a compound having a biphenyl skeleton or a phenylene skeleton or both skeletons, or a compound containing a phenolic hydroxyl group such as phenol, o-cresol, p-cresol, m-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol Phenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, Phenolic resins with various skeletons synthesized from phloroglucinol and others.
可使用例如酚酚醛清漆樹脂、烷基酚酚醛清漆樹脂、雙酚A酚醛清漆樹脂、二環戊二烯型酚樹脂、Xylok型酚樹脂、萜烯改質酚樹脂、聚乙烯酚類、雙酚F、雙酚S型酚樹脂、聚-對-羥基苯乙烯、萘酚與醛類之縮合物、二羥基萘與醛類之縮合物等之公知慣用之酚樹脂。For example, phenol novolak resin, alkylphenol novolac resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene modified phenol resin, polyvinyl phenols, bisphenol can be used. F. Bisphenol S type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes, etc. are well-known and commonly used phenol resins.
該等可單獨使用或組合2種以上使用。These can be used individually or in combination of 2 or more types.
作為該酚樹脂之市售品可列舉為例如HF-1M(明和化成公司製)、Phenolite TD-2090、Phenolite TD-2131(DIC公司製)、Besmol CZ-256-A(DIC公司製)、Shonol BRG-555、Shonol BRG-556(AICA公司製)、CGR-951(丸善石油公司製)、或聚乙烯酚之CST70、CST90、S-1P、S-2P(丸善石油公司製)等。該等酚樹脂可單獨或組合2種以上使用。Examples of commercially available phenolic resins include HF-1M (manufactured by Meiwa Kasei Co., Ltd.), Phenolite TD-2090, Phenolite TD-2131 (manufactured by DIC Co., Ltd.), Besmol CZ-256-A (manufactured by DIC Co., Ltd.), Shonol BRG-555, Shonol BRG-556 (manufactured by AICA), CGR-951 (manufactured by Maruzen Oil Co., Ltd.), or polyvinyl phenol CST70, CST90, S-1P, S-2P (manufactured by Maruzen Oil Co., Ltd.), etc. These phenolic resins can be used individually or in combination of 2 or more types.
[(B)光聚合起始劑] (B)光聚合起始劑係用以藉由能量線之照射而開始乙烯性不飽和基之自由基聚合而添加。[(B) Photopolymerization initiator] (B) The photopolymerization initiator is added to start radical polymerization of ethylenically unsaturated groups by irradiation with energy rays.
(B)光聚合起始劑舉例為例如苯偶因、苯偶因甲醚、苯偶因乙醚、苯偶因異丙醚等之苯偶因與苯偶因烷醚類;苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、1,1-二氯苯乙酮等之苯乙酮類;2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉丙烷-1-酮、2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮-1、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮等之胺基苯烷酮類;2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、1-氯蒽醌等之蒽醌類;2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2-氯噻噸酮、2,4-二異丙基噻噸酮等之噻噸酮類;苯乙酮二甲基縮醛、苄基二甲基縮醛等之縮醛類;4,4’-雙(二乙胺基)二苯甲酮等之二苯甲酮類;(2,6-二甲氧基苯甲醯基)-2,4,4-戊基氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦、2,4,6-三甲基苯甲醯基苯基次膦酸乙酯等之氧化膦類;1,2-辛二酮、1-[4-(苯硫基)-,2-(O-苯甲醯基肟)]、乙酮、1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯肟)等之肟酯類;各種過氧化物類、二茂鈦系起始劑等。該等亦可與如N,N-二甲胺基苯甲酸乙酯、N,N-二甲胺基苯甲酸異戊酯、4-二甲胺基苯甲酸戊酯、三乙胺、三乙醇胺等之三級胺類之光增感劑等併用。該等光聚合起始劑可單獨或可組合2種以上使用。(B) Examples of photopolymerization initiators include benzoin and benzoyl alkyl ethers such as benzoin, benzoin methyl ether, benzoin diethyl ether, benzoin isopropyl ether, etc.; acetophenone, 2 ,2-Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, Acetophenones such as 1,1-dichloroacetophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl- 2-Dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1- Aminophenanones such as [4-(4-morpholinyl)phenyl]-1-butanone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, Anthraquinones such as 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone Thioxanthones such as ketones; acetals such as acetophenone dimethyl acetal, benzyl dimethyl acetal, etc.; diphenyls such as 4,4'-bis(diethylamino)benzophenone etc. Ketones; (2,6-dimethoxybenzyl)-2,4,4-pentylphosphine oxide, bis(2,4,6-trimethylbenzyl)-phenyl oxide Phosphines, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphinate, etc.; 1,2 -Octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl) Oxime esters such as acyl)-9H-carbazol-3-yl]-,1-(O-acetyl oxime); various peroxides, titanocene-based starters, etc. These can also be combined with N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, 4-dimethylaminobenzoic acid amyl ester, triethylamine, triethanolamine Use in combination with tertiary amines, photosensitizers, etc. These photopolymerization initiators may be used individually or in combination of 2 or more types.
(B)光聚合起始劑之調配量,於本發明之硬化性組成物中,相對於(A)鹼可溶性樹脂100質量份(固形分)以0.01質量份以上30質量份以下之範圍,較佳以0.5質量份以上20質量份以下之範圍調配。(B) The amount of the photopolymerization initiator in the curable composition of the present invention is in the range of 0.01 to 30 parts by mass relative to 100 parts by mass (solid content) of the alkali-soluble resin (A). It is best to prepare it within the range of 0.5 parts by mass or more and 20 parts by mass or less.
[(C)環氧樹脂] (C)環氧樹脂係為了使本發明的硬化性組成物熱硬化而添加之化合物。[(C)Epoxy resin] (C) The epoxy resin is a compound added in order to thermally harden the curable composition of the present invention.
(C)環氧樹脂可使用1分子中具有至少2個環氧基之習知慣用多官能環氧樹脂。作為(C)環氧樹脂可舉例為例如三菱化學公司製之jER828、jER834、jER1001、jER1004,DIC公司製之EPICLON 840、EPICLON 850、EPICLON 850-S、EPICLON 1050、EPICLON 2055,東都化成公司製之EPOTOT YD-011、YD-013、YD-127、YD-128,道化學公司製之D.E.R.317、D.E.R.331、D.E.R.661、D.E.R.664,住友化學工業公司製之Sumi-epoxy ESA-011、ESA-014、ELA-115、ELA-128等(均為商品名)之雙酚A型環氧樹脂;三菱化學公司製之jER YL903,DIC公司製之EPICLON 152、EPICLON 165,東都化成公司製之EPOTOT YDB-400、YDB-500,道化學公司製之D.E.R.542,住友化學工業公司製之Sumi-epoxy ESB-400、ESB-700等(均為商品名)之溴化環氧樹脂;三菱化學公司製之jER 152、jER 154,道化學公司製之D.E.N.431、D.E.N.438,DIC公司製之EPICLON N-730、EPICLON N-770、EPICLON N-865,東都化成公司製之EPOTOT YDCN-701、YDCN-704,日本化藥公司製之EPPN-201、EOCN-1025、EOCN-1020、EOCN-104S、RE-306、NC-3000,住友化學工業公司製之Sumi-epoxy ESCN-195X、ESCN-220,新日鐵化學公司製之YDCN-700-2、YDCN-700-3、YDCN-700-5、YDCN-700-7、YDCN-700-10、YDCN-704、YDCN-704A,DIC公司製之EPICLON N-680、EPICLON N-690、EPICLON N-695(均為商品名)等之酚醛清漆型環氧樹脂;DIC公司製之EPICLON 830,三菱化學公司製之jER 807,東都化成公司製之EPOTOT YDF-170、YDF-175、YDF-2004等(均為商品名)之雙酚F型環氧樹脂;東都化成公司製之EPOTOT ST-2004、ST-2007、ST-3000(商品名),三菱化學公司製之YX8034等之氫化雙酚A型環氧樹脂;三菱化學公司製之jER 604,東都化成公司製之EPOTOT YH-434;住友化學工業公司製之Sumi-epoxy ELM-120等(均為商品名)之縮水甘油胺型環氧樹脂;乙內醯脲型環氧樹脂;Dicel化學工業公司製之Celloxide 2021等(均為商品名)之脂環式環氧樹脂;三菱化學公司製之YL-933,日本化藥公司製之EPPN-501、EPPN-502等(均為商品名)之三羥基苯基甲烷型環氧樹脂;三菱化學公司製之YL-6056、YX-4000、YL-6121(均為商品名)等之雙二甲苯酚型或聯酚型環氧樹脂或該等之混合物;日本化藥公司製之EBPS-200,ADEKA公司製之EPX-30,DIC公司製之EXA-1514(商品名)等之雙酚S型環氧樹脂;三菱化學公司製之jER 157S(商品名)等之雙酚A酚醛清漆型環氧樹脂;三菱化學公司製之jER YL-931等(均為商品名)之四羥苯基乙烷型環氧樹脂;日本油脂公司製之Blenmer DGT等之二縮水甘油基苯二甲酸酯樹脂;日產化學工業公司製之TEPIC等(均為商品名)等之雜環式環氧樹脂;東都化成公司製之ZX-1063等之四縮水甘油基二甲苯醯基乙烷樹脂;新日鐵化學公司製之ESN-190、ESN-360,DIC公司製之HP-4032、EXA-4750、EXA-4700等之含萘基之環氧樹脂;DIC公司製之HP-7200、HP-7200H等之具有二環戊二烯骨架之環氧樹脂;日本油脂公司製之CP-50S、CP-50M等之縮水甘油基甲基丙烯酸酯共聚物系環氧樹脂;進而有環己基馬來醯亞胺與縮水甘油基甲基丙烯酸酯之共聚合環氧樹脂;CTBN改質環氧樹脂(例如東都化成公司製之YR-102、YR-450等)等,但並不限於該等。(C) As the epoxy resin, a commonly used polyfunctional epoxy resin having at least two epoxy groups per molecule can be used. Examples of the (C) epoxy resin include jER828, jER834, jER1001, and jER1004 manufactured by Mitsubishi Chemical Corporation, EPICLON 840, EPICLON 850, EPICLON 850-S, EPICLON 1050, and EPICLON 2055 manufactured by DIC Corporation, and Tōto Kasei Corporation. EPOTOT YD-011, YD-013, YD-127, YD-128, D.E.R.317, D.E.R.331, D.E.R.661, D.E.R.664 manufactured by Dow Chemical Co., Ltd., Sumi-epoxy ESA-011, ESA-014 manufactured by Sumitomo Chemical Industries, Ltd. , ELA-115, ELA-128 and other bisphenol A-type epoxy resins (all are trade names); jER YL903 made by Mitsubishi Chemical Company, EPICLON 152 and EPICLON 165 made by DIC Company, EPOTOT YDB- made by Toto Chemical Company 400, YDB-500, D.E.R.542 manufactured by Dow Chemical Company, brominated epoxy resins such as Sumi-epoxy ESB-400, ESB-700 (all trade names) manufactured by Sumitomo Chemical Industry Company; jER manufactured by Mitsubishi Chemical Company 152. jER 154, D.E.N.431, D.E.N.438 made by Dow Chemical Co., Ltd., EPICLON N-730, EPICLON N-770, EPICLON N-865 made by DIC Co., Ltd., EPOTOT YDCN-701, YDCN-704 made by Toto Chemical Co., Ltd., Japan EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000 manufactured by Chemical Co., Ltd., Sumi-epoxy ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Industries, Ltd., Nippon Steel Chemical YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704, YDCN-704A made by the company, EPICLON N-680 made by DIC company, Novolak-type epoxy resins such as EPICLON N-690 and EPICLON N-695 (all are trade names); EPICLON 830 manufactured by DIC Corporation, jER 807 manufactured by Mitsubishi Chemical Corporation, EPOTOT YDF-170 and YDF manufactured by Toto Kasei Corporation - Bisphenol F-type epoxy resins such as 175 and YDF-2004 (all are trade names); EPOTOT ST-2004, ST-2007, ST-3000 (trade names) made by Toto Chemical Co., Ltd., and YX8034 made by Mitsubishi Chemical Co., Ltd. Hydrogenated bisphenol A type epoxy resin; jER 604 manufactured by Mitsubishi Chemical Company, EPOTOT YH-434 manufactured by Toto Chemical Industry Company; Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Industry Company, etc. (all are trade names) Glyceryl amine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin such as Celloxide 2021 manufactured by Dicel Chemical Industry Co., Ltd. (all are trade names); YL-933 manufactured by Mitsubishi Chemical Co., Ltd., Japaneseized Trihydroxyphenylmethane type epoxy resins such as EPPN-501 and EPPN-502 (all are trade names) manufactured by pharmaceutical companies; YL-6056, YX-4000, YL-6121 (all are trade names) manufactured by Mitsubishi Chemical Corporation ) and other bisxylenol type or bisphenol type epoxy resins or mixtures thereof; EBPS-200 manufactured by Nippon Chemical Company, EPX-30 manufactured by ADEKA Company, EXA-1514 (trade name) manufactured by DIC Company Bisphenol S-type epoxy resins such as jER 157S (trade name) manufactured by Mitsubishi Chemical Corporation, bisphenol A novolak-type epoxy resins such as jER YL-931 manufactured by Mitsubishi Chemical Corporation (all trade names) Tetrahydroxyphenyl ethane type epoxy resin; diglycidyl phthalate resin such as Blenmer DGT manufactured by Nippon Oils and Fats Co., Ltd.; heterocyclic type such as TEPIC manufactured by Nissan Chemical Industry Co., Ltd. (all are trade names), etc. Epoxy resin; Tetraglycidylxylylethane resin such as ZX-1063 made by Toto Chemical Co., Ltd.; ESN-190 and ESN-360 made by Nippon Steel Chemical Co., Ltd., HP-4032 and EXA made by DIC Co., Ltd. -Naphthyl-containing epoxy resins such as 4750 and EXA-4700; epoxy resins with dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; CP-50S and Glycidyl methacrylate copolymers such as CP-50M are epoxy resins; furthermore, there are copolymerized epoxy resins of cyclohexyl maleimide and glycidyl methacrylate; CTBN modified epoxy resin ( For example, YR-102, YR-450, etc. manufactured by Toto Kasei Co., Ltd.), etc., but are not limited to these.
調配(C)環氧樹脂時,以相對於(A)鹼可溶性樹脂之羧酸當量,成為0.8環氧當量以上2.0環氧當量以下之量調配。此處所謂羧酸當量表示獲得羧基1莫耳量之必要(A)鹼可溶性樹脂之重量,單位為g/mol。又,所謂環氧當量表示獲得環氧基1莫耳量之必要(C)環氧樹脂之重量,單位為g/mol。(C)環氧樹脂之質量相對於(A)鹼可溶性樹脂之羧酸當量為0.8環氧當量以上2.0環氧當量以下。環氧當量於此等範圍內時,可獲得耐熱性或電性特性、龜裂耐性優異之硬化物。When compounding (C) epoxy resin, it is compounded in the quantity which becomes 0.8 or more epoxy equivalents and 2.0 or less epoxy equivalents with respect to the carboxylic acid equivalent of (A) alkali-soluble resin. The carboxylic acid equivalent here means the weight of the alkali-soluble resin (A) necessary to obtain 1 mole of carboxyl groups, and the unit is g/mol. In addition, the epoxy equivalent means the weight of (C) epoxy resin necessary to obtain 1 mole of epoxy groups, and the unit is g/mol. The mass of (C) the epoxy resin is 0.8 or more epoxy equivalents and 2.0 or less epoxy equivalents relative to the carboxylic acid equivalent of (A) the alkali-soluble resin. When the epoxy equivalent is within these ranges, a cured product with excellent heat resistance, electrical properties, and crack resistance can be obtained.
[(D)聚矽氧化合物] (D)聚矽氧化合物係為了提高本發明之硬化性組成物對於貼銅基板(基材)之溼潤性、抑制其不沾著、提高調平性而調配。[(D)Polysilicone compound] (D) The polysiloxane compound is formulated to improve the wettability of the curable composition of the present invention to the copper-clad substrate (base material), suppress non-adhesion, and improve leveling properties.
(D)聚矽氧化合物為聚二甲基矽氧烷或以聚二甲基矽氧烷為基本構造之衍生物,舉例為聚二甲基矽氧烷、聚醚改質聚二甲基矽氧烷、聚酯改質聚二甲基矽氧烷、聚酯改質聚甲基烷基矽氧烷、聚醚改質聚甲基烷基矽氧烷、芳烷基改質聚甲基烷基矽氧烷、聚醚改質矽氧烷、聚酯改質含羥基聚二甲基矽氧烷等。(D) The polysiloxane compound is polydimethylsiloxane or a derivative with polydimethylsiloxane as its basic structure, such as polydimethylsiloxane and polyether-modified polydimethylsiloxane. Oxane, polyester modified polydimethylsiloxane, polyester modified polymethylalkylsiloxane, polyether modified polymethylalkylsiloxane, aralkyl modified polymethane siloxane, polyether modified siloxane, polyester modified hydroxyl-containing polydimethylsiloxane, etc.
作為(D)聚矽氧化合物之市售品舉例為BYK(註冊商標)-300、BYK(註冊商標)-302、BYK(註冊商標)-306、BYK(註冊商標)-307、BYK(註冊商標)-310、BYK(註冊商標)-315N、BYK(註冊商標)-320、BYK(註冊商標)-322、BYK(註冊商標)-323、BYK(註冊商標)-325、BYK(註冊商標)-330、BYK(註冊商標)-331、BYK(註冊商標)-333、BYK(註冊商標)-342、BYK(註冊商標)-345、BYK(註冊商標)-346、BYK(註冊商標)-347、BYK(註冊商標)-348、BYK(註冊商標)-349、BYK(註冊商標)-370、BYK(註冊商標)-377、BYK(註冊商標)-378、BYK(註冊商標)-3455(以上為日本BYK公司製)。Examples of commercially available products of the (D) polysiloxane compound 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)-348, BYK (registered trademark)-349, BYK (registered trademark)-370, BYK (registered trademark)-377, BYK (registered trademark)-378, BYK (registered trademark)-3455 (the above are Made by BYK Corporation of Japan).
(D)聚矽氧化合物於本發明之硬化性組成物中,以相對於(A)鹼可溶性樹脂100質量份(固形分)為0.1質量份以上10質量份以下之範圍,較佳為1質量份以上5質量份以下之範圍調配。藉由使(D)聚矽氧化合物為0.1質量份以上10質量份以下之範圍,可確保硬化性組成物對於貼銅基板(基材)之溼潤性,使調平性良好,並且助焊劑對於硬化物之溼潤性亦成為良好。(D) The polysiloxy compound in the curable composition of the present invention is in the range of 0.1 to 10 parts by mass relative to 100 parts by mass (solid content) of the alkali-soluble resin (A), preferably 1 part by mass It is prepared within the range of more than 5 parts by mass and less than 5 parts by mass. By setting the (D) polysiloxane compound 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) can be ensured, the leveling properties can be improved, and the flux can be The wettability of the hardened material also becomes good.
[(E)親水性二氧化矽] (E)親水性二氧化矽係為了抑制本發明之硬化性組成物之硬化收縮及用以強化所得硬化物之剛性而添加。[(E) Hydrophilic silica] (E) Hydrophilic silica is added in order to suppress the curing shrinkage of the curable composition of the present invention and to enhance the rigidity of the obtained cured product.
本發明中,所謂(E)親水性二氧化矽係指未對其親水性表面實施附加疏水性有機基之表面處理的未處理二氧化矽,舉例為熔融二氧化矽、球狀二氧化矽、無定形二氧化矽、結晶性二氧化矽等。In the present invention, (E) hydrophilic silica refers to untreated silica that has not been subjected to surface treatment to add a hydrophobic organic group to its hydrophilic surface. Examples include fused silica, spherical silica, Amorphous silica, crystalline silica, etc.
又,所謂附加疏水性有機基之表面處理係指以例如具有乙烯性不飽和基(光硬化性反應基)、烷基等之疏水性有機基之偶合劑等處理(未處理之)親水性二氧化矽表面,該施以表面處理之氧化矽不包含於上述(E)親水性二氧化矽。In addition, the surface treatment of adding a hydrophobic organic group means treating (untreated) hydrophilic diodes with a coupling agent having a hydrophobic organic group such as an ethylenically unsaturated group (photocurable reactive group), an alkyl group, etc. The silicon oxide surface and the surface-treated silicon oxide are not included in the above-mentioned (E) hydrophilic silicon dioxide.
作為市售品,舉例為FB-15D、FB-105、FB-105X、FB-5SDX、SFP-20M、SFP-130MC(以上為電氣化學工業公司製)、EXCELICA(註冊商標)(德山股份有限公司製)、SR-NP(M.TEC化學公司製)等。Examples of commercially available products include FB-15D, FB-105, FB-105X, FB-5SDX, SFP-20M, SFP-130MC (the above are manufactured by Denki Chemical Industry Co., Ltd.), EXCELICA (registered trademark) (Tokuyama Co., Ltd. Co., Ltd.), SR-NP (manufactured by M.TEC Chemical Co., Ltd.), etc.
(E)親水性二氧化矽於形成印刷配線板之硬化膜之用途時,中位直徑(D50)為30μm以下,於IC封裝基板上形成硬化膜之用途為5μm以下,中位直徑(D50)為0.2μm以上2μm以下之範圍時,基於於硬化性組成物中之分散性之觀點係較佳。又,中位直徑(D50)之測定方法如以下。(E) When hydrophilic silica is used to form a cured film on a printed wiring board, the median diameter (D50) is 30 μm or less. When used to form a cured film on an IC package substrate, the median diameter (D50) is 5 μm or less. A range of 0.2 μm to 2 μm is preferable from the viewpoint of dispersibility in the curable composition. In addition, the measurement method of the median diameter (D50) is as follows.
<中位直徑(D50)之測定方法> 將乙醇30ml與二氧化矽粉末1g放入容量100ml之燒杯中,以桌上型超音波洗淨機內攪拌3分鐘後,使用雷射繞射/散射式粒度分佈計(MICROTRAC BEL公司製)MICROTRAC MT-3300,於乙醇溶劑中測定體積基準中位直徑(D50)。<Measurement method of median diameter (D50)> Put 30 ml of ethanol and 1 g of silica powder into a beaker with a capacity of 100 ml, stir it for 3 minutes in a desktop ultrasonic cleaner, and use a laser diffraction/scattering particle size distribution meter (MICROTRAC BEL company) MT-3300, measure the volume-based median diameter (D50) in ethanol solvent.
又,(E)親水性二氧化矽於本發明之硬化性組成物中,以相對於(A)鹼可溶性樹脂100質量份(固形分)為10質量份以上200質量份以下之範圍,較佳為20質量份以上180質量份以下之範圍調配。藉由使(E)親水性二氧化矽為10質量份以上200質量份以下之範圍,可獲得硬化收縮抑制及硬化物之剛性強化效果,且分散性亦良好。Moreover, (E) hydrophilic silica is preferably in the range of 10 to 200 parts by mass relative to 100 parts by mass (solid content) of the alkali-soluble resin (A) in the curable composition of the present invention. It is prepared within the range of 20 parts by mass or more and 180 parts by mass or less. By setting (E) hydrophilic silica in the range of 10 parts by mass or more and 200 parts by mass or less, the effect of suppressing curing shrinkage and strengthening the rigidity of the cured product can be obtained, and the dispersibility is also good.
[(F)有機搖變劑] (F)有機搖變劑係為了抑制本發明之硬化性組成物中之(E)親水性二氧化矽之凝集、沉澱,及如本發明最初所明瞭,用以提高助焊劑對於本發明之硬化性組成物之硬化物的溼潤性而添加。[(F) Organic thixotropic agent] (F) The organic thixotropic agent is used to inhibit the aggregation and precipitation of (E) hydrophilic silica in the curable composition of the present invention, and as originally understood in the present invention, to improve the hardening of the flux for the present invention. It is added to improve the wettability of the hardened material of the sexual composition.
作為本發明之硬化性組成物中可使用之(F)有機搖變劑,包含由植物油脂肪酸與胺合成之脂肪酸醯胺類(芳醯胺蠟系);脂肪酸酯類、聚醚類、硫酸化油、高級醇硫酸酯等之界面活性劑系;聚羧酸酯類;聚羧酸醯胺類;尿素改質化合物,但不包含稱為蓖麻油蠟之氫化蓖麻油系者及對聚乙烯進行氧化處理導入極性基之蠟的氧化聚乙烯系者。(F) organic thixotropic agents that can be used in the curable composition of the present invention include fatty acid amides (arylamide wax series) synthesized from vegetable oil fatty acids and amines; fatty acid esters, polyethers, sulfated Surfactant systems such as oils and higher alcohol sulfate esters; polycarboxylate esters; polycarboxylic acid amides; urea modified compounds, but excluding hydrogenated castor oil systems called castor oil waxes and polyethylene Oxidized polyethylene series that introduces wax with polar groups through oxidation treatment.
作為(F)有機搖變劑之市售品舉例為BYK(註冊商標)-R606、BYK(註冊商標)-405、BYK(註冊商標)-R605、BYK(註冊商標)-R607、BYK(註冊商標)-410、BYK(註冊商標)-411、BYK(註冊商標)-415、BYK(註冊商標)-430、BYK(註冊商標)-431、BYK(註冊商標)-7410ET、BYK(註冊商標)-7411ES(以上為日本BYK公司製)、TALEN 1450、TALEN 2000、TALEN 2200A、TALEN 7200-20、TALEN 8200-20、TALEN 8300-20、TALEN 8700-20、TALEN BA-600、FLOWNON SH-290、FLOWNON SH-295S、FLOWNON SH-350、FLOWNON HR-2、FLOWNON HR-4AF(以上為共榮社化學公司製)。Examples of commercially available products as (F) organic thixotropes 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 (the above are made by BYK Corporation of Japan), TALEN 1450, TALEN 2000, TALEN 2200A, TALEN 7200-20, TALEN 8200-20, TALEN 8300-20, TALEN 8700-20, TALEN BA-600, FLOWNON SH-290, FLOWNON SH-295S, FLOWNON SH-350, FLOWNON HR-2, FLOWNON HR-4AF (the above are manufactured by Kyeisha Chemical Co., Ltd.).
(F)有機搖變劑於本發明之硬化性組成物中,相對於(E)親水性二氧化矽100質量份(固形分)為0.01質量份以上15質量份以下,較佳為0.05質量份以上10質量份以下。(F) The organic thixotrope in the curable composition of the present invention is 0.01 to 15 parts by mass, preferably 0.05 parts by mass, based on 100 parts by mass (solid content) of (E) hydrophilic silica. 10 parts by mass or less.
又,(F)有機搖變劑於本發明之硬化性組成物中,相對於(D)聚矽氧化合物2質量份為0.05質量份以上,較佳為0.1質量份以上。Moreover, the (F) organic thixotrope in the curable composition of the present invention is 0.05 parts by mass or more, preferably 0.1 part by mass or more based on 2 parts by mass of the (D) polysiloxane compound.
藉由為上述範圍內,成為(E)親水性二氧化矽良好分散,且助焊劑對於硬化性組成物之硬化物的溼潤性亦良好者。By being 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)抗氧化劑] 本發明之硬化性組成物較佳添加(G)抗氧化劑。(G)抗氧化劑藉由抑制貼銅基板(基材)之銅氧化而提高基材與硬化性組成物之密著性。[(G) Antioxidant] The curable composition of the present invention preferably adds (G) antioxidant. (G) The antioxidant improves the adhesion between the base material and the curable composition by inhibiting copper oxidation of the copper-clad substrate (base material).
作為(G)抗氧化劑舉例為3-(N-水楊醯基)胺基-1,2,4-三唑等之受阻酚化合物、2-巰基苯并咪唑之鋅鹽等之硫系抗氧化劑、三苯膦等之磷系抗氧化劑、二-第三丁基二苯基胺等之芳香族胺系抗氧化劑、三聚氰胺、苯并三唑、甲苯基三唑等之含有氮作為雜原子之雜環式化合物(硫系抗氧化劑除外)等。其中較佳為三聚氰胺。Examples of (G) antioxidants include hindered phenol compounds such as 3-(N-salicylicyl)amino-1,2,4-triazole, sulfur-based antioxidants such as zinc salts of 2-mercaptobenzimidazole, and triazole. Phosphorus-based antioxidants such as benzene phosphine, aromatic amine-based antioxidants such as di-tert-butyldiphenylamine, etc. Heterocyclic formulas containing nitrogen as heteroatoms such as melamine, benzotriazole, tolyltriazole, etc. Compounds (except sulfur antioxidants), etc. Among them, melamine is preferred.
(G)抗氧化劑之調配量,於本發明之硬化性組成物中,相對於(A)鹼可溶性樹脂100質量份(固形分)為0.1質量份以上5質量份以下,較佳為0.5質量份以上2質量份以下。The compounding amount of (G) antioxidant in the curable composition of the present invention is 0.1 to 5 parts by mass, preferably 0.5 part by mass relative to 100 parts by mass (solid content) of the alkali-soluble resin (A) 2 parts by mass or less.
[其他成分] 進而,本發明之硬化性組成物中,較佳添加光聚合性多官能單體。光聚合性多官能單體係於1分子中具有2個以上乙烯性不飽和基之化合物,(於(A)鹼可溶性樹脂中包含乙烯性不飽和基之情況下)係有助於藉由活性能量線照射而使(A)鹼可溶性樹脂光硬化,為使硬化性組成物光硬化而使用。[Other ingredients] Furthermore, it is preferable to add a photopolymerizable polyfunctional monomer to the curable composition of the present invention. A compound in which the photopolymerizable polyfunctional monosystem has two or more ethylenically unsaturated groups in one molecule (when (A) the alkali-soluble resin contains an ethylenically unsaturated group) contributes to the activity through The alkali-soluble resin (A) is photocured by irradiation with energy rays, and is used for photocuring the curable composition.
作為光聚合性多官能單體而使用之化合物舉例為例如慣用習知之聚酯(甲基)丙烯酸酯、聚醚(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯、碳酸酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯等。具體舉例為己二醇、三羥甲基丙烷、季戊四醇、二季戊四醇、三-羥乙基異氰脲酸酯等之多元醇或該等之環氧乙烷加成物、環氧丙烷加成物、或ε-己內酯加成物等之多元丙烯酸酯類;苯氧基丙烯酸酯、雙酚A二丙烯酸酯、及該等之酚類之環氧乙烷加成物或環氧丙烷加成物等之多元丙烯酸酯類;甘油二縮水甘油醚、甘油三縮水甘油醚、三羥甲基丙烷三縮水甘油醚、三縮水甘油基異氰脲酸酯等之縮水甘油醚之多元丙烯酸酯類;不限於前述,而為聚醚多元醇、聚碳酸酯二醇、羥基末端聚丁二烯、聚酯多元醇等之多元醇直接丙烯酸酯化、或經由二異氰酸酯基而胺基甲酸酯丙烯酸酯化之丙烯酸酯類及三聚氰胺丙烯酸酯、及與前述丙烯酸酯對應之各甲基丙烯酸酯類之至少任一種等。Examples of compounds used as photopolymerizable polyfunctional monomers include commonly known polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, and carbonates. (meth)acrylate, epoxy (meth)acrylate, etc. Specific examples include polyols such as hexylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tri-hydroxyethyl isocyanurate, or their ethylene oxide adducts and propylene oxide adducts. , or polyacrylates such as ε-caprolactone adducts; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols Polyacrylic acid esters of glycidyl ethers such as glycerol diglycidyl ether, glyceryl triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc.; Not limited to the above, but may be direct acrylation of polyols such as polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, polyester polyol, or urethane acrylate via diisocyanate group At least any one of acrylates, melamine acrylates, and methacrylates corresponding to the above-mentioned acrylates.
光聚合性多官能單體於本發明之硬化性組成物中,相對於(A)鹼可溶性樹脂100質量份(固形分)以3質量份以上30質量份以下之範圍,較佳為10質量份以上20質量份以下之範圍調配。In the curable composition of the present invention, the photopolymerizable polyfunctional monomer is in the range of 3 parts by mass to 30 parts by mass, preferably 10 parts by mass, based on 100 parts by mass (solid content) of the alkali-soluble resin (A) It is prepared within the range of above 20 parts by mass and below.
本發明之硬化性組成物較佳進而包含二氰基二醯胺、三氟化硼-胺觸媒、有機酸醯肼等之硬化觸媒。硬化觸媒於本發明之硬化性組成物中,相對於(A)鹼可溶性樹脂100質量份(固形分)以5質量份以下,較佳以0.1質量份以上2質量份以下之範圍的量添加。The curable composition of the present invention preferably further contains curing catalysts such as dicyanodiamide, boron trifluoride-amine catalyst, and organic acid hydrazine. The curing catalyst is added to the curable composition of the present invention in an amount of 5 parts by mass or less, preferably in an amount ranging from 0.1 part by mass to 2 parts by mass, based on 100 parts by mass (solid content) of the alkali-soluble resin (A). .
再者,本發明之硬化性組成物中,以著色為目的,亦可添加著色顏料或染料等。作為著色顏料或染料等,可使用以色彩指數表示之習知慣用者。舉例為例如顏料藍 15、15:1、15:2、15:3、15:4、15:6、16、60,溶劑藍 35、63、68、70、83、87、94、97、122、136、67、70,顏料綠 7、36、3、5、20、28,溶劑黃 163,顏料黃 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,顏料橙 1、5、13、14、16、17、24、34、36、38、40、43、46、49、51、61、63、64、71、73,顏料紅 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,溶劑紅 135、179、149、150、52、207,顏料紫 19、23、29、32、36、38、42,溶劑紫 13、36,顏料棕 23、25,顏料黑 1、7等。該等著色顏料.染料等相對於硬化性組成物100質量份,可以0.01質量份以上5質量份以下之範圍的量,較佳0.1質量份以上3質量份以下之範圍的量添加。Furthermore, for the purpose of coloring, coloring pigments, dyes, etc. may be added to the curable composition of the present invention. As coloring pigments, dyes, etc., those conventionally expressed by color indexes can be used. Examples include 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, 216, 122, 202, 206, 207, 209, solvent red 135, 179, 149, 150, 52, 207, pigment purple 19, 23, 29, 32, 36, 38 , 42, solvent violet 13, 36, pigment brown 23, 25, pigment black 1, 7, etc. Such coloring pigments. The dye and the like may be added in an amount ranging from 0.01 to 5 parts by mass, preferably from 0.1 to 3 parts by mass, based on 100 parts by mass of the curable composition.
進而,根據需要,可調配對苯二酚、對苯二酚單甲醚、第三丁基兒茶酚、焦棓酚、吩噻嗪等之習知慣用聚合抑制劑、光聚合增感劑、光安定劑、難燃劑、難燃助劑等之習知慣用添加劑類。Furthermore, as needed, conventionally used polymerization inhibitors, photopolymerization sensitizers, etc., such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, and phenothiazine, can be adjusted. Light stabilizers, flame retardants, flame retardant auxiliaries, etc. are commonly used additives.
又,本發明之硬化性組成物亦可含有用以調整黏度之有機溶劑。作為有機溶劑可使用甲基乙基酮、環己酮等酮類;甲苯、二甲苯、四甲基苯等之芳香族烴類;溶纖素、甲基溶纖素、丁基溶纖素、卡必醇、甲基卡必醇、丁基卡必醇、丙二醇單甲醚、二丙二醇單甲醚(DPM)、二丙二醇二乙醚、三丙二醇單甲醚等之二醇醚類;乙酸乙酯、乙酸丁酯、乳酸丁酯、溶纖素乙酸酯、丁基溶纖素乙酸酯、卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇單甲醚乙酸酯、二丙二醇單甲醚乙酸酯、碳酸伸丙酯等之酯類;辛烷、癸烷等之脂肪族烴類;石油醚、石油腦、溶劑石油腦等之石油系溶劑等。該等有機溶劑可單獨或組合2種以上使用。In addition, the curable composition of the present invention may also contain an organic solvent for adjusting the viscosity. As organic solvents, ketones such as methyl ethyl ketone and cyclohexanone can be used; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellulose, methyl cellulose, butyl cellulose, and carbisol. Alcohol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (DPM), dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether and other glycol ethers; ethyl acetate, acetic acid Butyl ester, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Esters such as acetate and propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha, solvent naphtha, etc. These organic solvents can be used alone or in combination of two or more.
<本發明之硬化性組成物之乾膜及硬化物> 本發明之硬化性組成物可塗佈於載體膜(支撐體)上並乾燥所得之乾膜形態。乾膜化時,以上述有機溶劑稀釋本發明之硬化性組成物調整為適當黏度,藉由缺角輪塗佈器、刮刀塗佈器、唇模塗佈器、桿塗佈器、橡皮輥塗佈器、逆輥塗佈器、傳送輥塗佈器、凹版塗佈器、噴霧塗佈器等,於載體膜上塗佈均一厚度,通常,於50~130℃之溫度乾燥1~30分鐘,可獲得乾燥塗膜。關於塗佈膜厚並未特別限制,但一般乾燥後之膜厚係於0.1~100μm,較好0.5~50μm之範圍適當選擇。<Dry film and cured product of the curable composition of the present invention> The curable composition of the present invention can be coated on a carrier film (support) and dried to form a dry film. During dry film formation, the curable composition of the present invention is diluted with the above-mentioned organic solvent to adjust to an appropriate viscosity, and is applied using a notch wheel coater, a blade coater, a lip die coater, a rod coater, or a rubber roller. Use a spreader, reverse roller coater, transfer roller coater, gravure coater, spray coater, etc. to coat the carrier film with a uniform thickness. Usually, dry at a temperature of 50~130°C for 1~30 minutes. A dry coating film is available. The coating film thickness is not particularly limited, but generally the film thickness after drying is within the range of 0.1 to 100 μm, preferably 0.5 to 50 μm.
作為載體膜係使用塑膠膜,可使用聚對苯二甲酸乙二酯等之聚酯膜、聚醯亞胺膜、聚醯胺醯亞胺膜、聚丙烯膜、聚苯乙烯膜等之塑膠膜。關於載體膜之厚度並未特別限制,但一般係於0.1~150μm之範圍適當選擇。As the carrier film, a plastic film is used, and plastic films such as polyester film such as polyethylene terephthalate, polyimide film, polyimide film, polypropylene film, and polystyrene film can be used. . The thickness of the carrier film is not particularly limited, but is generally appropriately selected within the range of 0.1 to 150 μm.
該情況下,於載體膜上成膜塗膜後,基於防止於塗膜表面附著灰塵等之目的,較佳於塗膜表面進而層合可剝離之覆蓋膜。可剝離之覆蓋膜可使用例如聚乙烯膜或聚四氟乙烯膜、聚丙烯膜、經表面處理之紙等,只要在剝離覆蓋膜時塗膜與覆蓋膜之接著力小於塗膜與載體膜之接著力即可。In this case, after the coating film is formed on the carrier film, it is preferable to laminate a peelable cover film on the surface of the coating film for the purpose of preventing dust and the like from adhering to the surface of the coating film. The peelable covering film can be, for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc., as long as the adhesion force between the coating film and the cover film is less than the bonding force between the coating film and the carrier film when peeling off the covering film. Then force it.
又,關於本發明之硬化性組成物,於使用上述有機溶劑調整為適於塗佈方法之黏度後,於基材上藉由浸漬塗佈法、流動塗佈法、輥塗佈法、棒塗佈法、網版印刷法、簾塗佈法、模嘴塗佈法等方法塗佈,於約50℃~ 90℃之溫度使組成物中所含之有機溶劑揮發乾燥(暫時乾燥),可形成無觸黏之乾燥塗膜。又,將本發明之硬化性組成物塗佈於載體膜後乾燥作成膜進行捲取之乾膜之情況下,藉由層壓機等使以硬化性組成物之塗膜與基材接觸之方式貼合於基材上後,剝離載體膜,藉此可於基材上形成塗膜層。Moreover, regarding the curable composition of the present invention, after using the above-mentioned organic solvent to adjust the viscosity suitable for the coating method, it is applied to the base material by a dip coating method, a flow coating method, a roll coating method, or a rod coating method. Coating by cloth method, screen printing method, curtain coating method, die nozzle coating method, etc., at about 50℃~ The temperature of 90°C causes the organic solvent contained in the composition to evaporate and dry (temporarily dry), forming a dry coating film that is non-tacky. In addition, when the curable composition of the present invention is applied to a carrier film and then dried to form a film and rolled up as a dry film, the coating film of the curable composition is brought into contact with the base material using a laminator or the like. After being bonded to the base material, the carrier film is peeled off, thereby forming a coating layer on the base material.
該等塗膜可藉由例如活性能量線照射而光硬化,或藉由加熱至100℃~250℃之溫度而熱硬化,可獲得硬化物。These coating films can be photocured by, for example, active energy ray irradiation, or thermally cured by heating to a temperature of 100°C to 250°C to obtain a cured product.
作為上述基材可舉例為預先形成電路之印刷配線板或軟性印刷配線板,此外舉例為紙+酚樹脂、紙+環氧樹脂、紙+玻璃布+環氧樹脂、玻璃不織布+環氧樹脂、玻璃織布+環氧樹脂、玻璃纖維+聚醯亞胺樹脂等之貼銅層合板。Examples of the above-mentioned substrate include a printed wiring board or a flexible printed wiring board with circuits formed in advance. In addition, examples include paper + phenol resin, paper + epoxy resin, paper + glass cloth + epoxy resin, glass nonwoven fabric + epoxy resin, Copper-clad laminates of glass fabric + epoxy resin, glass fiber + polyimide resin, etc.
塗佈本發明之硬化性組成物後進行之揮發乾燥可使用熱風循環式乾燥爐、IR爐、加熱板、強制烘箱等之具備利用蒸氣之空氣加熱方式之熱源者使乾燥機內之熱風對流接觸之方法及利用噴嘴吹附支撐體之方法進行。The volatilization drying after applying the curable composition of the present invention can use a hot air circulation drying oven, an IR oven, a heating plate, a forced oven, and other heat sources equipped with an air heating method using steam to make hot air convection contact in the dryer. method and the method of using a nozzle to blow the support body.
作為上述活性能量線照射所用之曝光機,若為搭載高壓水銀燈、超高壓水銀燈、金屬鹵素燈、水銀射弧燈等而照射350~450nm之範圍的紫外線之裝置即可,進而亦可使用直接描繪裝置(例如藉由來自電腦之CAD數據直接照射活性能量線而描繪圖像之直接成像裝置)。作為直接描繪機之光源,只要使用最大波長於350~410nm之範圍者即可。用於圖像形成之曝光量係隨膜厚等而異,但一般為20~1000mJ/cm2 ,較好為20~800mJ/cm2 之範圍內。The exposure machine used for the above-mentioned 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 arc lamp, etc., and can irradiate ultraviolet rays in the range of 350 to 450 nm. Direct drawing may also be used. Devices (such as direct imaging devices that draw images by directly irradiating active energy rays from CAD data from a computer). As the light source of the direct drawing machine, it is sufficient to use one with a maximum wavelength in the range of 350~410nm. The exposure amount used for image formation varies depending on the film thickness, etc., but is generally in the range of 20 to 1000 mJ/cm 2 , preferably in the range of 20 to 800 mJ/cm 2 .
又,作為顯像方法,可利用浸漬法、淋洗法、噴霧法、刷塗法等,作為顯影液,可使用氫氧化鉀、氫氧化鈉、碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨、胺類等之鹼水溶液。In addition, as the developing method, dipping method, rinsing method, spray method, brushing method, etc. can be used. As the developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, and sodium silicate can be used. , ammonia, amines, etc. alkali aqueous solution.
如此,依據由本發明之硬化性組成物所得之乾膜、硬化物,由於耐熱性、剛性、對基材之密著性、絕緣性優異,故可適用於各種用途,適用對象並未特別限制。例如可使用於製作印刷配線板之防蝕刻劑、防焊劑、標劑阻劑等,其中,由於焊接性提高,故可較佳地使用作為要求高耐熱性之防焊劑。In this way, the dry film and cured product obtained from the curable composition of the present invention have excellent heat resistance, rigidity, adhesion to the substrate, and insulation properties, so they can be applied to various applications, and the applicable objects are not particularly limited. For example, it can be used as an etching resist, solder resist, standard resist, etc. for manufacturing printed wiring boards. Among them, since the solderability is improved, it can be preferably used as a solder resist that requires high heat resistance.
<使用硬化性組成物之硬化物作為絕緣性硬化被膜之電子零件> 於上述基材上圖型印刷之硬化性組成物之硬化物使用作為防焊劑時,於用於零件安裝之焊接步驟中被加熱。手焊接可藉流動焊接、回焊焊接等任一者進行,但例如於回焊焊接時,供於將於100℃~140℃預熱1~4小時,與隨後於240℃~280℃加熱5~20秒左右重複複數次(例如2~4次)而加熱、熔融之回焊步驟,冷卻後,根據需要安裝零件而完成電子零件。<Electronic components using a cured product of a curable composition as an 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 during the soldering step for component mounting. Hand soldering can be performed by flow soldering, reflow soldering, etc., but for example, during reflow soldering, it is necessary to preheat at 100℃~140℃ for 1~4 hours, and then heat at 240℃~280℃ for 5 hours The resoldering step of heating and melting is repeated several times (for example, 2 to 4 times) for about 20 seconds. After cooling, the parts are installed as needed to complete the electronic parts.
以下顯示實施例具體說明本發明,但本發明並非限定於該等實施例者。又,以下只要未特別限制則「份」意指質量份。 [實施例]The following examples are shown to illustrate the present invention in detail, but the present invention is not limited to these examples. In addition, in the following, "parts" means parts by mass unless otherwise specified. [Example]
(鹼可溶性樹脂之合成) [合成例1] 將雙酚F型環氧樹脂(環氧當量950g/eq,軟化點85℃) 380份與表氯醇925份溶解於二甲基亞碸462.5份後,攪拌下於70℃以100分鐘添加98.5%NaOH 60.9份。添加後進而於70℃進行3小時反應。反應結束後,添加水250份進行水洗。油水分離後,減壓下自油層蒸餾回收大半的二甲基亞碸及過量未反應表氯醇,殘留之包含副製鹽與二甲基亞碸之反應產物溶解於甲基異丁基酮750份中,進而添加30% NaOH 10份,於70℃反應1小時。反應結束後,以水200份進行水洗2次。油水分離後,自油層蒸餾回收甲基異丁基酮,獲得環氧當量310g/eq、軟化點69℃之環氧樹脂(a)。所得環氧樹脂(a)若由環氧當量計算,則係前述起始物質雙酚F型環氧樹脂中之醇性羥基6.2個中約5個經環氧化者。將該環氧樹脂(a) 310份及卡必醇乙酸酯282份饋入燒瓶中,於90℃加熱、攪拌並溶解。所得溶液暫時冷卻至60℃,添加丙烯酸72份(1莫耳)、甲基對苯二酚0.5份、三苯膦2份,加熱至100℃,反應約60小時,獲得酸價為0.2mgKOH/g之反應物。於其中添加四氫鄰苯二甲酸乾140份(0.92莫耳),加熱至90℃進行反應,獲得感光性之含羧基之樹脂清漆(A-1)。所得含羧基之樹脂清漆(A-1)之固形分濃度為62.5%,固形分酸價(mgKOH/g)為100。(Synthesis of alkali-soluble resin) [Synthesis example 1] Dissolve 380 parts of bisphenol F epoxy resin (epoxy equivalent 950g/eq, softening point 85°C) and 925 parts of epichlorohydrin in 462.5 parts of dimethylsulfoxide, and add 98.5 parts over 100 minutes at 70°C while stirring. %NaOH 60.9 parts. After addition, reaction was further carried out at 70°C for 3 hours. After the reaction was completed, 250 parts of water was added for washing. After the oil and water are separated, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin are recovered from the oil layer by distillation under reduced pressure. The remaining reaction product containing by-product salts and dimethyl sulfoxide is dissolved in methyl isobutyl ketone 750 parts, further add 10 parts of 30% NaOH, and react at 70°C for 1 hour. After the reaction, wash twice with 200 parts of water. After the oil and water are separated, methyl isobutyl ketone is recovered by distillation from the oil layer to obtain epoxy resin (a) with an epoxy equivalent of 310 g/eq and a softening point of 69°C. If the obtained epoxy resin (a) is calculated based on the epoxy equivalent, approximately 5 of the 6.2 alcoholic hydroxyl groups in the bisphenol F-type epoxy resin as the starting material have been epoxidized. 310 parts of the epoxy resin (a) and 282 parts of carbitol acetate were put into a flask, heated, stirred and dissolved at 90°C. The resulting solution was temporarily cooled to 60°C, and 72 parts (1 mol) of acrylic acid, 0.5 parts of methylhydroquinone, and 2 parts of triphenylphosphine were added, heated to 100°C, and reacted for about 60 hours to obtain an acid value of 0.2 mgKOH/ g reactant. Add 140 parts (0.92 mol) of dry tetrahydrophthalic acid to it, heat to 90°C to react, and obtain a photosensitive carboxyl-containing resin varnish (A-1). The obtained carboxyl group-containing resin varnish (A-1) had a solid content concentration of 62.5% and a solid acid value (mgKOH/g) of 100.
[合成例2] 甲酚酚醛清漆型環氧樹脂(大日本墨水化學工業(股)製,註冊商標“EPICLON” N-695,環氧當量:220) 220份饋入附有攪拌機及回硫冷卻器之四頸燒瓶中,添加卡必醇乙酸酯214份,加熱溶解。其次,添加作為聚合抑制劑之對苯二酚0.1份及作為反應觸媒之二甲基苄胺2.0份。該混合物於95~105℃加熱,緩緩滴加丙烯酸72份,反應16小時。該反應生成物冷卻至80~90℃,添加四氫鄰苯二甲酸酐106份,反應8小時,冷卻後取出。 如此所得之同時具有乙烯性不飽和鍵及羧基之感光性樹脂之不揮發分為65%,固形分之酸價為85mgKOH/g,重量平均分子量Mw約3,500。以下將該樹脂溶液稱為清漆(A-2)。 又,所得樹脂之重量平均子量測定係利用島津製作所(股)製泵LC-804、KF-803、KF-802之3根連結之高速液體層析儀測定。[Synthesis example 2] Cresol novolak type epoxy resin (manufactured by Dainippon Ink Chemical Industry Co., Ltd., registered trademark "EPICLON" N-695, epoxy equivalent: 220) 220 parts are fed into a four-neck flask equipped with a mixer and a sulfur return cooler. , add 214 parts of carbitol acetate and heat to dissolve. Next, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 part of dimethylbenzylamine as a reaction catalyst were added. The mixture was heated at 95~105°C, 72 parts of acrylic acid was slowly added dropwise, and the reaction was carried out for 16 hours. The reaction product was cooled to 80~90°C, 106 parts of tetrahydrophthalic anhydride was added, the reaction was carried out for 8 hours, and then taken out after cooling. The photosensitive resin thus obtained having both ethylenically unsaturated bonds and carboxyl groups has a non-volatile content of 65%, an acid value of solid content of 85 mgKOH/g, and a weight average molecular weight Mw of approximately 3,500. This resin solution will be called varnish (A-2) below. In addition, the weight average subweight of the obtained resin was measured using three connected high-speed liquid chromatographs with pumps LC-804, KF-803, and KF-802 manufactured by Shimadzu Corporation.
<1.實施例1~9及比較例1~3之硬化性組成物之調製> 分別調配合成例之樹脂溶液及表1所示之各材料,以攪拌機預混合,其次藉由3根輥磨機混練而調製硬化性組成物。表1中,關於(A-1)~(A-3),表示分別包含溶劑之樹脂溶液之質量份。<1. Preparation of curable compositions of Examples 1 to 9 and Comparative Examples 1 to 3> The resin solution of the preparation example and each material shown in Table 1 were separately prepared, premixed with a mixer, and then kneaded with a three-roller mill to prepare a curable composition. In Table 1, (A-1) to (A-3) represent the parts by mass of the resin solution each containing the solvent.
針對上述各組成物進行以下所示之特性試驗。其結果示於表1。The following characteristic tests were performed on each of the above compositions. The results are shown in Table 1.
<2.硬化硬組成物對基材之不沾著、調平性評價> 於藉由化學研磨處理而使表面粗化之貼銅基板(基材)上,使用網版(鐵特龍100網眼),將<1.實施例1~9及比較例1~3之硬化性組成物之調製>中調整之各硬化性組成物印刷於貼銅基板全面以成為膜厚10μm。<2. Evaluation of the non-adhesion and leveling properties of the hardened hard composition to the substrate> On the copper-clad substrate (base material) whose surface has been roughened by chemical polishing treatment, use a screen plate (Titron 100 mesh) to harden <1. Examples 1 to 9 and Comparative Examples 1 to 3 Preparation of the curable composition > Each curable composition adjusted in the middle is printed on the entire surface of the copper-clad substrate so that the film thickness is 10 μm.
以目視觀察剛印刷後之塗膜,確認有無硬化性組成物不沾著及調平狀態(平滑性)。其次,將印刷基板於80℃乾燥30分鐘,恢復至室溫後同樣目視確認乾燥後之塗膜狀態。(又,本實施例中雖以目視確認,但於目視判定困難時,亦可使用表面粗糙度測定機(SurfCorder:小坂研究所股份有限公司製)或形狀測定雷射顯微鏡(VK-X-100/KEYENCE公司製)觀察表面粗糙度)。 評價基準如以下。Visually observe the coating film immediately after printing to confirm whether the curable composition does not stick to it and is in a leveled state (smoothness). Next, dry the printed circuit board at 80°C for 30 minutes, return to room temperature, and visually confirm the coating film state after drying. (Also, although visual confirmation is used in this example, when visual judgment is difficult, a surface roughness measuring machine (SurfCorder: manufactured by Kosaka Laboratory Co., Ltd.) or a shape measuring laser microscope (VK-X-100) may also be used. /KEYENCE Co., Ltd.) observe the surface roughness). The evaluation criteria are as follows.
○:無不沾著、無篩網痕跡 △:有不沾著,且無篩網痕跡,或無不沾著且有篩網痕跡 ×:有不沾著,且有篩網痕跡○: No adhesion or screen marks △: There is non-sticking and no traces of the screen, or there is no non-sticking and there are traces of the screen. ×: There is no adhesion, and there are traces of the screen
<3.助焊劑之不沾著評價> 使用網版(鐵特龍100網眼),將<1.實施例1~4及比較例1~4之硬化性組成物之調製>中調整之各硬化性組成物印刷於藉由化學研磨處理而使表面粗化之外形150×95mm、厚1.6mm之FR-4、35μm厚貼銅基板全面以成為膜厚10μm。<3. Evaluation of flux non-adhesion> Using a screen (Titron 100 mesh), print each curable composition adjusted in <1. Preparation of Curable Compositions of Examples 1 to 4 and Comparative Examples 1 to 4> on a surface treated with chemical polishing. The surface of the 150×95mm, 1.6mm thick FR-4, 35μm thick copper substrate was roughened to a film thickness of 10μm over the entire surface.
於80℃乾燥30分鐘後,使用用以形成圖型之95×150mm大小之曝光遮罩以600mJ/cm2 曝光,進行鹼顯像(1% Na2 CO3 水溶液,30℃、60秒顯像),以150℃/60分鐘熱硬化後,進行1000mJ/cm2 之後UV處理。After drying at 80°C for 30 minutes, use an exposure mask of 95×150mm size to form the pattern at 600mJ/ cm2 for exposure, and perform alkali development (1% Na 2 CO 3 aqueous solution, 30°C, 60 seconds development ), after thermal hardening at 150°C/60 minutes, perform UV treatment at 1000mJ/ cm2 .
對固定有硬化性組成物之硬化物的FR-4基板(基材)實施無電解鍍Sn處理(Sn:1.1μm/塚田理研工業(股)),重複實施1次至3次之回焊步驟(265℃),於無電解鍍Sn處理後回焊步驟前、回焊步驟1次後、回焊步驟2次後、回焊步驟3次後之各階段,對固定有硬化性組成物之硬化物的FR-4基板實施濕潤張力試驗。The FR-4 substrate (base material) to which the cured product of the curable composition is fixed is subjected to electroless Sn plating (Sn: 1.1 μm/Tsukada Riken Industry Co., Ltd.), and the reflow step is repeated from 1 to 3 times. (265℃), before the reflow step after electrolytic Sn plating, after the reflow step once, after the reflow step twice, and after the reflow step three times, hardening of the fixed hardenable composition Wet tension test was performed on the FR-4 substrate of the product.
溼潤張力試驗係基於JIS K6768進行,作為溼潤張力試驗用混合液,分別於無電解鍍Sn處理後回焊步驟前使用“溼潤張力試驗用混合液NO.60.0”,於回焊步驟1次後使用“溼潤張力試驗用混合液NO.38.0”,於回焊步驟2次後使用“溼潤張力試驗用混合液NO.36.0”,於回焊步驟3次後使用“溼潤張力試驗用混合液NO.34.0”。任一溼潤張力試驗用混合液均為富士軟片和光純藥公司製。又各混合液之NO.係表示該混合液之表面張力(單位:mN/m)。The wet tension test was conducted based on JIS K6768. As the wet tension test mixture, "Wet Tension Test Mixture No. 60.0" was used after the electroless Sn plating process and before the reflow step, and was used after the reflow step once. "Mixed solution for wet tension test NO.38.0", use "mixed solution for wet tensile test NO.36.0" after the reflow step 2 times, use "mixed solution NO.34.0 for wet tensile test" after the reflow step 3 times ". The mixed solution for any wet tension test was manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. In addition, the NO. of each mixed liquid represents the surface tension of the mixed liquid (unit: mN/m).
溼潤張力試驗具體而言係以附有溼潤張力試驗用混合液之棉棒描繪,觀察2秒後之液膜狀態。而且,於液膜未產生破裂,且保有2秒以上之塗佈時狀態之情況判斷為溼潤。Specifically, the wet tension test is drawn with a cotton swab with the mixed liquid for the wet tension test, and the liquid film state is observed after 2 seconds. Furthermore, it is judged as wet when the liquid film does not break and remains in the coating state for more than 2 seconds.
又,溼潤張力試驗用混合液之數值越高,助焊劑不沾著性越良好,故將溼潤張力試驗設為評價助焊劑不沾著性之試驗。In addition, the higher the numerical value of the mixed solution for the wet tension test, the better the flux non-stick property. Therefore, the wet tension test was set as a test to evaluate the flux non-stick property.
表1中,評價基準如以下。In Table 1, the evaluation criteria are as follows.
○:無電解鍍Sn處理後回焊步驟前~回焊步驟3次後之所有階段中,均判斷為有溼潤(無不沾著)。○: Wetting (no non-sticking) was judged in all stages after electroless Sn plating, before the reflow step to after three reflow steps.
×:無電解鍍Sn處理後回焊步驟前~回焊步驟3次後中,有判斷為1次未施潤(有不沾著)之情況。×: After the electroless Sn plating process, before the reflow step and after the reflow step three times, there were cases where it was judged that no moisturizing was applied once (there was no adhesion).
*1:CYCLOMER P(ACA) Z250(固形分45wt%之含不飽和基之含羧基共聚合樹脂溶液,DAICEL化學公司製) *2:2,4,6-三甲基苯甲醯基二苯基氧化膦(Omnirad TPO H:IGM Resins B.V.公司製) *3:2-二甲胺基-2-(4-甲基苄基)-1-(4-嗎啉-4-基苯基)-丁烷-1-酮(Omnirad 379:IGM Resins B.V.公司製) *4:雙酚A型環氧樹脂(JER(註冊商標)-834:三菱化學公司製) *5:異氰脲酸三縮水甘油酯(TEPIC-HP:日產化學工業公司製) *6:聚酯改質聚二甲基矽氧烷(BYK(註冊商標)-313:日本BYK公司製) *7:聚醚改質聚二甲基矽氧烷(BYK(註冊商標)-300:日本BYK公司製) *8:球狀二氧化矽(D50=0.6μm)(SFP-130MC:電氣化學工業公司製) *9:球狀二氧化矽(D50=0.4μm)(SFP-20M:電氣化學工業公司製) *10:聚羥基羧酸酯(BYK(註冊商標)-R 606:日本BYK公司製) *11:三聚氰胺(Melamine:日產化學工業公司製) *12:表面施以甲基丙烯基系烷處理之球狀二氧化矽(1.5μm SM-C4:ADOMATEX公司製) *13:二季戊四醇六丙烯酸酯(DPHA:日本化藥公司製) *14:二氰基二醯胺(C0454:東京化成工業公司製) *15:藍色顏料(Fastogen Blue-5380:DIC公司製),表1中表示固形分之質量份 *16:黃色顏料(Cromophtal(註冊商標) Yellow S1515:BASF公司製),表1中表示固形分之質量份 *17:二丙二醇甲醚(Dowanol(註冊商標) DPM:日本道化學公司製)*1: CYCLOMER P(ACA) Z250 (solid content 45wt%, unsaturated group-containing carboxyl group-containing copolymer resin solution, manufactured by DAICEL Chemical Co., Ltd.) *2: 2,4,6-trimethylbenzyldiphenylphosphine oxide (Omnirad TPO H: manufactured by IGM Resins B.V.) *3: 2-Dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one (Omnirad 379: IGM Resins B.V. (made) *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 Japan BYK Corporation) *7: Polyether modified polydimethylsiloxane (BYK (registered trademark)-300: manufactured by Japan BYK Corporation) *8: Spherical silica (D50=0.6μm) (SFP-130MC: Made by Denki Chemical Industry Co., Ltd.) *9: Spherical silica (D50=0.4μm) (SFP-20M: Made by Denki Chemical Industry Co., Ltd.) *10: Polyhydroxycarboxylate (BYK (registered trademark)-R 606: manufactured by Japan BYK Corporation) *11: Melamine (Melamine: manufactured by Nissan Chemical Industry Co., Ltd.) *12: Spherical silica with surface treated with methacrylic alkane (1.5 μm SM-C4: manufactured by ADOMATEX Corporation) *13: Dipentaerythritol hexaacrylate (DPHA: manufactured by Nippon Kayaku Co., Ltd.) *14: Dicyanodiamide (C0454: manufactured by Tokyo Chemical Industry Co., Ltd.) *15: Blue pigment (Fastogen Blue-5380: manufactured by DIC Corporation). Table 1 shows the solid content by mass. *16: Yellow pigment (Cromophtal (registered trademark) Yellow S1515: manufactured by BASF Co., Ltd.). Table 1 shows the solid content by mass. *17: Dipropylene glycol methyl ether (Dowanol (registered trademark) DPM: manufactured by Nippon Do Chemical Co., Ltd.)
如表1之實施例所示,調配(D)聚矽氧化合物、(E)親水性二氧化矽及(F)有機搖變劑時,維持了本發明之硬化性組成物對貼銅基板(基材)之溼潤性,調平性亦為良好,(E)親水性二氧化矽亦未發生凝集、沉澱。又,於固定有本發明之硬化性組成物之硬化物的基材上塗佈溼潤張力試驗用混合液時,於該硬化物上溼潤張力試驗用混合物亦無不沾著,維持了溼潤張力試驗用混合物對該硬化物之溼潤性。As shown in the examples in Table 1, when (D) polysiloxy compound, (E) hydrophilic silica and (F) organic thixotrope are formulated, the curable composition of the present invention is maintained against the copper substrate ( The wettability and leveling properties of the substrate) are also good, and (E) the hydrophilic silica does not agglomerate or precipitate. Furthermore, when the wet tension test mixture was applied to a base material having a cured product of the curable composition of the present invention fixed thereto, the wet tensile test mixture did not adhere to the cured product, and the wet tensile test was maintained. Use the mixture to improve the wettability of the hardened material.
另一方面,於二氧化矽表面施以疏水性處理之比較例1,即使調配(F)有機搖變劑,溼潤張力試驗用混合液對固定有本發明之硬化性組成物之硬化物的基材之溼潤性仍降低,認為焊接性降低者。又,未含有(F)有機搖變劑之比較例2,即使調配(D)聚矽氧化合物及(E)親水性二氧化矽,溼潤張力試驗用混合液對固定有本發明之硬化性組成物之硬化物的基材之溼潤性仍降低,認為焊接性降低者。再者,未含有(D)聚矽氧化合物之比較例3,硬化性組成物對貼銅基板(基材)之溼潤性不充分,或調平性惡化。On the other hand, in Comparative Example 1 in which hydrophobic treatment was applied to the surface of silica, even if (F) organic thixotropic agent was blended, the mixed liquid for the wet tension test was used to test the base of the cured product to which the curable composition of the present invention was fixed. If the wettability of the material is still reduced, it is considered that the weldability is reduced. Furthermore, in Comparative Example 2, which does not contain (F) organic thixotrope, even if (D) polysiloxane compound and (E) hydrophilic silica are blended, the mixed liquid for the wet tension test has the curable composition of the present invention. The wettability of the base material of the hardened material is still reduced, and the weldability is considered to be reduced. Furthermore, in Comparative Example 3 which does not contain (D) the polysiloxane compound, the wettability of the curable composition to the copper-clad substrate (base material) was insufficient, or the leveling property was deteriorated.
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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 |
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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 |
JP2013156506A (en) * | 2012-01-31 | 2013-08-15 | Taiyo Ink Mfg Ltd | Photosensitive resin composition and printed wiring board |
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