JPS62235496A - Production of substrate having resist pattern - Google Patents
Production of substrate having resist patternInfo
- Publication number
- JPS62235496A JPS62235496A JP7782186A JP7782186A JPS62235496A JP S62235496 A JPS62235496 A JP S62235496A JP 7782186 A JP7782186 A JP 7782186A JP 7782186 A JP7782186 A JP 7782186A JP S62235496 A JPS62235496 A JP S62235496A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- film
- resin composition
- parts
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 239000011342 resin composition Substances 0.000 claims abstract description 18
- 238000004070 electrodeposition Methods 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 13
- 239000003999 initiator Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 6
- 230000003472 neutralizing effect Effects 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052753 mercury Inorganic materials 0.000 abstract description 3
- 230000001678 irradiating effect Effects 0.000 abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000007766 curtain coating Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000004665 fatty acids Chemical group 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HSKPJQYAHCKJQC-UHFFFAOYSA-N 1-ethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC HSKPJQYAHCKJQC-UHFFFAOYSA-N 0.000 description 1
- DKTOWFDVEJQWPF-UHFFFAOYSA-N 1-ethylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC DKTOWFDVEJQWPF-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- VSYIJNDEXXBJFH-UHFFFAOYSA-N 5-isocyanato-2-methylpent-1-en-3-one Chemical compound CC(=C)C(=O)CCN=C=O VSYIJNDEXXBJFH-UHFFFAOYSA-N 0.000 description 1
- 101100008049 Caenorhabditis elegans cut-5 gene Proteins 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- -1 Mihiraketone Chemical compound 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- ROVRRJSRRSGUOL-UHFFFAOYSA-N victoria blue bo Chemical compound [Cl-].C12=CC=CC=C2C(NCC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 ROVRRJSRRSGUOL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
- H05K3/0079—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the method of application or removal of the mask
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は１表面に硬化樹脂皮膜からなるレジストパター
ンを有する基板ＯＪ造法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an OJ manufacturing method for a substrate having a resist pattern made of a cured resin film on one surface.
（従来の技術）
現在１表面に硬化樹脂皮膜パターンを有する基板は、光
硬化性樹脂組成物を用いて行なわれている。その際には
、まず基板上に光硬化性樹脂組成物の層を形成し、つい
で活性光線を画像状に照射し、未硬化部分を現像除去す
る。この工程に於て。(Prior Art) Currently, substrates having a cured resin film pattern on one surface are produced using a photocurable resin composition. In this case, a layer of a photocurable resin composition is first formed on a substrate, and then active light is irradiated in an imagewise manner, and uncured portions are developed and removed. In this process.
光硬化性樹脂組成物の層の形成には９種々の方法が採用
されている。例えばディップコート、ロールコート、カ
ーテンコート等の光硬化性樹脂組成物ｄ奴（ω液）を用
いる方法、あるいは光硬化性組成物のフィルムを積層す
る方法が知られている。Nine different methods have been adopted for forming layers of photocurable resin compositions. For example, methods using a photocurable resin composition (ω liquid) such as dip coating, roll coating, and curtain coating, or methods of laminating films of photocurable compositions are known.
これらの方法のうち、フィルムを積層する方法は。Among these methods, what is the method of laminating films?
簡便に均一な厚みの光硬化性組成物の層が形成できるこ
とから、現在特に印刷配線板製造の分野では主流の方法
として採用されている。Since it is possible to easily form a layer of a photocurable composition with a uniform thickness, this method is currently being adopted as the mainstream method, particularly in the field of printed wiring board manufacturing.
（発明が解決しようとする問題点）
最近、印刷配線板の高密度、高精度化が進むに伴い、レ
ジストパターンはより高品質のものが必要となってきて
いる。即ち、ピンホールがなく。(Problems to be Solved by the Invention) Recently, as printed wiring boards have become more dense and precise, resist patterns of higher quality have become necessary. In other words, there are no pinholes.
下地の基板表面によく密着したレジストパターンである
ことが望まれている。かかる要求に対して。It is desired that the resist pattern be in close contact with the surface of the underlying substrate. for such requests.
現在主流となっているフィルムを積層する方法では、限
界があることが知られている。この方法では、基板製造
時の打痕、研磨の不均一性、基板内層のガラス布の網目
１表面への銅めっきのビット等の不均一等によって生起
する基板表面の凹凸への追従性が乏しく、十分な密着性
を得ることが困難である。この困難は、フィルムの積層
を減圧下で行なうこと（特公昭５９−３７４０号公報参
照）によって回避できるが、これには特殊で高価な装置
が必要となる。このようなことが理由となって。It is known that the currently mainstream method of laminating films has its limitations. This method has poor ability to follow irregularities on the substrate surface caused by dents during substrate manufacturing, non-uniform polishing, non-uniform bits of copper plating on the surface of the mesh 1 of the glass cloth in the inner layer of the substrate, etc. , it is difficult to obtain sufficient adhesion. This difficulty can be avoided by laminating the films under reduced pressure (see Japanese Patent Publication No. 59-3740), but this requires special and expensive equipment. This is the reason.
近年再びディップコート、ロールコート、カーテンコー
ト等の溶液塗布の方法が見回されるようになってきた。In recent years, solution coating methods such as dip coating, roll coating, and curtain coating have become popular again.
しかしこれらの塗布法では膜厚の制御が困難、膜厚の均
一性が不十分、ピンホールの発生等の問題がある。However, these coating methods have problems such as difficulty in controlling the film thickness, insufficient uniformity of the film thickness, and occurrence of pinholes.
本発明は、均一な厚膜で、基板表面に十分密着した樹脂
硬化皮膜からなるレジストパターンを有する基板の製造
法を提供するものである。The present invention provides a method for manufacturing a substrate having a resist pattern made of a cured resin film that is uniformly thick and sufficiently adheres to the surface of the substrate.
（問題点を解決するための手段）
本発明は、水浴性または水分散性の光硬化性樹脂組成物
を含む電着塗装浴中に、その表面に銅金属膚を形成した
基板を浸漬し、これを陽極として通電することにより電
着塗装を行なって塗膜金得。(Means for Solving the Problems) The present invention involves immersing a substrate with a copper metal skin formed on its surface in an electrodeposition coating bath containing a water-bathable or water-dispersible photocurable resin composition, By applying electricity to this as an anode, electrodeposition coating is performed to obtain a coating film.
しかる後に活性光線を画像状に塗膜に照射し、ついで活
性光を照射していない未硬化の塗膜部分を現像除去する
表面に硬化樹脂皮膜からなるレジストパターンを有する
基板の製造法に関する。The present invention relates to a method for producing a substrate having a resist pattern made of a cured resin film on its surface, in which the coating film is imagewise irradiated with actinic light, and then uncured parts of the coating film that have not been irradiated with actinic light are developed and removed.
本発明に用いる水浴性または水分散性の光硬化性樹脂組
成物は、カルボキシル基含有ポリマのアルカリ中和物、
−分子中に重合性不飽和結合を少なくとも１個有するエ
チレン性不飽和化合物及び光重合開始剤を主成分とする
。カルボキシル基含有ポリマーとしてはアクリル酸、メ
タクリル酸。The water-bathable or water-dispersible photocurable resin composition used in the present invention is an alkali-neutralized product of a carboxyl group-containing polymer,
- The main components are an ethylenically unsaturated compound having at least one polymerizable unsaturated bond in the molecule and a photopolymerization initiator. Examples of carboxyl group-containing polymers include acrylic acid and methacrylic acid.
イタコン酸等とアクリル酸エステル、メタクリル酸エス
テル、スチレン等との共重合物が好ましい。Copolymers of itaconic acid and the like with acrylic esters, methacrylic esters, styrene, etc. are preferred.
また、カルボキシル基の含有量は、酸価が５０〜３００
、特に酸価が１００〜２００となるように調節すること
が好ましい。酸価が５０より低くなると水分散性が劣り
、一方、酸価が３００より高いと電着塗装が困難になる
。また、その数平均分子量は１０００以上であることが
好ましく、これ未満では塗膜形成能が低下し、粘着性が
大きくなりすぎる。カルボキシル基含有ポリマーは、更
に重合性不飽和基を含むものであってもよく、それによ
って、光硬化性の向上が行なわれる。かかるポリマーは
、カルボキシル基含有ポリマーに、メタクリル酸グリシ
ジルを付加反応させたり、水酸基含有モノマを更に共重
合成分とする共重合ポリマーに９分子中に重合性不飽和
を有するモノインシアナート化合物９例えばβ−メタク
リロイルエチルイソシアナートヲ反応させることによっ
て製造できる。In addition, the content of carboxyl groups has an acid value of 50 to 300.
In particular, it is preferable to adjust the acid value to 100 to 200. If the acid value is lower than 50, water dispersibility will be poor, while if the acid value is higher than 300, electrodeposition coating will be difficult. Moreover, it is preferable that the number average molecular weight is 1000 or more, and if it is less than this, the coating film forming ability will be reduced and the tackiness will be too high. The carboxyl group-containing polymer may further contain a polymerizable unsaturated group, thereby improving photocurability. Such a polymer can be produced by adding glycidyl methacrylate to a carboxyl group-containing polymer, or adding a monoincyanate compound 9 having polymerizable unsaturation in each molecule to a copolymer containing a hydroxyl group-containing monomer as a copolymerization component. It can be produced by reacting β-methacryloyl ethyl isocyanate.
カルボキシル基含有ポリマーの他の例としては。Other examples of carboxyl group-containing polymers include:
エポキシ樹脂と不飽和脂肪酸とのエステル化物における
脂肪酸鎖中の不飽和結合にα、β−エチレン性不飽和二
塩基酸又はその無水物を付加させたポリマーがある。ま
た、不飽和脂肪酸変性の高酸価アルキド樹脂も本発明に
用い得る。これらの酸価及び分子量はいずれも前述の範
囲の値であることが好ましい。There is a polymer in which α,β-ethylenically unsaturated dibasic acid or its anhydride is added to an unsaturated bond in a fatty acid chain in an esterified product of an epoxy resin and an unsaturated fatty acid. Further, high acid value alkyd resins modified with unsaturated fatty acids can also be used in the present invention. It is preferable that these acid values and molecular weights are both within the above-mentioned ranges.
これらのカルボキシル基含有ポリマーのアルカリ中和物
は、ポリマー中のカルボキシル基をアルカリで中和する
ことによって製造される。中和剤としてはアルカノール
アミン、アルキルアミン等のアミン類、カセイソーダ、
カセイヵリ、炭酸ソーダ、アンモニアなどがあり、これ
らは単独または混合物として使用できる。中和剤の使用
量はポリマー中のカルボキシル基１当量に対して０．４
〜１．０当量が好ましく、０．４当量より少なくなると
水分散性が低下するので好ましくない。Alkali-neutralized products of these carboxyl group-containing polymers are produced by neutralizing the carboxyl groups in the polymer with an alkali. As neutralizing agents, amines such as alkanolamines and alkylamines, caustic soda,
Examples include caustic potash, soda carbonate, and ammonia, which can be used alone or in mixtures. The amount of neutralizing agent used is 0.4 per equivalent of carboxyl group in the polymer.
-1.0 equivalent is preferable, and less than 0.4 equivalent is not preferable because water dispersibility decreases.
本発明の光硬化性樹脂組成物の第２の主要成分である一
分子中に重合性不飽和結合を少なくとも１個有するエチ
レン性不飽和化合物としては、エチレングリコールジメ
タクリレート、トリメチロールプロパントリアクリレー
ト等の多価アルコールのアクリル酸あるいはメタクリル
酸エステルを挙げることができる。ビスフェノールＡの
アルキレンオキシド付加物のアクリル酸あるいはメタク
リル酸エステルも有用である。Examples of the ethylenically unsaturated compound having at least one polymerizable unsaturated bond in one molecule, which is the second main component of the photocurable resin composition of the present invention, include ethylene glycol dimethacrylate, trimethylolpropane triacrylate, etc. Examples include acrylic acid or methacrylic acid esters of polyhydric alcohols. Acrylic or methacrylic acid esters of alkylene oxide adducts of bisphenol A are also useful.
本発明の光硬化性組成物の第３の主要成分である光重合
開始剤には、ベンゾフェノン、ミヒラケトン、エチルア
ントラキノン、エチルチオキサントン等、公知の光重合
開始剤が用いられる。As the photopolymerization initiator, which is the third main component of the photocurable composition of the present invention, known photopolymerization initiators such as benzophenone, Mihiraketone, ethyl anthraquinone, and ethylthioxanthone are used.
本発明の光硬化性樹脂組成物は、前記のカルボキシル基
含有ポリマー１００重量部に対して、−分子中に重合性
不飽和結合を少なくとも１個有するエチレン性不飽和化
合物を２０〜５０重量部。The photocurable resin composition of the present invention contains -20 to 50 parts by weight of an ethylenically unsaturated compound having at least one polymerizable unsaturated bond in the molecule, based on 100 parts by weight of the carboxyl group-containing polymer.
光重合開始剤を２〜１０重量部の割合で含有しているこ
とが好ましい。このエチレン性不飽和化合物が５０重量
部より多くなると組成物の水分散性が低下し、一方２０
重量部より少ないと組成物の光硬化性が低下する傾向が
ある。光重合開始剤についても上記の範囲より多すぎる
と水分散性が低下し、少なすぎると光硬化性が低下する
傾向がある。It is preferable that the photopolymerization initiator is contained in an amount of 2 to 10 parts by weight. When the amount of this ethylenically unsaturated compound exceeds 50 parts by weight, the water dispersibility of the composition decreases;
When the amount is less than 1 part by weight, the photocurability of the composition tends to decrease. Regarding the photopolymerization initiator, if the amount is too large than the above range, the water dispersibility tends to decrease, and if it is too small, the photocurability tends to decrease.
本発明における光硬化性樹脂組成物は前記の３成分に加
えて１着色剤、光発色剤、熱重合防止剤。In addition to the above three components, the photocurable resin composition of the present invention contains a colorant, a photocoloring agent, and a thermal polymerization inhibitor.
可塑剤、フィシなどを主々の目的のために副次成分とし
て含有せしめることができる。これらの使用にあたって
は、光硬化性樹脂組成物の製造時の通常の注意が払われ
るべきである。Plasticizers, plasticizers, etc. can be included as secondary ingredients for the primary purpose. When using these, the usual precautions when manufacturing photocurable resin compositions should be taken.
本発明における電着塗装は通常次のごとくにして行なわ
れる。水浴性または水分散性の光硬化性樹脂組成物を含
む水溶液又は水分散液とした電着塗装浴をｐＨ６，５〜
９．光硬化性樹脂組成物の濃度を５〜２０重量％、浴温
度を１５〜４０℃に管理し、この浴に表面に銅金属層を
形成した基板を陽極として浸漬し、を着塗装浴を陰極と
して４０〜４００ｖの直流電流を通電する。３０秒〜１
０分の通電により、基板の銅金属層上に光硬化性樹脂組
成物が析出して塗膜が形成される。電着浴から基板を取
り出し、水洗する。その後、電着塗膜中に含まれる水分
を乾燥除去する。この際、電着浴から基板を取り出し軽
く水洗した後、乾燥前に０．１〜５重量％の塩酸をスプ
レィあるいは浸漬等。Electrodeposition coating in the present invention is usually carried out as follows. An electrodeposition coating bath containing an aqueous solution or aqueous dispersion containing a water-bathable or water-dispersible photocurable resin composition has a pH of 6.5 to
9. The concentration of the photocurable resin composition was controlled at 5 to 20% by weight, and the bath temperature was controlled at 15 to 40°C. A substrate with a copper metal layer formed on the surface was immersed in this bath as an anode, and the coating bath was used as a cathode. As a result, a DC current of 40 to 400 V is applied. 30 seconds ~ 1
By applying current for 0 minutes, the photocurable resin composition is deposited on the copper metal layer of the substrate to form a coating film. Remove the substrate from the electrodeposition bath and wash with water. Thereafter, water contained in the electrodeposition coating film is removed by drying. At this time, the substrate is taken out from the electrodeposition bath, washed lightly with water, and then sprayed or immersed in 0.1 to 5% by weight hydrochloric acid before drying.
酸で基板上の塗膜を処理、更に水洗を行なうことが好ま
しく、この処理によって、基板上の塗膜表面の光硬化性
樹脂組成物中のカルボキシル基含有ポリマーのアルカリ
中和物をフリーのカルボキシル基含有ポリマー状態にで
きるので、後述の現像操作時の露光部分の現像液への耐
性向上効果が得られる。It is preferable to treat the coating film on the substrate with an acid and further wash with water. By this treatment, the alkali neutralized product of the carboxyl group-containing polymer in the photocurable resin composition on the surface of the coating film on the substrate is converted to free carboxyl. Since it can be made into a group-containing polymer state, it is possible to obtain the effect of improving the resistance of the exposed area to the developer during the development operation described below.
電着塗装により得られた塗膜への活性光線の画情状の照
射は、水銀灯等を光源として、所望の画像を有するネガ
マスクを通した露光によって行なわれる。勿論、アルゴ
ンレーザ等の小径にしぼったビームの走査露光によって
も行なえる。照射後。The pattern-like irradiation of active light onto the coating film obtained by electrodeposition is carried out by exposure through a negative mask having a desired image using a mercury lamp or the like as a light source. Of course, scanning exposure using a narrow beam such as an argon laser can also be used. After irradiation.
活性光を照射していない未硬化の塗膜部分を現像除去す
ることによって、基板上に硬化樹脂皮膜からなるレジス
トパターンが形成される。現像は。By developing and removing the uncured coating film portions that have not been irradiated with actinic light, a resist pattern consisting of a cured resin film is formed on the substrate. As for development.
炭酸ソーダ水浴液等の弱アルカリ性水溶液のスプレィで
行なうことが好ましい。It is preferable to spray a weakly alkaline aqueous solution such as a sodium carbonate water bath solution.
（実施例） 以下に実施例にエリ本発明を説明する。(Example) The present invention will be explained below with reference to Examples.
実施例１
メタクリル酸／メタクリル酸メチル／アクリル酸エチル
／アクリル酸オクチル（２０１５０／２０／１０重量比
）共重合体（分子量７０，０００）の５０重量％ジオキ
サン溶液１３０重量部、トリメチロールプロパントリア
クリレート２０重量部。Example 1 130 parts by weight of a 50% dioxane solution of methacrylic acid/methyl methacrylate/ethyl acrylate/octyl acrylate (20150/20/10 weight ratio) copolymer (molecular weight 70,000), trimethylolpropane triacrylate 20 parts by weight.
テトラエチレングリコールジアクリレート１０１ｉ量部
の混合溶液をカセイソーダを０．６当竜用いて中和した
ものに、光重合開始剤としてベンゾフェノン３重量部、
ミヒラーケトン１重量部、安定剤としてハイドロキノン
０．５重量部及び着色剤としてビクトリアピュアブルー
０．２重量部を１０重量部のメチルエチルケトンに溶解
した溶液を添加したのち、固形分含有率が１０重量％に
なるよう水を加えて電着塗装浴（ｐＨ９）とした。A mixed solution of 101 parts of tetraethylene glycol diacrylate was neutralized using 0.6 parts of caustic soda, and 3 parts by weight of benzophenone was added as a photopolymerization initiator.
After adding a solution of 1 part by weight of Michler's ketone, 0.5 parts by weight of hydroquinone as a stabilizer and 0.2 parts by weight of Victoria Pure Blue as a coloring agent dissolved in 10 parts by weight of methyl ethyl ketone, the solid content was reduced to 10 parts by weight. Water was added to make an electrodeposition coating bath (pH 9).
この塗装浴中に銅張り積層板を浸漬して、電圧４０Ｖの
直流′電流を２分間、２０℃で通電して電着塗装を行な
った。銅張り積層板はあらかじめ清浄化処理したのち、
ナイフを用いて１ｃｍおきに１０ｃｍ程度の長さで、５
μｍ程度の深さのきすを入れておいた。塗装された銅張
り積層板を浴中からひきあげ、塗面を１０秒間水に浸漬
し、０．１重量係の塩酸水溶液に１０秒間、最後に３０
秒間水をスプレィした。つづいて８０℃で１０分間加熱
し乾燥した。The copper-clad laminate was immersed in this coating bath and electrocoated by applying a direct current of 40 V for 2 minutes at 20°C. After cleaning the copper-clad laminate in advance,
Using a knife, cut 5 pieces in length of about 10cm every 1cm.
A slit with a depth of about μm was made. The painted copper-clad laminate was lifted out of the bath, the painted surface was immersed in water for 10 seconds, and then immersed in a 0.1% by weight hydrochloric acid aqueous solution for 10 seconds, and finally for 30 seconds.
Sprayed with water for seconds. Subsequently, it was heated and dried at 80° C. for 10 minutes.
５００μｍ幅のレジストパターンが、銅張り積層板にあ
らかじめ入れたナイフきずと直角に形成されるようにし
てネガマスクを通して３謂超高圧水銀灯を用い１５０
ｍＪ ／ ｃｍ２で露光した。露光後。A resist pattern with a width of 500 μm was formed at right angles to the knife scratches previously made in the copper-clad laminate, and was passed through a negative mask using a so-called ultra-high-pressure mercury lamp at 150 µm.
Exposure was at mJ/cm2. After exposure.
１重量％炭酸ソーダ水溶液を現像液として、６０秒間現
像した。銅張り積層板上に５００μｍ幅のレジストパタ
ーンが形成された。このものを更に塩化銅エツチングし
たのち、レジストを５重量％カセイソーダ水溶液を用い
てはく離した。５００μｍ幅のレジストが形成されてい
た部分は、ナイフきず部分もエツチングで侵されておら
ず、明瞭な輪かくを有する銅パターンが得られた。Development was performed for 60 seconds using a 1% by weight aqueous sodium carbonate solution as a developer. A resist pattern with a width of 500 μm was formed on the copper-clad laminate. After this material was further etched with copper chloride, the resist was removed using a 5% by weight aqueous solution of caustic soda. In the part where the 500 μm wide resist was formed, even the knife scratch part was not etched, and a copper pattern with a clear ring was obtained.
比較例
実施例１と同様に、ただカセイソーダによる中和を行な
わずに、光重合開始剤等を添加した溶液を２５μｍのポ
リエステルフィルム上に乾燥厚が１５μｍになるよう塗
布乾燥した。このものを実施例１と同様の銅張り積層板
上に市販の感光性フィルム用ラミネーター（デュポン社
＃！Ａ−２４ラミネータ）を用いて、１２０℃で積層し
た。積層後、実施例１と同様に露光・現像し、エツチン
グ後、レジストをはく離した。全体としては５００μｍ
幅の銅パターンが得られていたが、ナイフきず部分は両
側からおよそ４０μｍ程度ずつ、エンチングで侵されて
いた。Comparative Example In the same manner as in Example 1, a solution containing a photopolymerization initiator and the like was applied onto a 25 μm polyester film and dried to a dry thickness of 15 μm, without neutralizing with caustic soda. This product was laminated on the same copper-clad laminate as in Example 1 at 120° C. using a commercially available laminator for photosensitive films (DuPont #!A-24 laminator). After lamination, exposure and development were carried out in the same manner as in Example 1, and after etching, the resist was peeled off. Overall 500μm
Although a copper pattern with a wide width was obtained, the knife scratch portion was etched by about 40 μm from both sides.
実施例２
エピコート８２８（シェル化学製エポキシ樹脂）３００
重量部とあまに油脂肪酸１０００重量部とを酸価が１０
になるよう加熱してエステル化したのち、無水マレイン
酸３５０重量部を加え、２３０℃で２時間マレイン化反
応を行なった。次いで。Example 2 Epicoat 828 (epoxy resin manufactured by Shell Chemical Co., Ltd.) 300
parts by weight and 1000 parts by weight of linseed oil fatty acid with an acid value of 10.
After heating to esterify the mixture, 350 parts by weight of maleic anhydride was added, and a maleation reaction was carried out at 230° C. for 2 hours. Next.
ブタノールを３００ｍ１．を部加え、１８０℃で酸無水
基を開環させた。300 ml of butanol. was added to open the acid anhydride group at 180°C.
エチレングリコールモツプチルエーテルを加え。Add ethylene glycol motuputyl ether.
固形分が７００重量部なるように調節したのち。After adjusting the solid content to 700 parts by weight.
カセイソーダを０．６当量用いて中和した。トリメチロ
ールプロパントリアクリレート２５重量部。Neutralization was performed using 0.6 equivalents of caustic soda. 25 parts by weight of trimethylolpropane triacrylate.
メタクリル酸メチル／メタクリル酸共重合体（９０／１
０重量比１分子量６０，０００）５重量部、更に実施例
１と同様のベンゾフェノン３重量部、ミヒラーケトン１
重量部、ハイドロキノン０．５重量部。Methyl methacrylate/methacrylic acid copolymer (90/1
0 weight ratio 1 molecular weight 60,000) 5 parts by weight, further 3 parts by weight of benzophenone as in Example 1, 1 part by weight of Michler's ketone
parts by weight, 0.5 parts by weight of hydroquinone.
ビク） ＩＪアピュアプルー０．２重量部のメチルエチ
ルケトン溶液を添加した後、固形分含有率が１０重量％
になるように水を加えて電着塗装浴（ｐＨ＆５）とした
。After adding 0.2 parts by weight of methyl ethyl ketone solution of IJ Pure Blue, the solid content is 10% by weight.
Water was added to make an electrodeposition coating bath (pH & 5).
実施例１と同様に銅張り積層板に電着塗装、露光、現像
を行ないレジストパターンを得た。エツチング後ンジス
トはく離をすると実施例１と同様にナイフきす部分もエ
ツチングで侵されておらず。In the same manner as in Example 1, a copper-clad laminate was electrocoated, exposed, and developed to obtain a resist pattern. When the resist was removed after etching, as in Example 1, the knife scratch areas were not attacked by the etching.
レジストによる保趨作用が十分であることが確認できた
。It was confirmed that the trend-protecting effect of the resist was sufficient.
（発明の効果）
本発明により従来のフィルム積層法で問題であった基板
へのレジストの密着性、特に、基板表面の凹凸への追従
性が改善されたレジストパターンを有する基板が得られ
る。(Effects of the Invention) According to the present invention, it is possible to obtain a substrate having a resist pattern in which the adhesion of the resist to the substrate, which has been a problem with conventional film lamination methods, and in particular, the ability to follow irregularities on the substrate surface are improved.
Claims (1)
電着塗装浴中に、その表面に銅金属層を形成した基板を
浸漬し、これを陽極として通電することにより電着塗装
を行なつて塗膜を得、しかる後に活性光線を画像状に塗
膜に照射し、ついで活性光を照射していない未硬化の塗
膜部分を現像除去することを特徴とする表面に硬化樹脂
皮膜からなるレジストパターンを有する基板の製造法。1. A substrate with a copper metal layer formed on its surface is immersed in an electrodeposition coating bath containing a water-bathable or water-dispersible photocurable resin composition, and this is used as an anode to apply electricity to perform electrodeposition coating. to obtain a coating film, and then irradiate the coating film with active light in an imagewise manner, and then develop and remove the uncured coating film portions that have not been irradiated with active light. A method for manufacturing a substrate having a resist pattern consisting of:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7782186A JPS62235496A (en) | 1986-04-04 | 1986-04-04 | Production of substrate having resist pattern |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7782186A JPS62235496A (en) | 1986-04-04 | 1986-04-04 | Production of substrate having resist pattern |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62235496A true JPS62235496A (en) | 1987-10-15 |
Family
ID=13644700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7782186A Pending JPS62235496A (en) | 1986-04-04 | 1986-04-04 | Production of substrate having resist pattern |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62235496A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01243493A (en) * | 1988-03-25 | 1989-09-28 | Hitachi Ltd | Manufacture of printed circuit board |
| US5384229A (en) * | 1992-05-07 | 1995-01-24 | Shipley Company Inc. | Photoimageable compositions for electrodeposition |
| US6436132B1 (en) * | 2000-03-30 | 2002-08-20 | Advanced Cardiovascular Systems, Inc. | Composite intraluminal prostheses |
| US6596022B2 (en) * | 1991-10-28 | 2003-07-22 | Advanced Cardiovascular Systems, Inc. | Expandable stents and method for making same |
| JP2007067427A (en) * | 2006-10-13 | 2007-03-15 | Tdk Corp | Sheet used for constituting electronic component |
| US9108028B2 (en) | 2007-05-31 | 2015-08-18 | Abbott Cardivascular Systems Inc. | Method and apparatus for delivering an agent to a kidney |
| US9144509B2 (en) | 2007-05-31 | 2015-09-29 | Abbott Cardiovascular Systems Inc. | Method and apparatus for delivering an agent to a kidney |
| US9149610B2 (en) | 2007-05-31 | 2015-10-06 | Abbott Cardiovascular Systems Inc. | Method and apparatus for improving delivery of an agent to a kidney |
| US9364586B2 (en) | 2007-05-31 | 2016-06-14 | Abbott Cardiovascular Systems Inc. | Method and apparatus for improving delivery of an agent to a kidney |
| US10130465B2 (en) | 2016-02-23 | 2018-11-20 | Abbott Cardiovascular Systems Inc. | Bifurcated tubular graft for treating tricuspid regurgitation |
-
1986
- 1986-04-04 JP JP7782186A patent/JPS62235496A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01243493A (en) * | 1988-03-25 | 1989-09-28 | Hitachi Ltd | Manufacture of printed circuit board |
| US6596022B2 (en) * | 1991-10-28 | 2003-07-22 | Advanced Cardiovascular Systems, Inc. | Expandable stents and method for making same |
| US5384229A (en) * | 1992-05-07 | 1995-01-24 | Shipley Company Inc. | Photoimageable compositions for electrodeposition |
| US6436132B1 (en) * | 2000-03-30 | 2002-08-20 | Advanced Cardiovascular Systems, Inc. | Composite intraluminal prostheses |
| JP2007067427A (en) * | 2006-10-13 | 2007-03-15 | Tdk Corp | Sheet used for constituting electronic component |
| JP4618442B2 (en) * | 2006-10-13 | 2011-01-26 | Ｔｄｋ株式会社 | Manufacturing method of sheet used for configuration of electronic component |
| US9108028B2 (en) | 2007-05-31 | 2015-08-18 | Abbott Cardivascular Systems Inc. | Method and apparatus for delivering an agent to a kidney |
| US9144509B2 (en) | 2007-05-31 | 2015-09-29 | Abbott Cardiovascular Systems Inc. | Method and apparatus for delivering an agent to a kidney |
| US9149610B2 (en) | 2007-05-31 | 2015-10-06 | Abbott Cardiovascular Systems Inc. | Method and apparatus for improving delivery of an agent to a kidney |
| US9364586B2 (en) | 2007-05-31 | 2016-06-14 | Abbott Cardiovascular Systems Inc. | Method and apparatus for improving delivery of an agent to a kidney |
| US10130465B2 (en) | 2016-02-23 | 2018-11-20 | Abbott Cardiovascular Systems Inc. | Bifurcated tubular graft for treating tricuspid regurgitation |
| US11583399B2 (en) | 2016-02-23 | 2023-02-21 | Abbott Cardiovascular Systems Inc. | Bifurcated tubular graft for treating tricuspid regurgitation |
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