JPH04218049A - Resist composition - Google Patents
Resist compositionInfo
- Publication number
- JPH04218049A JPH04218049A JP3088880A JP8888091A JPH04218049A JP H04218049 A JPH04218049 A JP H04218049A JP 3088880 A JP3088880 A JP 3088880A JP 8888091 A JP8888091 A JP 8888091A JP H04218049 A JPH04218049 A JP H04218049A
- Authority
- JP
- Japan
- Prior art keywords
- resist composition
- resist
- shear rate
- fluid
- fine powder
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 66
- 239000000843 powder Substances 0.000 claims abstract description 28
- 239000012530 fluid Substances 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000004033 plastic Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 15
- 238000007598 dipping method Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 29
- 239000000463 material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 5
- 230000009974 thixotropic effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- -1 and among these Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】この発明は、ＩＣ回路、プリント
配線板、フォトマスク等の製造に有用なレジスト組成物
に関する。FIELD OF THE INVENTION This invention relates to a resist composition useful for manufacturing IC circuits, printed wiring boards, photomasks, etc.
【０００２】0002
【従来の技術】従来、プリント配線板用フォトレジスト
としてドライフィルムフォトレジストが主として使われ
ている。しかし、ドライフィルムフォトレジストは、そ
の工法上の理由からカバーシートをレジスト層上部に設
けなくてはならず、また、レジスト層そのものの薄膜化
にも限界があった。そのため、１００μｍより微細な回
路形成を産業レベルで実施することは困難であった。2. Description of the Related Art Conventionally, dry film photoresists have been mainly used as photoresists for printed wiring boards. However, for dry film photoresists, a cover sheet must be provided on top of the resist layer due to its construction method, and there is also a limit to how thin the resist layer itself can be. Therefore, it has been difficult to form circuits finer than 100 μm at an industrial level.
【０００３】レジスト被膜の薄膜化のために、近年、電
気泳動によりレジスト成分を基材に塗布する電着工法が
考案されている（特開昭５０−１７８２７号、同６０−
２０７１３９号の各公報等参照）。しかし、これらの工
法は、レジスト被膜の厚みを均一にすることが困難であ
る、レジスト被膜にピンホールが生じやすい等の欠点を
有するため、まだ産業化されるに至っていない。[0003] In order to make the resist film thinner, an electrodeposition method has been devised in recent years in which resist components are applied to the base material by electrophoresis (Japanese Patent Application Laid-open Nos. 17827-1982 and 60-1982).
(Refer to various publications such as No. 207139). However, these methods have not been industrialized yet because they have drawbacks such as difficulty in making the thickness of the resist film uniform and pinholes are likely to occur in the resist film.
【０００４】そこで、膜厚の均一な薄いレジスト被膜を
形成するための工法としてディップ工法を用いてスルー
ホール付配線板を製造する方法が特許出願されている（
特願平１−４４１１５号、同１−２７９１９３号、同２
−１７３７８号、同２−４３４３１号等参照）。[0004] Therefore, a patent application has been filed for a method of manufacturing a wiring board with through holes using a dip method as a method of forming a thin resist film with a uniform film thickness.
Patent Application No. 1-44115, No. 1-279193, No. 2
-17378, 2-43431, etc.).
【０００５】[0005]
【発明が解決しようとする課題】ところが、上記ディッ
プ工法では、基材をディップ（浸漬）する液状のレジス
ト組成物の流動特性によっては、膜厚の均一な薄いレジ
スト被膜を得ることが出来ない場合があった。たとえば
、基材をレジスト組成物にディップした後引き上げる際
、レジスト組成物の粘度が高すぎると、基材にレジスト
組成物が厚く付きすぎてしまう。また、基材をレジスト
組成物から引き上げ終えた後静止する際、レジスト組成
物の粘度が低すぎると、レジスト組成物が基材から垂れ
落ちすぎるため、レジスト組成物が薄く付きすぎてしま
う。また、液垂れのために、レジスト組成物が不均一に
付きやすい。[Problems to be Solved by the Invention] However, with the dip method described above, depending on the flow characteristics of the liquid resist composition in which the substrate is dipped, it may not be possible to obtain a thin resist film with a uniform thickness. was there. For example, when a substrate is dipped in a resist composition and then pulled up, if the viscosity of the resist composition is too high, the resist composition will adhere too thickly to the substrate. Further, when the substrate is stopped after being lifted from the resist composition, if the viscosity of the resist composition is too low, the resist composition will drip from the substrate too much, resulting in the resist composition being applied too thinly. In addition, the resist composition tends to adhere unevenly due to dripping.
【０００６】このような事情に鑑み、この発明は、ディ
ップ工法によって厚みの均一な薄いレジスト被膜を形成
することができる流動特性を有するレジスト組成物を提
供することを課題とする。[0006] In view of the above circumstances, an object of the present invention is to provide a resist composition having flowability that allows a thin resist film with a uniform thickness to be formed by a dip method.
【０００７】[0007]
【課題を解決するための手段】上記課題を解決するため
、鋭意検討した結果、発明者らは、ディップ工法によっ
て基材上にレジスト被膜を形成する際、レジスト組成物
として、せん断速度に応じて粘度が変化する非ニュート
ン流体を用い、しかも、その見かけ粘度が、基材をレジ
スト組成物から引き上げる状態（以下、これを「高せん
断速度状態」と称する）では低く、基材を引き上げ終え
た後基材を静止する状態（以下、これを「低せん断速度
状態」と称する）では高くなるようなものを用いれば、
厚みの均一な薄いレジスト被膜を形成することができる
ことを見出し、この発明を完成するに至った。[Means for Solving the Problems] In order to solve the above problems, as a result of intensive studies, the inventors discovered that when forming a resist film on a substrate by a dip method, a resist composition that A non-Newtonian fluid whose viscosity changes is used, and its apparent viscosity is low in the state in which the base material is pulled up from the resist composition (hereinafter referred to as the "high shear rate state"), and the apparent viscosity is low in the state in which the base material is pulled up from the resist composition. If you use something that increases when the base material is stationary (hereinafter referred to as "low shear rate state"),
The inventors discovered that it is possible to form a thin resist film with a uniform thickness, and completed the present invention.
【０００８】すなわち、この発明にかかるレジスト組成
物は、液状のレジスト組成物であって、下記三つの条件
（ａ）、（ｂ）、（ｃ）を満たすことを特徴とする。
（ａ）塑性流体ないし擬塑性流体であること。
（ｂ）見かけ粘度が、せん断速度３０ｓ−１以上の時に
は２００ｃｐｓ以下であり、せん断速度５ｓ−１以下の
時には２５０ｃｐｓ以上であること。That is, the resist composition according to the present invention is a liquid resist composition, and is characterized by satisfying the following three conditions (a), (b), and (c). (a) It is a plastic fluid or a pseudoplastic fluid. (b) The apparent viscosity is 200 cps or less when the shear rate is 30 s-1 or more, and 250 cps or more when the shear rate is 5 s-1 or less.
【０００９】（ｃ）上記流動特性（ａ）および（ｂ）を
得るために、少なくとも一部が疎水化処理された粒径１
μｍ以下の微粉体が添加されている。
上述したように、この発明のレジスト組成物は、塑性流
体ないし擬塑性流体である必要がある。前記非ニュート
ン流体としては、塑性流体、擬塑性流体の他にチキソト
ロピー性流体があるが、チキソトロピー性流体は、この
発明のレジスト組成物としては用いられない。チキソト
ロピー性流体の場合は、流動性を持たせるためには、振
動を与えたり、かき混ぜたりしなければならず、しかも
、静止するとゲル状に固まってしまうといった特性があ
るため、チキソトロピー性のレジスト組成物を基材に塗
布すると、レジスト被膜に厚みムラが生じるからである
。(c) In order to obtain the above-mentioned flow characteristics (a) and (b), particles having a particle size 1 at least partially subjected to hydrophobization treatment
Fine powder of µm or less is added. As mentioned above, the resist composition of the present invention needs to be a plastic fluid or a pseudoplastic fluid. In addition to plastic fluids and pseudoplastic fluids, the non-Newtonian fluids include thixotropic fluids, but thixotropic fluids are not used in the resist composition of the present invention. In the case of thixotropic fluids, they must be vibrated or stirred in order to have fluidity, and they solidify into a gel-like state when they stand still, so thixotropic resist compositions This is because when a substance is applied to a base material, the thickness of the resist film becomes uneven.
【００１０】また、この発明のレジスト組成物は、上述
したように、高せん断速度状態と低せん断速度状態のそ
れぞれの状態において、所定の範囲の見かけ粘度を有す
る必要がある。図１は、この発明の一実施例であるレジ
スト組成物をディップ工法によって基材に塗布する工程
を模式的に表す。また、図２のグラフは、同レジスト組
成物の見かけ粘度とせん断速度の関係を表す。図１の（
ａ）にみるように、基材１をレジスト組成物２から引き
上げる時の○印の部分のレジスト組成物にかかるせん断
速度（高せん断速度）は、通常、３０ｓ−１以上である
。この時のレジスト組成物２の見かけ粘度は、２００ｃ
ｐｓ以下であることが必要であり、１５０ｃｐｓ以下で
あることが好ましい。すなわち、図２にみるように、粘
度曲線Ｃは、高せん断速度状態時には、領域Ａを通る必
要がある。高せん断速度状態時の見かけ粘度が２００ｃ
ｐｓを超えるレジスト組成物を用いた場合は、レジスト
組成物が基材に厚く付きすぎるからである。また、図１
の（ｂ）にみるように、基材１をレジスト組成物２から
引き上げ終えた後、基材１を静止する時のレジスト組成
物にかかるせん断速度（低せん断速度）は、通常、５ｓ
−１以下である。この時のレジスト組成物２の見かけ粘
度は、２５０ｃｐｓ以上であることが必要であり、４０
０ｃｐｓ以上であることが好ましい。すなわち、図２に
みるように、粘度曲線Ｃは、低せん断速度状態時には、
領域Ｂを通る必要がある。低せん断速度状態時の見かけ
粘度が２５０ｃｐｓを下回るレジスト組成物を用いた場
合は、レジスト組成物が基材から垂れ落ちるため、レジ
スト被膜がムラになったり、薄く付きすぎたりするから
である。Further, as described above, the resist composition of the present invention needs to have an apparent viscosity within a predetermined range in both the high shear rate state and the low shear rate state. FIG. 1 schematically represents a process of applying a resist composition according to an embodiment of the present invention to a base material by a dip method. Moreover, the graph of FIG. 2 represents the relationship between the apparent viscosity and shear rate of the same resist composition. In Figure 1 (
As shown in a), the shear rate (high shear rate) applied to the resist composition in the part marked with ◯ when the base material 1 is pulled up from the resist composition 2 is usually 30 s-1 or more. At this time, the apparent viscosity of resist composition 2 was 200c.
ps or less, and preferably 150 cps or less. That is, as shown in FIG. 2, the viscosity curve C needs to pass through region A in a high shear rate state. Apparent viscosity at high shear rate is 200c
This is because if a resist composition exceeding ps is used, the resist composition will adhere too thickly to the base material. Also, Figure 1
As shown in (b), the shearing rate (low shearing rate) applied to the resist composition when the substrate 1 is stopped after it has been pulled up from the resist composition 2 is usually 5 seconds.
-1 or less. At this time, the apparent viscosity of resist composition 2 needs to be 250 cps or more, and 40 cps or more is required.
It is preferable that it is 0 cps or more. That is, as shown in FIG. 2, the viscosity curve C is
It is necessary to pass through area B. If a resist composition with an apparent viscosity of less than 250 cps at a low shear rate is used, the resist composition will drip from the substrate, resulting in a resist film that is uneven or too thin.
【００１１】この発明では、レジスト組成物に上述した
ような流動特性を持たせるため、微粉体をレジスト組成
物に添加して粘度を調整するようにする。この発明で用
いられる微粉体としては、レジスト組成物の粘度を所望
の値に調整することができ、しかも、同微粉体の添加に
よってレジスト組成物の性能が低下しないようなもので
あることが必要である。また、レジスト組成物の感光領
域の波長において透明もしくはほぼ透明であることが好
ましい。このような微粉体の具体例としては、シリカ、
ジルコニア、チタニアなどの無機微粉体、アクリル樹脂
、スチレン樹脂などの有機微粉体等が挙げられ、これら
のうちでもシリカの使用が好ましいが、特に限定されな
い。In the present invention, in order to give the resist composition the above-mentioned flow characteristics, fine powder is added to the resist composition to adjust the viscosity. The fine powder used in this invention must be able to adjust the viscosity of the resist composition to a desired value, and must not deteriorate the performance of the resist composition by adding the fine powder. It is. Further, it is preferable that the resist composition be transparent or nearly transparent at wavelengths in the photosensitive region of the resist composition. Specific examples of such fine powder include silica,
Examples include inorganic fine powders such as zirconia and titania, organic fine powders such as acrylic resins and styrene resins, and among these, silica is preferably used, but is not particularly limited.
【００１２】この発明で用いられる微粉体は、その一部
もしくは全部が疎水化処理されている必要がある。もし
も、微粉体が表面に水酸基やカルボキシル基等の親水基
を持つ場合、それら親水基の間に水素結合が生じやすい
ため、レジスト組成物の流動特性がチキソトロピー性を
示すようになったり、微粉体の二次凝集が起きたりして
、非ニュートン性が得られなかったり、レジスト被膜に
厚みムラが生じやすくなったりするので、好ましくない
からである。疎水化処理の方法としては、特に限定され
ないが、微粉体に疎水化処理剤を添加混合して微粉体の
表面を疎水化する方法等が挙げられる。そのような疎水
化処理剤としては、たとえば、シランカップリング剤、
エステル化剤、アルキル化剤等が挙げられるが、特に限
定されない。また、疎水化処理微粉体（Ａ）と未処理微
粉体（Ｂ）との重量割合（Ａ／Ｂ）については、特に限
定されないが、５０／５０以上が好ましく、７５／２５
以上がより好ましい。[0012] The fine powder used in the present invention must be partially or entirely hydrophobically treated. If the fine powder has hydrophilic groups such as hydroxyl groups or carboxyl groups on the surface, hydrogen bonds are likely to occur between these hydrophilic groups, and the flow characteristics of the resist composition may become thixotropic. This is because secondary aggregation may occur, making it impossible to obtain non-Newtonian properties, and making it easy for the resist film to have uneven thickness, which is undesirable. The method of hydrophobizing treatment is not particularly limited, but includes a method of adding and mixing a hydrophobizing agent to fine powder to make the surface of fine powder hydrophobic. Examples of such hydrophobizing agents include silane coupling agents,
Examples include esterifying agents, alkylating agents, etc., but are not particularly limited. Further, the weight ratio (A/B) of the hydrophobized fine powder (A) and the untreated fine powder (B) is not particularly limited, but is preferably 50/50 or more, and 75/25.
The above is more preferable.
【００１３】また、前記微粉体の粒径については、１μ
ｍ以下であることが必要である。もしも粒径が１μｍを
超える微粉体を用いた場合、目的とする回路形成に支障
を来したり、レジスト被膜に厚みムラが生じやすくなっ
たりするからである。この発明のレジスト組成物に含ま
れる前記微粉体以外の成分としては、特に限定されず、
たとえば、従来のレジスト組成物に通常含まれている（
感光性）樹脂、感光剤、溶媒、増感剤、着色剤、粘度調
整剤、変色剤等が挙げられる。これら成分および前記微
粉体の配合割合についても、特に限定されず、レジスト
組成物が前記流動特性（ａ）および（ｂ）を持つように
適宜選択される。[0013] Furthermore, the particle size of the fine powder is 1 μm.
It is necessary that it is less than m. This is because, if a fine powder with a particle size exceeding 1 μm is used, it may interfere with the formation of the intended circuit, or the resist film may become uneven in thickness. Components other than the fine powder contained in the resist composition of the present invention are not particularly limited,
For example, (
Examples include photosensitive) resins, photosensitizers, solvents, sensitizers, colorants, viscosity modifiers, color-changing agents, and the like. The proportions of these components and the fine powder are not particularly limited, and are appropriately selected so that the resist composition has the fluidity characteristics (a) and (b).
【００１４】[0014]
【作用】レジスト組成物の見かけ粘度を、高せん断速度
状態時には低く、低せん断速度状態時には高くなるよう
に調整すると、ディップ工法によって膜厚の均一な薄い
レジスト被膜が形成する。[Function] By adjusting the apparent viscosity of the resist composition so that it is low when the shear rate is high and high when the shear rate is low, a thin resist film with a uniform thickness can be formed by the dip method.
【００１５】[0015]
【実施例】以下に、この発明の具体的な実施例を比較例
と併せて説明するが、この発明は、下記実施例に限定さ
れない。
─実施例１〜５および比較例１〜５─
後記表１に示す配合割合で各成分を配合して、実施例１
〜５および比較例１〜５のレジスト組成物を調整した。[Examples] Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. ─Examples 1 to 5 and Comparative Examples 1 to 5─ Example 1 was prepared by blending each component in the proportions shown in Table 1 below.
-5 and Comparative Examples 1-5 were prepared.
【００１６】ただし、表中の固形分の配合割合は、下記
■、■、■の総量の、レジスト組成物全体に対する重量
％を示す。なお、下記■と■の重量比（■／■）は、２
５／７５である。■ ２，３，４−トリヒドロキシベ
ンゾフェノンと１−ナフトキノン−２−ジアジド−５−
スルホン酸塩化物からのエステル化物。[0016] However, the blending ratio of solid content in the table indicates the weight percent of the total amount of the following (1), (2), and (2) based on the entire resist composition. In addition, the weight ratio (■/■) of ■ and ■ below is 2
It is 5/75. ■ 2,3,4-trihydroxybenzophenone and 1-naphthoquinone-2-diazide-5-
Esterified product from sulfonic acid chloride.
【００１７】■ クレゾールノボラック樹脂。■
粒径７〜２０ｎｍのシリカ微粉体。表中の液状成分の配
合割合は、エチレングリコールモノエチルエーテルアセ
テート、酢酸エチル、トルエンを適宜配合した総量の、
レジスト組成物全体に対する重量％を示す。■ Cresol novolak resin. ■
Fine silica powder with a particle size of 7 to 20 nm. The blending ratio of liquid components in the table is the total amount of ethylene glycol monoethyl ether acetate, ethyl acetate, and toluene blended as appropriate.
Weight % based on the entire resist composition is shown.
【００１８】表中の微粉体の配合割合は、上記■のシリ
カ微粉体の、前記固形分全体に対する重量％を示す。表
中の微粉体の疎水化率は、上記■のシリカ微粉体全体中
に含まれる疎水化処理シリカ微粉体の、シリカ微粉体全
体に対する重量割合を示す。次に、得られたレジスト組
成物の流体性状と見かけ粘度を調べ、その結果を第１表
に示した。見かけ粘度については、レオメータ（ＨＡＫ
ＫＥ社製、ＲＶ−２０）を用い、せん断速度を０ｓ−１
から１００ｓ−１まで１分間で変化させ、１分間１００
ｓ−１でホールドした後、１００ｓ−１から０ｓ−１ま
で１分間で変化させた時に得られた粘度曲線から、低せ
ん断速度（５ｓ−１）時および高せん断速度（３０ｓ−
１）時の見かけ粘度を求めた。なお、レジスト組成物が
チキソトロピー性を示す場合（比較例４）の高せん断速
度時および低せん断速度時の見かけ粘度については、せ
ん断速度を０ｓ−１から１００ｓ−１まで１分間で変化
させた時（昇せん断速度時）に得られた粘度曲線から求
めた。The blending ratio of fine powder in the table indicates the weight percent of the fine silica powder (2) above based on the total solid content. The hydrophobization rate of the fine powder in the table indicates the weight ratio of the hydrophobized fine silica powder contained in the whole fine silica powder (2) above to the whole fine silica powder. Next, the fluid properties and apparent viscosity of the obtained resist composition were examined, and the results are shown in Table 1. For apparent viscosity, use a rheometer (HAK
(manufactured by KE, RV-20), the shear rate was set to 0 s-1.
to 100 s-1 in 1 minute, and 100 s-1 for 1 minute.
From the viscosity curves obtained when holding at s-1 and then changing from 100 s-1 to 0 s-1 in 1 minute, the viscosity curves at low shear rate (5 s-1) and at high shear rate (30 s-1)
1) The apparent viscosity at the time was determined. Note that when the resist composition exhibits thixotropy (Comparative Example 4), the apparent viscosity at high shear rate and at low shear rate is determined by changing the shear rate from 0 s to 100 s in 1 minute. It was determined from the viscosity curve obtained (at increasing shear rate).
【００１９】次に、前記得られたレジスト組成物を用い
、通常のディップ条件で、スルーホール付き銅張り板上
にレジスト被膜を形成させ、スルーホールエッジ部の被
膜形成状態を調べ、その結果を表１に示した。Next, using the resist composition obtained above, a resist film was formed on a copper clad plate with through holes under normal dipping conditions, and the state of film formation at the edge of the through holes was examined. It is shown in Table 1.
【００２０】[0020]
【表１】[Table 1]
【００２１】表１にみるように、実施例１〜５にかかる
レジスト組成物を用いて形成されたレジスト被膜は、い
ずれも膜厚が適度に薄いものであり、しかも、膜厚にバ
ラツキが少ない良好な被膜であることが確認された。一
方、比較例１〜２にかかるレジスト組成物のように、擬
塑性流体であるが、粘度範囲が不適当なレジスト組成物
から形成されたレジスト被膜は、厚く付きすぎたり薄く
付きすぎたりしており、満足のいく被膜性状ではなかっ
た。また、比較例３にかかるレジスト組成物のように、
せん断速度に関わらず粘度が一定のニュートン流体であ
るレジスト組成物から形成されたレジスト被膜は、薄く
付きすぎており、満足のいく被膜性状ではなかった。さ
らに、比較例４にかかるレジスト組成物のようにチキソ
トロピー性を示すレジスト組成物、および、比較例５に
かかるレジスト組成物のように、疎水化率が０％の微粉
体の添加により粘度調整されたレジスト組成物から形成
されたレジスト被膜は、いずれも膜厚にバラツキが大き
く、満足のいく被膜性状ではなかった。As shown in Table 1, all of the resist films formed using the resist compositions according to Examples 1 to 5 had a suitably thin film thickness, and there was little variation in film thickness. It was confirmed that the coating was good. On the other hand, a resist film formed from a resist composition that is a pseudoplastic fluid but has an inappropriate viscosity range, such as the resist compositions according to Comparative Examples 1 and 2, may be too thick or too thin. However, the film properties were not satisfactory. In addition, like the resist composition according to Comparative Example 3,
A resist film formed from a resist composition that is a Newtonian fluid with a constant viscosity regardless of the shear rate was too thin and had unsatisfactory film properties. Furthermore, the viscosity of a resist composition exhibiting thixotropy, such as the resist composition of Comparative Example 4, and the resist composition of Comparative Example 5, is adjusted by adding fine powder with a hydrophobization rate of 0%. All of the resist films formed from the resist compositions had large variations in film thickness and had unsatisfactory film properties.
【００２２】[0022]
【発明の効果】この発明にかかるレジスト組成物によれ
ば、膜厚が均一で適度に薄い良好な被膜性状を有するレ
ジスト被膜を形成することができる。According to the resist composition according to the present invention, a resist film having a uniform thickness, a moderately thin film thickness, and good film properties can be formed.
【図１】この発明の一実施例であるレジスト組成物をデ
ィップ工法によって基材に塗布する工程を模式的に説明
する図である。FIG. 1 is a diagram schematically illustrating a process of applying a resist composition according to an embodiment of the present invention to a base material by a dip method.
【図２】同レジスト組成物の見かけ粘度とせん断速度の
関係を表すグラフである。FIG. 2 is a graph showing the relationship between the apparent viscosity and shear rate of the same resist composition.
２ レジスト組成物 2 Resist composition
Claims (2)
三つの条件（ａ）、（ｂ）、（ｃ）を満たすことを特徴
とするレジスト組成物。 （ａ）塑性流体ないし擬塑性流体であること。 （ｂ）見かけ粘度が、せん断速度３０ｓ −１以上の時
には２００ｃｐｓ以下であり、せん断速度５ｓ−１以下
の時には２５０ｃｐｓ以上であること。 （ｃ）上記流動特性（ａ）および（ｂ）を得るために、
少なくとも一部が疎水化処理された粒径１μｍ以下の微
粉体が添加されていること。1. A liquid resist composition, which satisfies the following three conditions (a), (b), and (c). (a) It is a plastic fluid or a pseudoplastic fluid. (b) The apparent viscosity is 200 cps or less when the shear rate is 30 s -1 or more, and 250 cps or more when the shear rate is 5 s -1 or less. (c) To obtain the above flow characteristics (a) and (b),
Added is a fine powder with a particle size of 1 μm or less that has been at least partially hydrophobized.
レジスト組成物。2. The resist composition according to claim 1, wherein the fine powder is silica.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3088880A JPH04218049A (en) | 1990-07-20 | 1991-04-20 | Resist composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2-193248 | 1990-07-20 | ||
| JP19324890 | 1990-07-20 | ||
| JP3088880A JPH04218049A (en) | 1990-07-20 | 1991-04-20 | Resist composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04218049A true JPH04218049A (en) | 1992-08-07 |
Family
ID=26430222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3088880A Pending JPH04218049A (en) | 1990-07-20 | 1991-04-20 | Resist composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04218049A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06180499A (en) * | 1992-12-14 | 1994-06-28 | Matsushita Electric Works Ltd | Liquid resist composition |
| JP2001194775A (en) * | 1999-11-01 | 2001-07-19 | Kansai Research Institute | Active particles, photosensitive resin composition and pattern forming method |
| EP1058697A4 (en) * | 1998-03-05 | 2002-10-16 | Du Pont | Polymeric films having controlled viscosity response to temperature and shear |
| WO2008123049A1 (en) * | 2007-03-30 | 2008-10-16 | Jsr Corporation | Method for film formation, resin composition for use in the method, structure having insulating film, process for producing the structure, and electronic component |
| JP2008277771A (en) * | 2007-03-30 | 2008-11-13 | Jsr Corp | Method for film formation, structure having insulating film and its manufacturing method and electronic component |
| JP2009133924A (en) * | 2007-11-28 | 2009-06-18 | Jsr Corp | Method for film formation and positive photosensitive resin composition for use in the same |
| WO2009150918A1 (en) * | 2008-06-11 | 2009-12-17 | Jsr株式会社 | Structure having insulating coating film, method for producing the same, positive photosensitive resin composition and electronic device |
-
1991
- 1991-04-20 JP JP3088880A patent/JPH04218049A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06180499A (en) * | 1992-12-14 | 1994-06-28 | Matsushita Electric Works Ltd | Liquid resist composition |
| EP1058697A4 (en) * | 1998-03-05 | 2002-10-16 | Du Pont | Polymeric films having controlled viscosity response to temperature and shear |
| JP2001194775A (en) * | 1999-11-01 | 2001-07-19 | Kansai Research Institute | Active particles, photosensitive resin composition and pattern forming method |
| WO2008123049A1 (en) * | 2007-03-30 | 2008-10-16 | Jsr Corporation | Method for film formation, resin composition for use in the method, structure having insulating film, process for producing the structure, and electronic component |
| JP2008277771A (en) * | 2007-03-30 | 2008-11-13 | Jsr Corp | Method for film formation, structure having insulating film and its manufacturing method and electronic component |
| JP2009133924A (en) * | 2007-11-28 | 2009-06-18 | Jsr Corp | Method for film formation and positive photosensitive resin composition for use in the same |
| WO2009150918A1 (en) * | 2008-06-11 | 2009-12-17 | Jsr株式会社 | Structure having insulating coating film, method for producing the same, positive photosensitive resin composition and electronic device |
| JP5246259B2 (en) * | 2008-06-11 | 2013-07-24 | Ｊｓｒ株式会社 | Structure having insulating film and method for producing the same, positive photosensitive resin composition, and electronic component |
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