TWI392962B - Photosensitive resin composition and method for producing the same - Google Patents
Photosensitive resin composition and method for producing the same Download PDFInfo
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本發明係關於一種具有可用鹼水溶液顯影的感光功能、以聚醯亞胺樹脂為主成分、耐熱性、耐藥性、絕緣性與可撓性優異之適合作為正型光阻的光阻組成物及其製造方法。The present invention relates to a photoresist composition suitable for use as a positive photoresist having a photosensitive function developed by an aqueous alkali solution, a polyimide-based resin as a main component, heat resistance, chemical resistance, insulation, and flexibility. And its manufacturing method.
傳統作為感光性的聚醯亞胺系材料，係利用作為聚醯亞胺的先驅物之聚醯胺酸的材料，例如已有提案聚醯胺酸的羧基藉由與酯基鍵結導入感光基者(日本公開專利特開昭49－115541號公報以及特開昭55－45746號公報)、具有聚醯胺酸與感光基的胺化合物構成的材料(日本公開專利特開昭54－145794號公報)等。但是這些發明形成圖形化的薄膜後，為了得到目的的聚醯亞胺薄膜，必須進行超過300℃的高溫的醯亞胺化處理，為承受此高溫，有限制底基材、配線的銅氧化等的問題。Conventionally, as a photosensitive polyimine-based material, a material which is a poly-proline which is a precursor of polyimine, for example, a carboxyl group of a poly-proline has been proposed to be bonded to a photosensitive group by bonding with an ester group. (Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. )Wait. However, in order to obtain the intended polyimide film, it is necessary to carry out a ruthenium imidization treatment at a high temperature of more than 300 ° C in order to obtain the high temperature, and to limit the copper oxidation of the base substrate and the wiring. The problem.
作為改善方法，亦有提案完全以該後段硬化溫度的低溫化為目的，使用醯亞胺化的可溶於溶劑的樹脂之感光性聚醯亞胺(日本公開專利特開平10－274850號公報、特開平10－265571號公報、特開平13－335619號公報等)任一種都是利用(甲基)丙烯酸基賦予樹脂感光性，由於光硬化機構上容易受氧的阻礙，顯影時殘膜性不足等的原因，難以提高解像力，無法完全滿足被要求的特性。As an improvement method, there is a proposal to use a photosensitive polyimide which is a solvent-soluble resin which is yttrium imidized for the purpose of lowering the temperature of the post-stage hardening temperature (Japanese Laid-Open Patent Publication No. Hei 10-274850, In any of the above, the (meth)acrylic acid group imparts photosensitivity to the resin, and the photocuring mechanism is easily hindered by oxygen, and the residual film property is insufficient during development. For other reasons, it is difficult to improve the resolution and cannot fully satisfy the required characteristics.
另一方面，也有提案具有酚性羥基的聚醯亞胺架構、(日本公開專利特開平3－209478號公報)聚醯胺架構(日本公開專利特公平1－46862號公報、特開平11－65107號公報)與重氮萘醌的組合之正型者。這些為了確保顯影性，樹脂的分子量為低分子，作為感光劑的重氮萘醌的添加量對樹脂變成多量，具有難以得到樹脂原本的硬化特性的問題。On the other hand, there is also a polyimine structure which has a phenolic hydroxyl group, and a polyamine structure (Japanese Laid-Open Patent Publication No. Hei 3-209478) The positive type of the combination of the bullet and the diazonaphthoquinone. In order to ensure developability, the molecular weight of the resin is low molecular weight, and the amount of diazonaphthoquinone added as a sensitizer becomes a large amount of the resin, and it is difficult to obtain the original hardening property of the resin.
而且，上述樹脂以及重氮萘醌混合系的正型，顯影時殘膜性不足。Further, the positive type of the above-mentioned resin and the diazonaphthoquinone mixed system is insufficient in residual film properties during development.
〔專利文獻1〕日本公開專利特開昭49－115541號公報〔專利文獻2〕日本公開專利特開昭55－45746號公報〔專利文獻3〕日本公開專利特開昭54－145794號公報〔專利文獻4〕日本公開專利特開平10－274850號公報〔專利文獻5〕日本公開專利特開平10－265571號公報〔專利文獻6〕日本公開專利特開平13－335619號公報〔專利文獻7〕日本公開專利特開平3－209478號公報〔專利文獻8〕日本公開專利特公平1－46862號公報〔專利文獻9〕日本公開專利特開平11－65107號公報[Patent Document 1] Japanese Laid-Open Patent Publication No. SHO-54-145746 (Patent Document No. 5). Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei. Hei.
本發明有鑑於上述之情事，係提供一種兼具鹼可溶性樹脂與感光劑兩者功能、以聚醯亞胺樹脂為主成分、耐熱性、耐藥性、絕緣性、可撓性及殘膜性優異之適合作為正型光阻的感光性樹脂組成物及其製造方法。In view of the above, the present invention provides a function of both an alkali-soluble resin and a sensitizer, a polyiminoimine resin as a main component, heat resistance, chemical resistance, insulation, flexibility, and residual film property. An excellent photosensitive resin composition suitable as a positive photoresist and a method for producing the same.
本發明人等為達上述目的反覆專心檢討的結果，藉由使用下述一般式(1)表示的具有酚性羥基的聚醯亞胺的羥基的氫原子以每一氫原子為0.02~0.25莫耳的比例被1,2－萘醌二疊氮磺醯基取代之聚醯亞胺樹脂，作為鹼可溶性樹脂及感光劑而得到的感光性樹脂組成物，因而完成本發明。As a result of the above-mentioned purpose, the inventors of the present invention have repeatedly conducted the above-mentioned purpose, and the hydrogen atom of the hydroxyl group of the polyimine having a phenolic hydroxyl group represented by the following general formula (1) is 0.02 to 0.25 per hydrogen atom. The present invention has been completed as a photosensitive resin composition obtained by using a 1,2-naphthoquinonediazidesulfonyl group-substituted polyimine resin as an alkali-soluble resin and a sensitizer.
下述一般式(1)表示的具有酚性羥基的聚醯亞胺。Polyimine having a phenolic hydroxyl group represented by the following general formula (1).
本發明係使具有酚性羥基的聚醯亞胺樹脂的羥基的氫原子以每一氫原子為0.02~0.25莫耳的比例被1,2－萘醌二疊氮磺醯基取代之聚醯亞胺樹脂，作為鹼可溶性樹脂及感光劑。In the present invention, the hydrogen atom of the hydroxyl group of the polyimine resin having a phenolic hydroxyl group is substituted by a 1,2-naphthoquinonediazidesulfonyl group at a ratio of 0.02 to 0.25 mol per hydrogen atom. An amine resin as an alkali-soluble resin and a sensitizer.
藉由使用本發明的具有酚性羥基的聚醯亞胺樹脂的羥基的氫原子的一部分被1,2－萘醌二疊氮磺醯基取代之聚醯亞胺樹脂，可在寬廣的波長範圍的光下曝光，顯影時的殘膜性良好、且不受氧的阻礙、可容易地形成薄膜。而且，可形成解像力優異的圖形，更進一步由該組成物所得的薄膜與基材的密合性、耐熱性、絕緣性優異，可適用於電氣、電子構件、半導體元件等的保護膜。A polyimine resin substituted with a 1,2-naphthoquinonediazidesulfonyl group by using a hydrogen atom of a hydroxyl group of a phenolic hydroxyl group-containing polyimine resin of the present invention in a wide wavelength range Under the light exposure, the residual film property at the time of development is good, and it is not inhibited by oxygen, and a film can be formed easily. In addition, it is possible to form a pattern having excellent resolution, and further, the film obtained from the composition is excellent in adhesion to a substrate, heat resistance, and insulation, and is applicable to a protective film such as an electric or electronic member or a semiconductor element.
以下，更詳細說明本發明。作為本發明的先驅物之聚醯亞胺，係具有下述一般式(1)表示的重複單元者。Hereinafter, the present invention will be described in more detail. The polyimine which is a precursor of the present invention has a repeating unit represented by the following general formula (1).
上式中，一般式(1)的X為四價有機基，具體地為包含下述式表示的至少1種基。In the above formula, X in the general formula (1) is a tetravalent organic group, and specifically includes at least one group represented by the following formula.
一般式(1)中的Y為下述一般式(2)表示的2價有機基。Y in the general formula (1) is a divalent organic group represented by the following general formula (2).
式中A、a、b、c、R1 係如上述，B、C分別為碳數1~4的烷基或氫原子，可為相同或相異，具體地例如甲基、乙基、丙基、丁基，其中以甲基、氫原子從原料取得容易度的點上較理想。Wherein A, a, b, c, and R 1 are as defined above, and B and C are each an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, which may be the same or different, specifically, for example, methyl, ethyl or propyl. The base and the butyl group are preferable in that the methyl group and the hydrogen atom are easily obtained from the raw material.
作為Y，具體地例如下述的構造。Specifically, Y is, for example, the following structure.
而且，一般式(1)中的Z為下述一般式(3)表示的二價有機基。Further, Z in the general formula (1) is a divalent organic group represented by the following general formula (3).
上述式中，D為選自
作為Z，具體地例如下述的構造。Specifically, Z is, for example, the following structure.
而且，一般式(1)中的W為下述一般式(4)表示的二價有機基。Further, W in the general formula (1) is a divalent organic group represented by the following general formula (4).
一般式(4)中，R2 為碳數1~8的一價烴基，分別可為相同或相異。具體地，例如甲基、乙基、丙基、丁基、戊基、己基等的烷基、環戊基、環己基等的環烷基、苯基等的芳香基、苯甲基、苯乙基等的芳烷基、乙烯基、烯丙基、丙烯基、異丙烯基、丁烯基等烯基、丙烯醯基、甲基丙烯醯基等。從原料取得容易度的點，以甲基、乙基、苯基、乙烯基較理想。又h為1至80為止的正數，較理想為3~70，更理想為5~50。In the general formula (4), R 2 is a monovalent hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different. Specifically, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; an aromatic group such as a phenyl group; a benzyl group or a phenyl group; An alkenyl group such as an aralkyl group such as a arylalkyl group, a vinyl group, an allyl group, a propenyl group, an isopropenyl group or a butenyl group; an acryl group; a methacryl group; A point which is easy to obtain from a raw material is preferably a methyl group, an ethyl group, a phenyl group or a vinyl group. Further, h is a positive number from 1 to 80, preferably from 3 to 70, more preferably from 5 to 50.
而且，一般式(1)中的l、m、n分別為2≦l≦2000、0≦m≦2000、0≦n≦2000的正數，滿足0.1≦l/(l＋m＋n)≦1、0≦m/(l＋m＋n)≦0.8、0≦n/(l＋m＋n)≦0.8的正數。Moreover, l, m, and n in the general formula (1) are positive numbers of 2≦l≦2000, 0≦m≦2000, 0≦n≦2000, respectively, satisfying 0.1≦l/(l+m+n)≦1, 0≦m /(l+m+n) ≦ 0.8, 0≦n/(l+m+n) 正 0.8 positive number.
本發明的一般式(1)表示的聚醯亞胺的分子量，通常可為2000至800000的程度，較理想為5000至500000。分子量為5000以下，因所得的聚醯亞胺的覆膜強度低，故不理想，5000000以上因缺乏對溶劑的相溶性，故不理想。The molecular weight of the polyimine represented by the general formula (1) of the present invention may be usually from 2,000 to 800,000, more preferably from 5,000 to 500,000. When the molecular weight is 5,000 or less, the obtained polyimide pigment has a low film strength, which is not preferable, and 5,000,000 or more is not preferable because it lacks compatibility with a solvent.
本發明將具有如此的酚性羥基的聚醯亞胺樹脂的羥基的氫原子的一部分被1,2－萘醌二疊氮磺醯基取代，雖可得目的的感光性組成物，作為1,2－醌二疊氮化合物部分酯化的方法可採用部分酯化的一般方法而得。In the present invention, a part of a hydrogen atom of a hydroxyl group of a polyimine resin having such a phenolic hydroxyl group is substituted with 1,2-naphthoquinonediazidesulfonyl group, and a photosensitive composition of interest can be obtained as 1, The partial esterification of the 2-indolyl compound can be carried out by a general method of partial esterification.
上述具有酚性羥基的聚醯亞胺，可使具有酚性羥基的二胺以及二酸酐，需要時以不含酚基的二胺與/或二胺基矽酮反應，得到聚醯胺酸後，藉由脫水閉環(ring closure)反應而得到。The polyimine having a phenolic hydroxyl group can be a diamine having a phenolic hydroxyl group and a dianhydride, and if necessary, reacting with a phenol group-free diamine and/or a diamino fluorenone to obtain a polyamine acid. It is obtained by a ring closure reaction.
作為用於聚醯胺酸的聚合之二酸酐，例如3,3’,4,4’－二苯碸四羧酸二酐、3,3’,4,4’－聯苯四羧酸二酐、2,3’,3,4’－聯苯四羧酸二酐、5－(2,5－二氧四氫－3－呋喃基)－3－甲基－3－環己烷－1,2－二羧酸酐、4－(2,5－二氧四氫呋喃－3－醯基)－1,2,3,4－四氫萘－1,2－二羧酸酐、1,2,3,4－丁四羧酸二酐、3,3’,4,4’－苯酮四羧酸二酐、4,4’－六氟二異亞丙基二酞酸二酐、2,2－雙(對苯三酸苯基)丙烷、1,3－四甲基二矽氧烷二酞酸二酐、4,4－氧二酞酸二酐。As a dianhydride for the polymerization of polylysine, for example, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride , 2,3',3,4'-biphenyltetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1, 2-Dicarboxylic anhydride, 4-(2,5-dioxotetrahydrofuran-3-indenyl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 1,2,3,4 - butyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-hexafluorodiisopropylidene dicarboxylic acid dianhydride, 2,2-dual ( Phenyltrimethanol phenyl)propane, 1,3-tetramethyldioxane dicarboxylic acid dianhydride, 4,4-oxadic acid dianhydride.
而且，作為具有酚性羥基、羧基之二胺，例如3,3’－二胺基－4,4’－二羥基聯苯、2,2’－二胺基－4,4’－二羥基聯苯、2,2－雙(4－胺基－3－羥苯基)丙烷、2,2－雙(3－胺基－4－羥苯基)丙烷、9,9’－雙(3－胺基－4－羥苯基)芴、2,2’－亞甲基雙〔6－(4－胺基－3,5－二甲基苯甲基)－4－甲基〕酚、3,3’－二胺基－4,4’－二羥基苯醚、2,2－雙(3－胺基－4－羥苯基)六氟丙烷等的具有酚基的二胺等。Further, as a diamine having a phenolic hydroxyl group or a carboxyl group, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 2,2'-diamino-4,4'-dihydroxyl linkage Benzene, 2,2-bis(4-amino-3-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 9,9'-bis(3-amine 4-hydroxyphenyl)indole, 2,2'-methylenebis[6-(4-amino-3,5-dimethylbenzyl)-4-methyl]phenol, 3,3 A diamine having a phenol group such as -diamino-4,4'-dihydroxyphenyl ether or 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.
又作為不含酚基的二胺，例如4,4’－二胺基苯醯替苯胺(4,4’－diaminobenzanilide)、4,4’－二胺基苯醚、3,4’－二胺基苯醚、4,4’－二胺基二苯碸、3,3’－二甲基－4,4’－二胺基聯苯、4,4’－(對亞苯基二異亞丙基)二苯胺、4,4’－(間亞苯基二異亞丙基)二苯胺、1,3－雙(4－胺基苯氧基)苯、1,4－雙(4－胺基苯氧基)苯、1,3－雙(3－胺基苯氧基)苯、2,2－雙〔4－(4－胺基苯氧基)苯基〕丙烷、2,2－雙〔4－(4－胺基苯氧基)苯基〕六氟丙烷、雙〔4－(4－胺基苯氧基)苯基〕碸、雙〔4－(3－胺基苯氧基)苯基〕碸、4,4’－雙(4－胺基苯氧基)聯苯、9,9－雙(4－胺基苯基)芴等。Also as a phenol-free diamine, such as 4,4'-diaminobenzidine (4,4'-diaminobenzanilide), 4,4'-diaminophenyl ether, 3,4'-diamine Phenylphenyl ether, 4,4'-diaminodiphenyl hydrazine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-(p-phenylene diisopropylene Diphenylamine, 4,4'-(m-phenylene diisopropylidene)diphenylamine, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-amino Phenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-dual 4-(4-Aminophenoxy)phenyl]hexafluoropropane, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)benzene碸, 4,4'-bis(4-aminophenoxy)biphenyl, 9,9-bis(4-aminophenyl)anthracene, and the like.
於聚醯胺酸的合成，對四羧酸二酐成分之二胺成分的比例，根據調整聚醯亞胺的分子量而適當決定，通常莫耳比為0.95~1.05，更理想為0.98~1.02的範圍。而且，為調整聚醯亞胺的分子量，可添加酞酸酐、苯胺等的一官能基的酸酐以及胺化合物。該情況的添加量，對四羧酸二酐成分或二胺成分為5莫耳%以下較理想。The ratio of the polyamine derivative to the diamine component of the tetracarboxylic dianhydride component is appropriately determined depending on the molecular weight of the polyimine, and the molar ratio is usually 0.95 to 1.05, more preferably 0.98 to 1.02. range. Further, in order to adjust the molecular weight of the polyimine, an acid anhydride such as phthalic anhydride or an aniline or an amine compound may be added. The amount of addition in this case is preferably 5 mol% or less to the tetracarboxylic dianhydride component or the diamine component.
聚醯亞胺的合成係由上述所得的聚醯胺酸溶液，升溫至通常為80~200℃，較理想為140~180℃的溫度範圍，或將醋酸酐/吡啶混合溶液添加於聚醯胺酸溶液，接著所得的溶液升溫至50℃上下，聚醯胺酸的醯胺部分進行脫水閉環反應，得到聚醯亞胺。The polyimine synthesis is carried out by heating the polyamic acid solution obtained above to a temperature of usually 80 to 200 ° C, preferably 140 to 180 ° C, or adding a acetic anhydride/pyridine mixed solution to polyamine. The acid solution is then heated to 50 ° C or higher, and the guanamine portion of the poly-proline is subjected to a dehydration ring-closure reaction to obtain a polyimine.
二胺與二酸酐的反應，通常在溶劑中進行。作為如此的溶劑，只要可溶解聚醯亞胺即可。作為溶劑的具體例，四氫呋喃、苯甲醚等的醚類；環己酮、2－丁酮、甲基異丁基酮、2－庚酮、2－辛酮、苯乙酮等的配類；醋酸丁酯、苯甲酸甲酯、γ－丁內酯等的酯類；丁基醋酸溶纖劑、丙二醇單甲醚醋酸酯等的甲基纖維素類(cellosolve)；N,N－二甲基甲醯胺、N,N－二甲基乙醯胺、N－甲基－2－吡咯烷酮等的醯胺類與甲苯、二甲苯等的芳香族烴類，較理想為酮類、酯類以及甲基纖維素類，特別理想為γ－丁內酯、丙二醇單甲醚醋酸酯、N,N－二甲基乙醯胺、n－甲基－2－吡咯烷酮。這些溶劑可使用單獨1種或2種以上的組合。通常每一批次的產量，考慮溶解黏度，聚醯亞胺的濃度調整為10~40重量%的範圍。The reaction of the diamine with the dianhydride is usually carried out in a solvent. As such a solvent, it is sufficient to dissolve the polyimine. Specific examples of the solvent include ethers such as tetrahydrofuran and anisole; and ligands such as cyclohexanone, 2-butanone, methyl isobutyl ketone, 2-heptanone, 2-octanone, and acetophenone; An ester of butyl acetate, methyl benzoate or γ-butyrolactone; a cellosolve such as cellosolve butyl acetate or propylene glycol monomethyl ether acetate; N,N-dimethyl Anthracene such as formamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone, and aromatic hydrocarbons such as toluene and xylene are preferably ketones, esters and The base cellulose is particularly preferably γ-butyrolactone, propylene glycol monomethyl ether acetate, N,N-dimethylacetamide or n-methyl-2-pyrrolidone. These solvents may be used alone or in combination of two or more. Usually, the yield of each batch, considering the dissolved viscosity, the concentration of polyimine is adjusted to a range of 10 to 40% by weight.
具有1,2－萘醌二疊氮磺醯基的感光性組成物的合成，係藉由於上述所得的聚醯亞胺溶液中添加1,2－醌二疊氮基磺醯氯以及鹼性化合物，於室溫攪拌，可得目的的感光性組成物。The photosensitive composition having a 1,2-naphthoquinonediazidesulfonyl group is synthesized by adding 1,2-quinonediazidesulfonyl chloride and a basic compound to the polyimine solution obtained above. The mixture was stirred at room temperature to obtain the intended photosensitive composition.
亦即，使具有酚性羥基的二胺以及二酸酐，需要時以不含酚性羥基的二胺與/或二胺基矽酮反應，得到聚醯胺酸後，藉由脫水閉環(ring closure)反應得到一般式(5)表示的具有酚性羥基的聚醯亞胺，然後與1,2－醌二疊氮化合物反應所製造得到。That is, a diamine having a phenolic hydroxyl group and a dianhydride are reacted with a diamine and/or a diamine fluorenone which does not contain a phenolic hydroxyl group, if necessary, to obtain a polylysine, followed by a dehydration ring closure (ring closure) The reaction is carried out by obtaining a polyimine having a phenolic hydroxyl group represented by the general formula (5) and then reacting with a 1,2-quinonediazide compound.
於該情況，作為用於1,2－萘醌二疊氮磺醯基的導入之1,2－醌二疊氮化合物，例如1,2－萘醌二疊氮基－4－磺醯氯、1,2－萘醌二疊氮基－5－磺醯氯。In this case, as an introduced 1,2-quinonediazide compound for 1,2-naphthoquinonediazidesulfonyl group, for example, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride.
此時聚醯亞胺樹脂的羥基的氫原子以1個0.02~0.25莫耳%的比例被1,2－萘醌二疊氮磺醯基取代。超過0.25莫耳%被取代時，感光性樹脂溶液為高濃度的情況，保溫溫度高以及二疊氮可能分解，分解的情況，有歷久增黏、取用困難的情形。而且，少於0.02莫耳%被取代時，顯影時殘膜性差，圖形無法切斷，無法使用作為感光性樹脂組成物。At this time, the hydrogen atom of the hydroxyl group of the polyimine resin is substituted with 1,2-naphthoquinonediazidesulfonyl group at a ratio of 0.02 to 0.25 mol%. When more than 0.25 mol% is substituted, the photosensitive resin solution is in a high concentration, the holding temperature is high, and the diazide may be decomposed and decomposed, and it may be difficult to obtain adhesion for a long time. Further, when it is substituted by less than 0.02 mol%, the residual film property during development is poor, the pattern cannot be cut, and it is not possible to use it as a photosensitive resin composition.
而且，作為此時的鹼性化合物，只要是反應時與生成的氯化氫反應產生鹽，促進反應者，無特別限制。舉例如二乙胺、三乙胺等。In addition, the basic compound at this time is not particularly limited as long as it reacts with the generated hydrogen chloride to form a salt during the reaction and promotes the reaction. For example, diethylamine, triethylamine, and the like.
於本發明，如此導入1,2－萘醌二疊氮磺醯基的聚醯亞胺使用作為成膜材料樹脂及感光劑，可再調配添加成分。作為如此的添加成分，例如為提高塗佈性，可添加慣用的界面活性劑。作為界面活性劑，以非離子性者較理想，例如氟系界面活性劑，具體地例如全氟烷基聚氧乙烯乙醇、氟化烷酯、全氟烷基氧化物胺、含氟有機矽氧烷系化合物等。In the present invention, the polyimine which is introduced into the 1,2-naphthoquinonediazidesulfonyl group is used as a film-forming material resin and a sensitizer, and the additive component can be further formulated. As such an additive component, for example, in order to improve coatability, a conventional surfactant can be added. As the surfactant, it is preferred to be nonionic, such as a fluorine-based surfactant, specifically, for example, perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkyl oxide amine, fluorine-containing organic oxime An alkyl compound or the like.
這些可以使用市售產品，例如FLUORAD「FC－4430」(任一種皆為住友3M(股)製)、SAFRON「S－141」以及「S－145」(任一種皆為旭硝子(股)製)、UNIDYNE「DS－401」、「DS－4031」以及「DS－451」(任一種皆為大金工業(股)製)、MEGAFACE「F－8151」(大日本油墨工業(股)製)、「X－70－093」(任一種皆為信越化學工業(股)製)等。這些之中，較理想為FLUORAD「FC－4430」(住友3M(股)製)以及「X－70－093」(信越化學工業(股)製)。These can be used as commercially available products, such as FLUORAD "FC-4430" (any one is Sumitomo 3M (share)), SAFRON "S-141" and "S-145" (any one is Asahi Glass Co., Ltd.) UNIDYNE "DS-401", "DS-4031" and "DS-451" (any one is Daikin Industries Co., Ltd.), MEGAFACE "F-8151" (Daily Ink Industry Co., Ltd.), "X-70-093" (any one is Shin-Etsu Chemical Co., Ltd.). Among them, FLUORAD "FC-4430" (Sumitomo 3M (share) system) and "X-70-093" (Shin-Etsu Chemical Industry Co., Ltd.) are preferable.
作為其他添加成分，作為密合性提升劑可添加例如環氧系矽烷偶合劑KBM－403(信越化學製)等之矽烷偶合劑。此外，本發明的感光性組成物用於光阻材料等的情況，通常用於光阻材料等可添加其他任意的添加成分。而且，上述添加成分的添加量為在不妨礙本發明的效果的範圍內之一般量。As the other additive component, a decane coupling agent such as an epoxy decane coupling agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be added as the adhesion-improving agent. Further, when the photosensitive composition of the present invention is used for a photoresist or the like, it is usually used for a photoresist or the like, and any other additive component may be added. Further, the amount of the above-mentioned additive component added is a general amount within a range that does not impair the effects of the present invention.
再者，為提高殘膜性，可依需要調配其他感光劑而得。與樹脂互相產生作用、對顯影液產生溶解阻止效果之感光劑較理想，具體地例如「NT－300P」(東洋合成工業(股)製)。Further, in order to improve the residual film property, other sensitizers may be prepared as needed. A sensitizer which acts on the resin and has a dissolution preventing effect on the developer is preferable, and specifically, for example, "NT-300P" (manufactured by Toyo Seiki Co., Ltd.).
本發明的光硬化性樹脂組成物的調製可以一般的方法進行，攪拌混合上述各成分以及依據需要之上述有機溶劑、添加劑等，然後依需要以過濾器等過濾固體成分，可調製本發明的感光性樹脂組成物。The preparation of the photocurable resin composition of the present invention can be carried out by a general method, and the above components and the above-mentioned organic solvent, additives, and the like are stirred and mixed, and then the solid component is filtered by a filter or the like as needed to prepare the photosensitive material of the present invention. Resin composition.
如此調製的本發明的感光性樹脂組成物，適合使用於例如半導體元件的保護膜、配線的保護膜、保護膜、防焊劑，更進一步作為細微加工用光阻等的材料。The photosensitive resin composition of the present invention prepared as described above is suitably used for, for example, a protective film for a semiconductor element, a protective film for a wiring, a protective film, a solder resist, and the like as a material for photoresist for fine processing.
作為使用上述感光性樹脂組成物形成圖形之圖形的形成方法，係包含下述步驟。The method of forming a pattern for forming a pattern using the above-mentioned photosensitive resin composition includes the following steps.
(i)將上述的感光性樹脂組成物塗佈於基板上或以其他方法製膜的步驟；(ii)透過光罩，用包含波長240~500nm的光源的光進行曝光步驟以及需要時進行曝光後的加熱(所謂PEB步驟)步驟；(iii)以顯影液進行顯影的步驟。(i) a step of applying the above-mentioned photosensitive resin composition onto a substrate or forming a film by another method; (ii) passing through a photomask, performing an exposure step with light including a light source having a wavelength of 240 to 500 nm, and performing exposure as needed a subsequent heating (so-called PEB step) step; (iii) a step of developing with a developing solution.
藉由以上3個步驟形成圖形後，再經(iV)形成圖形後，進行後段硬化之加熱的步驟，可得最終目的的保護膜。After the pattern is formed by the above three steps, and then the pattern is formed by (iV), the step of heating in the subsequent stage hardening is performed to obtain a protective film of the final purpose.
於本發明的圖形的形成方法，首先將上述的感光性樹脂組成物塗佈於基板上。作為上述基板，例如矽晶圓、塑膠、陶瓷製電路基板等。而且，該溶液可以別的方法薄膜化，再將其貼合於基板之方法。In the method of forming a pattern of the present invention, first, the above-mentioned photosensitive resin composition is applied onto a substrate. Examples of the substrate include a germanium wafer, a plastic, a ceramic circuit board, and the like. Further, the solution can be thinned by another method and attached to the substrate.
作為塗佈法，可採用習知的微影技術進行。例如浸漬法、旋轉塗佈法、滾輪塗佈法等的手法進行塗佈。塗佈的量，可依目的適當選擇，以膜厚為0.1~100μm較理想。而且，可預先形成該組成物的薄膜，將該薄膜貼合於基材。As the coating method, it can be carried out by a conventional lithography technique. For example, it is applied by a method such as a dipping method, a spin coating method, or a roll coating method. The amount of coating can be appropriately selected depending on the purpose, and the film thickness is preferably 0.1 to 100 μm. Further, a film of the composition may be formed in advance, and the film may be bonded to a substrate.
此時，為有效進行光分解反應，需要時藉由預熱可先將溶劑揮發。預熱係例如於40~140℃下1分~1小時的程度進行。然後，透過光罩，以波長240~500nm的光進行曝光，使其分解。上述光罩可例如挖出所期望的圖形者。又光罩的材質為可遮蔽上述波長240~500nm的光者較理想，例如適合使用鉻等，但不限於這些。At this time, in order to carry out the photodecomposition reaction efficiently, the solvent may be volatilized first by preheating as needed. The preheating system is carried out, for example, at a temperature of from 40 to 140 ° C for 1 minute to 1 hour. Then, it is exposed to light having a wavelength of 240 to 500 nm through a photomask to be decomposed. The reticle can for example dig out the desired figure. Further, the material of the photomask is preferably such that light having a wavelength of 240 to 500 nm can be shielded. For example, chromium or the like is preferably used, but it is not limited thereto.
作為上述波長240~500nm的光，例如藉由輻射線產生裝置產生各種波長的光，例如g線、i線等的紫外線、遠紫外線(248nm)等。曝光量例如為10~2000mJ/cm2 較理想。需要時為再提高顯影感度，可進行曝光後的加熱處理。上述曝光後的加熱處理，例如於40~140℃下0.5分~10分鐘。As the light having the wavelength of 240 to 500 nm, light of various wavelengths is generated by, for example, a radiation generating device, for example, ultraviolet rays such as g-line or i-line, far ultraviolet rays (248 nm), or the like. The exposure amount is preferably, for example, 10 to 2000 mJ/cm 2 . If necessary, in order to further improve the development sensitivity, heat treatment after exposure can be performed. The heat treatment after the above exposure is, for example, 0.5 to 10 minutes at 40 to 140 °C.
上述曝光或曝光後加熱處理後，以顯影液進行顯影。作為顯影液，使用有機溶劑系作為溶劑，例如二甲基乙醯胺、環己酮等。顯影可以一般方法，例如浸漬圖形形成物等進行。然後，依需要進行洗淨、洗滌、乾燥等，得到具有所期望的圖形之組成物薄膜。而且，圖形的形成方法雖如上述，無需形成圖形時，例如只要形成均勻的薄膜的情況，除不使用上述光罩外，可以上述圖形的形成方法相同的方式進行。After the above exposure or heat treatment after exposure, development is carried out with a developer. As the developer, an organic solvent is used as a solvent, for example, dimethylacetamide, cyclohexanone or the like. The development can be carried out by a general method such as impregnation of a pattern formation or the like. Then, washing, washing, drying, and the like are carried out as needed to obtain a film having a desired pattern. Further, the pattern forming method is as described above, and when it is not necessary to form a pattern, for example, a uniform film may be formed, and the method of forming the pattern may be carried out in the same manner as the above method without using the mask.
而且，所得的圖形再使用烘箱、加熱板，於120~300℃下10分鐘~10小時的程度進行加熱，藉由除去殘存的揮發成分，可形成對基材的密合力優異、耐熱性、強度、又電的特性亦良好的薄膜。Further, the obtained pattern is heated by using an oven or a hot plate at a temperature of 120 to 300 ° C for 10 minutes to 10 hours, and by removing the remaining volatile components, the adhesion to the substrate is excellent, heat resistance and strength are formed. A film that is also good in electrical properties.
如此由上述感光性樹脂組成物所得的硬化薄膜，與基材的密合性、耐熱性、電絕緣性優異，除適合作為電氣、電子構件、半導體元件等的保護膜，可用於細微圖形的形成，所形成的薄膜對基材的接著性、電的特性、機械特性等優異，適合使用於半導體元件的保護膜、配線的保護膜、保護膜、防焊劑。The cured film obtained from the above-mentioned photosensitive resin composition is excellent in adhesion to a substrate, heat resistance, and electrical insulation, and can be used as a protective film for electric, electronic members, semiconductor elements, etc., and can be used for formation of fine patterns. The formed film is excellent in adhesion to the substrate, electrical properties, mechanical properties, and the like, and is suitable for use as a protective film for a semiconductor element, a protective film for wiring, a protective film, and a solder resist.
以下，以合成例、實施例以及比較例具體地說明本發明，但本發明不限於這些例示。Hereinafter, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these examples.
於具備攪拌機、溫度計以及氮氣取代裝置之燒瓶內，置入4,4’－氧二酞酸二酐31.0g(0.1莫耳)以及n－甲基－2－吡咯烷酮150g。然後，將2,2－雙(4－胺基－3－羥苯基)丙烷25.8g(0.1莫耳)溶解於n－甲基－2－吡咯烷酮100g的溶液一邊調節反應系統的溫度不超過50℃，一邊滴入上述燒瓶內。滴完後，再於室溫下攪拌10小時。接著，設置附水分接受器之回流冷卻器於該燒瓶後，加入二甲苯70g，升溫至150℃，保持於該溫度6小時，可得棕色的溶液。Into a flask equipped with a stirrer, a thermometer, and a nitrogen substitution device, 31.0 g (0.1 mol) of 4,4'-oxydiphthalic acid dianhydride and 150 g of n-methyl-2-pyrrolidone were placed. Then, 25.8-bis (4-amino-3-hydroxyphenyl)propane 25.8 g (0.1 mol) was dissolved in a solution of 100 g of n-methyl-2-pyrrolidone while adjusting the temperature of the reaction system to not exceed 50. At ° C, it was dropped into the above flask. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, a reflux condenser equipped with a water receiver was placed in the flask, and 70 g of xylene was added thereto, and the temperature was raised to 150 ° C, and the temperature was maintained at this temperature for 6 hours to obtain a brown solution.
如此所得的棕色的溶液冷卻至室溫(25℃)後，分析其IR光譜，沒有觀察到來自聚醯胺酸的吸收，觀察到1780cm－ 1 以及1720cm－ 1 基於醯亞胺基的吸收，而且觀察到3400cm－ 1 附近來自酚基的吸收，得知為以下述式為重複單元的樹脂。而且，凝膠滲透色譜分析法(GPC)分析的結果，以聚苯乙烯換算的數量平均分子量(Mn)為52300。After thus resulting brown solution was cooled to room temperature (25 deg.] C), its IR spectrum analysis, no absorption was observed from the polyamide acid was observed 1780cm - 1 and 1720 - based on the absorption of an imino acyl, and observed 3400cm - 1 absorbed from the vicinity of the phenolic group, that is a repeating unit represented by the following formula as a resin. Further, as a result of gel permeation chromatography (GPC) analysis, the number average molecular weight (Mn) in terms of polystyrene was 52,300.
然後，將所得的樹脂溶液200g(樹脂固體成分17%)以及1,2－萘醌二疊氮基－5－磺醯氯3.43g、三乙胺1.37g置入燒瓶，室溫下攪拌6小時。反應結束後，反應溶液放入1公升的甲醇，乾燥後，得到目的的聚醯亞胺。該樹脂的1H－NMR分析的結果，來自酚性羥基之10ppm的峰減少90%，反之觀察到5.3ppm來自鍵結於與二疊氮基鍵結的碳相鄰的碳之氫的峰，得知下述式表示的重複單元的構造之樹脂(A－1)。而且，凝膠滲透色譜分析法(GPC)分析的結果，該樹脂的數量平均分子量為59200。Then, 200 g of the obtained resin solution (resin solid content: 17%), 1.43 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 1.37 g of triethylamine were placed in a flask, and stirred at room temperature for 6 hours. . After completion of the reaction, the reaction solution was placed in 1 liter of methanol, and after drying, the desired polyimine was obtained. As a result of 1H-NMR analysis of the resin, the peak of 10 ppm from the phenolic hydroxyl group was reduced by 90%, whereas 5.3 ppm of the peak derived from hydrogen bonded to the carbon bonded to the diazide group was observed. The resin (A-1) having the structure of the repeating unit represented by the following formula is known. Further, as a result of gel permeation chromatography (GPC) analysis, the resin had a number average molecular weight of 59,200.
於具備攪拌機、溫度計以及氮氣取代裝置之燒瓶內，置入4,4’－氧二酞酸二酐54.3g(0.175莫耳)、4,4’－六氟異亞丙基二酞酸二酐33.3g(0.075莫耳)以及n－甲基－2－吡咯烷酮400g。然後，將2,2－雙(4－胺基－3－羥苯基)丙烷64.6g(0.25莫耳)溶解於n－甲基－2－吡咯烷酮200g的溶液一邊調節反應系統的溫度不超過50℃，一邊滴入上述燒瓶內。滴完後，再於室溫下攪拌10小時。接著，設置附水分接受器之回流冷卻器於該燒瓶後，加入甲苯70g，升溫至150℃，保持於該溫度6小時，可得棕色的溶液。In a flask equipped with a stirrer, a thermometer, and a nitrogen substitution device, 54.3 g (0.175 mol) of 4,4'-oxydiphthalic acid dianhydride and 4,4'-hexafluoroisopropylidene dicarboxylic acid dianhydride were placed. 33.3 g (0.075 mol) and n-methyl-2-pyrrolidone 400 g. Then, 64.6 g (0.25 mol) of 2,2-bis(4-amino-3-hydroxyphenyl)propane was dissolved in a solution of 200 g of n-methyl-2-pyrrolidone while adjusting the temperature of the reaction system to not exceed 50. At ° C, it was dropped into the above flask. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, a reflux condenser equipped with a water receiver was placed in the flask, and 70 g of toluene was added thereto, and the temperature was raised to 150 ° C, and the temperature was maintained at this temperature for 6 hours to obtain a brown solution.
如此所得的棕色的溶液冷卻至室溫(25℃)後，得到具有酚性羥基之聚醯亞胺(樹脂固體成分20.3%)。然後，將該聚醯亞胺溶液300g以及1,2－萘醌二疊氮基－5－磺醯氯5.71g、三乙胺2.28g置入燒瓶，於室溫下攪拌6小時。反應結束後，反應溶液放入1公升的甲醇，乾燥後，得到目的的聚醯亞胺。該樹脂的1H－NMR分析的結果，來自酚性羥基之10ppm的峰減少90%，反之觀察到5.3ppm來自鍵結於與二疊氮基鍵結的碳相鄰的碳之氫的峰，得知下述式表示的重複單元的構造之樹脂(A－2)。而且，凝膠滲透色譜分析法(GPC)分析的結果，該樹脂的數量平均分子量為63000。The brown solution thus obtained was cooled to room temperature (25 ° C) to obtain a polyimine having a phenolic hydroxyl group (resin solid content: 20.3%). Then, 300 g of the polyimine solution and 5.71 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 2.28 g of triethylamine were placed in a flask, and the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the reaction solution was placed in 1 liter of methanol, and after drying, the desired polyimine was obtained. As a result of 1H-NMR analysis of the resin, the peak of 10 ppm from the phenolic hydroxyl group was reduced by 90%, whereas 5.3 ppm of the peak derived from hydrogen bonded to the carbon bonded to the diazide group was observed. The resin (A-2) having a structure of a repeating unit represented by the following formula is known. Further, as a result of gel permeation chromatography (GPC) analysis, the resin had a number average molecular weight of 63,000.
於具備攪拌機、溫度計以及氮氣取代裝置之燒瓶內，置入3,3’,4,4’－二苯碸四羧酸二酐89.6g(0.25莫耳)以及N,N’－二甲基乙醯胺500g。然後，將2,2－雙(4－胺基－3－羥苯基)丙烷32.3g(0.125莫耳)以及9,9－雙(4－胺基苯基)芴43.6g(0.125莫耳)溶解於N,N’－二甲基乙醯胺200g的溶液一邊調節反應系統的溫度不超過50℃，一邊滴入上述燒瓶內。滴完後，再於室溫下攪拌10小時。接著，設置附水分接受器之回流冷卻器於該燒瓶後，加入甲苯180g，升溫至150℃，保持於該溫度6小時，可得棕色的溶液。In a flask equipped with a stirrer, a thermometer, and a nitrogen substitution device, 89.6 g (0.25 m) of 3,3',4,4'-diphenyltetracarboxylic dianhydride and N,N'-dimethyl B were placed. Guanamine 500g. Then, 32.3 g (0.125 mol) of 2,2-bis(4-amino-3-hydroxyphenyl)propane and 43.6 g (0.125 mol) of 9,9-bis(4-aminophenyl)anthracene. A solution dissolved in 200 g of N,N'-dimethylacetamide was added dropwise to the flask while adjusting the temperature of the reaction system to not more than 50 °C. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, a reflux condenser equipped with a water receiver was placed in the flask, and 180 g of toluene was added thereto, and the temperature was raised to 150 ° C, and the temperature was maintained at this temperature for 6 hours to obtain a brown solution.
如此所得的棕色的溶液冷卻至室溫(25℃)後，得到具有酚性羥基之聚醯亞胺(樹脂固體成分20.0%)。然後，將該聚醯亞胺溶液300g以及1,2－萘醌二疊氮基－5－磺醯氯2.64g、三乙胺1.05g置入燒瓶，於室溫下攪拌6小時。反應結束後，反應溶液放入1公升的甲醇，乾燥後，得到目的的聚醯亞胺。該樹脂的1H－NMR分析的結果，來自酚性羥基之10ppm的峰減少90%，反之觀察到5.3ppm來自鍵結於與二疊氮基鍵結的碳相鄰的碳之氫的峰，得知下述式表示的重複單元的構造之樹脂(A－3)。而且，凝膠滲透色譜分析法(GPC)分析的結果，該樹脂的數量平均分子量為56800。The brown solution thus obtained was cooled to room temperature (25 ° C) to obtain a polyiminoimine having a phenolic hydroxyl group (resin solid content 20.0%). Then, 300 g of the polyimine solution and 2.64 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 1.05 g of triethylamine were placed in a flask, and the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the reaction solution was placed in 1 liter of methanol, and after drying, the desired polyimine was obtained. As a result of 1H-NMR analysis of the resin, the peak of 10 ppm from the phenolic hydroxyl group was reduced by 90%, whereas 5.3 ppm of the peak derived from hydrogen bonded to the carbon bonded to the diazide group was observed. The resin (A-3) having the structure of the repeating unit represented by the following formula is known. Further, as a result of gel permeation chromatography (GPC) analysis, the resin had a number average molecular weight of 56,800.
於具備攪拌機、溫度計以及氮氣取代裝置之燒瓶內，置入4,4’－氧二酞酸二酐77.6g(0.25莫耳)以及N,N’－二甲基乙醯胺500g。然後，將2,2－雙(4－胺基－3－羥苯基)丙烷51.7g(0.2莫耳)以及二胺基矽氧烷(但一般式(6)的f平均為9者)45.8g(0.05莫耳)溶解於N,N’－二甲基乙醯胺200g的溶液一邊調節反應系統的溫度不超過50℃，一邊滴入上述燒瓶內。滴完後，再於室溫下攪拌10小時。接著，設置附水分接受器之回流冷卻器於該燒瓶後，加入甲苯150g，升溫至150℃，保持於該溫度6小時，可得棕色的溶液。In a flask equipped with a stirrer, a thermometer, and a nitrogen substitution device, 77.6 g (0.25 mol) of 4,4'-oxydiphthalic acid dianhydride and 500 g of N,N'-dimethylacetamide were placed. Then, 51.7 g (0.2 mol) of 2,2-bis(4-amino-3-hydroxyphenyl)propane and diamine decane (but the average f of the general formula (6) is 9) 45.8 g (0.05 mol) was dissolved in a solution of 200 g of N,N'-dimethylacetamide while the temperature of the reaction system was adjusted to not exceed 50 ° C, and the mixture was dropped into the flask. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, a reflux condenser equipped with a water receiver was placed in the flask, and 150 g of toluene was added thereto, and the temperature was raised to 150 ° C, and the temperature was maintained at this temperature for 6 hours to obtain a brown solution.
如此所得的棕色的溶液冷卻至室溫(25℃)後，得到具有酚性羥基之聚醯亞胺(樹脂固體成分20.5%)。然後，將該聚醯亞胺溶液300g以及1,2－萘醌二疊氮基－5－磺醯氯3.98g、三乙胺1.59g置入燒瓶，於室溫下攪拌6小時。反應結束後，反應溶液放入1公升的甲醇，乾燥後，得到目的的聚醯亞胺。該樹脂的1H－NMR分析的結果，來自酚性羥基之10ppm的峰減少90%，反之觀察到5.3ppm來自鍵結於與二疊氮基鍵結的碳相鄰的碳之氫的峰，得知下述式表示的重複單元的構造之樹脂(A－4)。而且，凝膠滲透色譜分析法(GPC)分析的結果，該樹脂的數量平均分子量為63200。The brown solution thus obtained was cooled to room temperature (25 ° C) to obtain a polyimine having a phenolic hydroxyl group (resin solid content: 20.5%). Then, 300 g of the polyimine solution, 3.98 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 1.59 g of triethylamine were placed in a flask, and the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the reaction solution was placed in 1 liter of methanol, and after drying, the desired polyimine was obtained. As a result of 1H-NMR analysis of the resin, the peak of 10 ppm from the phenolic hydroxyl group was reduced by 90%, whereas 5.3 ppm of the peak derived from hydrogen bonded to the carbon bonded to the diazide group was observed. The resin (A-4) having the structure of the repeating unit represented by the following formula is known. Further, as a result of gel permeation chromatography (GPC) analysis, the resin had a number average molecular weight of 63,200.
除1,2－萘醌二疊氮基－5－磺醯氯為7.72g、三乙胺為3.07g以外，其他與合成例1相同，得到聚醯亞胺。該樹脂的1H－NMR分析的結果，來自酚性羥基之10ppm的峰減少15%，反之觀察到5.3ppm來自鍵結於與二疊氮基鍵結的碳相鄰的碳之氫的峰，得知下述式表示的重複單元的構造之樹脂(A－5)。而且，凝膠滲透色譜分析法(GPC)分析的結果，該聚合物的數量平均分子量為65400。The polyimine was obtained in the same manner as in Synthesis Example 1 except that 1,2-naphthoquinonediazide-5-sulfonyl chloride was 7.72 g and triethylamine was 3.07 g. As a result of 1H-NMR analysis of the resin, the peak of 10 ppm from the phenolic hydroxyl group was reduced by 15%, whereas 5.3 ppm of the peak derived from hydrogen bonded to the carbon bonded to the diazide group was observed. A resin (A-5) having a structure of a repeating unit represented by the following formula is known. Further, as a result of gel permeation chromatography (GPC) analysis, the polymer had a number average molecular weight of 65,400.
除1,2－萘醌二疊氮基－5－磺醯氯為20.59g、三乙胺為8.20g以外，其他與合成例1相同，得到聚醯亞胺。該樹脂的1H－NMR分析的結果，來自酚性羥基之10ppm的峰減少40%，反之觀察到5.3ppm來自鍵結於與二疊氮基鍵結的碳相鄰的碳之氫的峰，得知下述式表示的重複單元的構造之樹脂(B－1)。而且，凝膠滲透色譜分析法(GPC)分析的結果，該聚合物的數量平均分子量為73000。The polyimine was obtained in the same manner as in Synthesis Example 1 except that 1,2-naphthoquinonediazide-5-sulfonyl chloride was 20.59 g and triethylamine was 8.20 g. As a result of 1H-NMR analysis of the resin, a peak of 10 ppm from the phenolic hydroxyl group was reduced by 40%, whereas 5.3 ppm of a peak derived from hydrogen bonded to the carbon bonded to the diazide group was observed. The resin (B-1) having a structure of a repeating unit represented by the following formula is known. Further, as a result of gel permeation chromatography (GPC) analysis, the polymer had a number average molecular weight of 73,000.
除1,2－萘醌二疊氮基－5－磺醯氯為0.51g、三乙胺為0.20g以外，其他與合成例1相同，得到聚醯亞胺。該樹脂的1H－NMR分析的結果，來自酚性羥基之10ppm的峰減少1%，反之觀察到5.3ppm來自鍵結於與二疊氮基鍵結的碳相鄰的碳之氫的峰，得知下述式表示的重複單元的構造之樹脂(B－2)。而且，凝膠滲透色譜分析法(GPC)分析的結果，該聚合物的數量平均分子量為54000。The polyimine was obtained in the same manner as in Synthesis Example 1 except that 1,2-naphthoquinonediazide-5-sulfonyl chloride was 0.51 g and triethylamine was 0.20 g. As a result of 1H-NMR analysis of the resin, a peak of 10 ppm from the phenolic hydroxyl group was decreased by 1%, whereas a peak of 5.3 ppm of hydrogen derived from carbon bonded to the carbon bonded to the diazide group was observed. A resin (B-2) having a structure of a repeating unit represented by the following formula is known. Further, as a result of gel permeation chromatography (GPC) analysis, the polymer had a number average molecular weight of 54,000.
使用上述合成例1~6所合成的感光性聚醯亞胺樹脂使樹脂固體成分為20.0%地溶解於環己酮的溶液，以記載於表1中的組成調配界面活性劑、感光劑等，然後攪拌、混合、溶解後，以聚四氟乙烯製0.2μm的過濾器進行精密的過濾，得到實施例1至6的本發明的光硬化性樹脂組成物。而且，為進行比較，用以得到合成例1的式(8)之作為中間體的式(7)所示的樹脂使樹脂固體成分為20.0%地溶解於環己酮的溶液，準備樹脂溶液C－1。Using the photosensitive polyimine resin synthesized in the above Synthesis Examples 1 to 6, a resin solid content of 20.0% was dissolved in a cyclohexanone solution, and the composition described in Table 1 was used to prepare a surfactant, a sensitizer, and the like. Then, the mixture was stirred, mixed, and dissolved, and then precisely filtered through a 0.2 μm filter made of polytetrafluoroethylene to obtain the photocurable resin compositions of the present invention of Examples 1 to 6. Further, for comparison, a resin represented by the formula (7) which is an intermediate of the formula (8) of Synthesis Example 1 was obtained by dissolving a resin solid component in a solution of 20.0% in cyclohexanone to prepare a resin solution C. -1.
然後，經六甲基二矽氮烷進行底塗處理之6吋矽晶圓2片以及6吋矽晶圓的全部表面電鍍膜厚2μm的銅之銅基板1片，使用旋轉塗佈機，以表中記載的膜厚塗佈各實施例的組成物。準備的3片晶圓中，就1片矽基板，為了除去溶劑於100℃ 1分鐘以加熱板加熱乾燥後，透過具有等間隔的線與空白之線寬1μm至20的石英製的光罩，以表1中記載的波長的光與曝光量進行照射。而且，此處NSR－1755i7A表示尼康(Nikon)製步進型曝光裝置，PLA－600FA表示佳能(Canon)製接觸對準型曝光裝置。照射後，於80℃下加熱1小時，然後冷卻。Then, two sheets of a 6-inch wafer and six sides of a 6-inch wafer, which were subjected to primer treatment with hexamethyldiazane, were plated with a copper copper substrate having a thickness of 2 μm, and a spin coater was used. The composition of each example was applied to the film thickness described in the table. Among the prepared three wafers, one ruthenium substrate was heated and dried by a hot plate at 100 ° C for 1 minute to remove the solvent, and then passed through a quartz mask having a line width of 1 μm to 20 with a line of equal intervals. The light of the wavelength described in Table 1 was irradiated with the exposure amount. Further, here, NSR-1755i7A represents a stepper exposure apparatus manufactured by Nikon, and PLA-600FA represents a contact alignment type exposure apparatus manufactured by Canon. After the irradiation, it was heated at 80 ° C for 1 hour and then cooled.
然後，將上述塗佈的基板浸漬於2.38%四甲基氫氧化銨水溶液中3分鐘，進行顯影。此時顯影的線寬記載於表2中。而且，顯影後的膜厚亦合併記載。另一方面，對剩下的矽晶圓與銅基板，也以相同條件，塗佈表1記載的各實施例的組成物，進行除去溶劑之預加熱，然後浸漬於二甲基乙醯胺。進行該操作後殘留的薄膜再於200℃的烘箱加熱3小時，得到薄膜。利用該薄膜，分別測定薄膜的絕緣性、接著性，如表2中記載。Then, the coated substrate was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution for 3 minutes to carry out development. The line width of development at this time is shown in Table 2. Further, the film thickness after development is also described in combination. On the other hand, the composition of each of the examples described in Table 1 was applied to the remaining tantalum wafer and the copper substrate under the same conditions, preheating with removal of the solvent, and then immersing in dimethylacetamide. The film remaining after this operation was further heated in an oven at 200 ° C for 3 hours to obtain a film. The insulating properties and adhesion of the film were measured by the film, as described in Table 2.
使用的其他添加劑的內容如下。The contents of the other additives used are as follows.
FC－4430：界面活性劑(住友3M(股)製商品名)KBE－403：接著助劑(信越化學工業(股)製商品名)X－70－093：界面活性劑(信越化學工業(股)製商品名)NT－300P：感光劑(東洋合成工業(股)製商品名)FC-4430: Surfactant (commercial name of Sumitomo 3M (share)) KBE-403: Next auxiliary (trade name of Shin-Etsu Chemical Co., Ltd.) X-70-093: Surfactant (Shin-Etsu Chemical Industry Co., Ltd. ) product name) NT-300P: sensitizer (trade name of Toyo Synthetic Industrial Co., Ltd.)
上述表2中，密合性的評價係於飽和2大氣壓的壓力鍋中，基板放置24小時後，以棋盤格剝離測試，測定其剝離數。In the above Table 2, the adhesion was evaluated in a pressure cooker saturated at 2 atm, and the substrate was allowed to stand for 24 hours, and then the number of peeling was measured by a checkerboard peeling test.
以上的結果，實施例1~8的組成物係從1μm程度的薄膜，對如膜厚超過10μm之寬廣範圍的膜厚，具有良好的殘膜性與解像力，作為感光性材料亦顯示充分的特性的同時，其硬化膜於各種基材具有良好的接著性、具有所謂絕緣耐壓的電的特性，可得有用於作為電路、電子構件的保護膜的結果。As a result of the above, the compositions of Examples 1 to 8 have a film thickness of about 1 μm, and have a good residual film property and resolution for a wide film thickness of a film thickness of more than 10 μm, and exhibit sufficient characteristics as a photosensitive material. At the same time, the cured film has good adhesion to various substrates and electrical properties having a so-called insulation withstand voltage, and can be obtained as a protective film for a circuit or an electronic member.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001421A (en) * | 2015-07-03 | 2015-10-28 | 中科院广州化学有限公司南雄材料生产基地 | Preparation of polyimide solid powder containing phenolic hydroxyl group and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040180286A1 (en) * | 2001-07-03 | 2004-09-16 | Tomohiro Nagoya | Photosensitive resin composition, process of forming patterns with the same, and electronic components |
| JP2004310076A (en) * | 2003-03-26 | 2004-11-04 | Sumitomo Bakelite Co Ltd | Positive photosensitive resin composition, and semiconductor device and display element |
-
2006
- 2006-02-13 TW TW95104756A patent/TWI392962B/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040180286A1 (en) * | 2001-07-03 | 2004-09-16 | Tomohiro Nagoya | Photosensitive resin composition, process of forming patterns with the same, and electronic components |
| JP2004310076A (en) * | 2003-03-26 | 2004-11-04 | Sumitomo Bakelite Co Ltd | Positive photosensitive resin composition, and semiconductor device and display element |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001421A (en) * | 2015-07-03 | 2015-10-28 | 中科院广州化学有限公司南雄材料生产基地 | Preparation of polyimide solid powder containing phenolic hydroxyl group and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200634431A (en) | 2006-10-01 |
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