JP5867197B2 - Photosensitive composition, protective film using the same, and insulating film for touch panel - Google Patents
Photosensitive composition, protective film using the same, and insulating film for touch panel Download PDFInfo
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- JP5867197B2 JP5867197B2 JP2012056780A JP2012056780A JP5867197B2 JP 5867197 B2 JP5867197 B2 JP 5867197B2 JP 2012056780 A JP2012056780 A JP 2012056780A JP 2012056780 A JP2012056780 A JP 2012056780A JP 5867197 B2 JP5867197 B2 JP 5867197B2
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- 238000005406 washing Methods 0.000 description 1
- 238000004394 yellowing prevention Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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Description
本発明は感光性組成物、ならびにそれを用いた保護膜およびタッチパネル用絶縁膜に関する。 The present invention relates to a photosensitive composition, a protective film using the same, and an insulating film for a touch panel.
近年、電子機器の高機能化や多様化や小型軽量化が進むに伴い、液晶等の表示素子の前面に透明タッチパネルを装着し、この透明タッチパネルを通して表示素子に表示された文字や記号、絵柄などの視認、選択を行い、透明タッチパネルの操作によって機器の各機能の切り替えを行うものが増えている。 In recent years, as electronic devices have become more sophisticated, diversified, and smaller and lighter, a transparent touch panel is mounted on the front surface of a display element such as a liquid crystal, and characters, symbols, patterns, etc. displayed on the display element through this transparent touch panel There are an increasing number of devices that perform visual recognition and selection, and switch each function of the device by operating a transparent touch panel.
タッチパネルは、例えば、銀行ATM、自動販売機、携帯情報端末(PDA、UMPC)、複写機、ファクシミリ、携帯ゲーム機、案内板、カーナビゲーション、マルチメディアステーション(コンビニエンスストアに設置されている多機能端末)、携帯電話、鉄道車両のモニタ装置、クイズ番組などの回答用機器等の入力機器として急激に普及している。 The touch panel is, for example, a bank ATM, a vending machine, a personal digital assistant (PDA, UMPC), a copier, a facsimile, a portable game machine, a guide board, a car navigation, a multimedia station (a multifunction terminal installed in a convenience store) ), And rapidly becoming widespread as input devices such as mobile phones, railway vehicle monitoring devices, and answering devices such as quiz programs.
既存のタッチパネルの方式としては、抵抗膜方式、光学方式、静電容量方式、超音波方式、圧力方式、電磁波誘導方式、画像認識方式、振動検出方式などに分けられる。
液晶などの表示装置上に配置されるタッチパネルとしての具体例としては、抵抗膜方式や静電容量方式があり、抵抗膜方式は押圧された位置を電圧によって検知する方式であり、静電容量方式は押圧することによって起きる静電容量の変化を捉えて位置を検出するものである。
静電容量方式は、特許文献1〜3などが開示され、接触した位置の誤認識を防ぐ為にその積層構造の中に絶縁膜や保護膜を設けることが行なわれている。
Existing touch panel systems can be classified into a resistive film system, an optical system, an electrostatic capacity system, an ultrasonic system, a pressure system, an electromagnetic wave induction system, an image recognition system, a vibration detection system, and the like.
Specific examples of a touch panel arranged on a display device such as a liquid crystal include a resistance film method and a capacitance method. The resistance film method is a method of detecting a pressed position by voltage, and a capacitance method. Detects the position by capturing the change in capacitance caused by pressing.
As for the electrostatic capacity method, Patent Documents 1 to 3 and the like are disclosed, and an insulating film and a protective film are provided in the laminated structure in order to prevent erroneous recognition of a contact position.
この絶縁膜や保護膜において要求される性能は、基材、下地、その他の層(ガラス、無機材料、金属材料、ITOなどの透明電極、有機材料など)との密着性、ITOやモリブデンのエッチング液などへの耐性(エッチャント耐性)、タッチパネル製造工程での高温焼成工程への耐熱性、積層基板にした際の透過率、絶縁性などが求められている。 The performance required for this insulating film and protective film is: adhesion to substrates, bases, and other layers (glass, inorganic materials, metal materials, transparent electrodes such as ITO, organic materials, etc.), etching of ITO and molybdenum Resistance to liquids (etchant resistance), heat resistance to a high-temperature baking process in the touch panel manufacturing process, transmittance when formed into a multilayer substrate, insulation, and the like are required.
またタッチパネル用途に用いられる絶縁膜や保護膜は高い表面硬度が要求され、特許文献4には、樹脂成分に無機酸化物微粒子を添加する方法が開示されている。
さらに特許文献5にはイソシアネート基含有シラン化合物を用いて基材密着性を向上する方法が開示されている。
In addition, an insulating film and a protective film used for touch panel applications are required to have high surface hardness, and Patent Document 4 discloses a method of adding inorganic oxide fine particles to a resin component.
Further, Patent Document 5 discloses a method of improving the substrate adhesion using an isocyanate group-containing silane compound.
しかし、これらの方法では、高温での焼成工程により黄変し、透過率が低くなったり、絶縁性が悪化したり、安定性が不十分であるなどの問題が見られる。
すなわち従来の感光性組成物では、基材密着性や、鉛筆硬度、耐性にも優れ、透過率、絶縁性、安定性など、すべてを満足することはできなかった。
However, these methods have problems such as yellowing due to a baking process at a high temperature, low transmittance, poor insulation, and insufficient stability.
That is, the conventional photosensitive composition is excellent in substrate adhesion, pencil hardness, and durability, and cannot satisfy all of transmittance, insulation, and stability.
本発明の目的は、基材や下地などとの密着性が良好であり、鉛筆硬度、エッチャント耐性に優れる塗膜を形成でき、経時安定性に優れた感光性組成物と、それを用いた保護膜あるいはタッチパネル用絶縁膜を提供することを目的とする。 An object of the present invention is to provide a photosensitive composition having good adhesion to a base material, a base, and the like, capable of forming a coating film having excellent pencil hardness and etchant resistance, and having excellent temporal stability, and protection using the same. An object is to provide a film or an insulating film for a touch panel.
本発明者らは、前記課題を解決しうる新たな手段について鋭意検討の結果、少なくともエチレン性不飽和二重結合を有する化合物(A)と、特定構造を有するシラン化合物(B)とを含む感光性組成物により、前述の課題を解決できることを見出し、本発明に至った。 As a result of intensive studies on new means that can solve the above-mentioned problems, the present inventors have developed a photosensitivity containing at least a compound (A) having an ethylenically unsaturated double bond and a silane compound (B) having a specific structure. The present inventors have found that the above-mentioned problems can be solved by the composition, and have reached the present invention.
即ち、本発明は、少なくともエチレン性不飽和二重結合を有する化合物(A)と、下記一般式(1)で表わされるシラン化合物(B)とを含有する感光性組成物に関する。
一般式(1):
Xは炭素数1〜20のアルキレン基、炭素数1〜20のアリーレン基、または、炭素数1〜20のアルコキシレン基を表し、
R2、R3およびR4は互いに独立して、炭素数1〜20のアルコキシ基、炭素数6〜20のアリールオキシ基、炭素数1〜20のアルキル基、炭素数6〜20のアリール基、炭素数7〜30のアルアルキル基、炭素数7〜30のアルカリール基、置換基を有するシロキサン、ハロゲン、ヒドロキシおよび水素を表す。]
That is, this invention relates to the photosensitive composition containing the compound (A) which has an ethylenically unsaturated double bond at least, and the silane compound (B) represented by following General formula (1).
General formula (1):
X represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 1 to 20 carbon atoms, or an alkoxylene group having 1 to 20 carbon atoms,
R 2 , R 3 and R 4 are independently of each other an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Represents an aralkyl group having 7 to 30 carbon atoms, an alkaryl group having 7 to 30 carbon atoms, a siloxane having a substituent, halogen, hydroxy and hydrogen. ]
また、本発明は、シラン化合物(B)の重量平均分子量(Mw)が100以上5000未満であり、かつ感光性組成物の固形分合計100重量%中の該シラン化合物(B)の含有量が5重量%以上60重量%未満であることを特徴とする上記感光性組成物に関する。 In the present invention, the weight average molecular weight (Mw) of the silane compound (B) is 100 or more and less than 5000, and the content of the silane compound (B) in the total solid content of 100% by weight of the photosensitive composition is It is related with the said photosensitive composition characterized by being 5 weight% or more and less than 60 weight%.
また、本発明は、エチレン性不飽和二重結合を有する化合物(A)が、二重結合当量350g/mol以上1200g/mol未満であり、かつ重量分子量Mw500以上40000未満である化合物を含むことを特徴とする、上記感光性組成物に関する。 In addition, the present invention includes that the compound (A) having an ethylenically unsaturated double bond includes a compound having a double bond equivalent of 350 g / mol or more and less than 1200 g / mol and a weight molecular weight Mw of 500 or more and less than 40000. It is related with the said photosensitive composition characterized.
また、本発明は、さらに、ケイ素、アルミニウム、ジルコニウム、チタニウムおよび亜鉛よりなる群から選ばれる少なくとも一つの元素の酸化物微粒子(C)を含むことを特徴とする上記感光性組成物に関する。 The present invention also relates to the above photosensitive composition, further comprising oxide fine particles (C) of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium and zinc.
また、本発明は、酸化物微粒子(C)の含有量が、感光性組成物の固形分合計100重量%中、5重量%以上50重量%未満であり、シラン化合物(B)の重量(b)と酸化物微粒子(C)の重量(c)との比率(b/c)が、0.4以上20.0未満であることを特徴とする上記感光性組成物に関する。 Further, in the present invention, the content of the oxide fine particles (C) is 5 wt% or more and less than 50 wt% in the total solid content of the photosensitive composition of 100 wt%, and the weight of the silane compound (B) (b ) And the weight (c) of the fine oxide particles (C) (b / c) is 0.4 or more and less than 20.0.
また、本発明は、さらに、溶剤(D)を含有し、溶剤(D)の20℃での水に対する溶解度が1g/100ml以上30g/100ml未満であることを特徴とする上記感光性組成物に関する。 Furthermore, the present invention relates to the above photosensitive composition, further comprising a solvent (D), wherein the solubility of the solvent (D) in water at 20 ° C. is 1 g / 100 ml or more and less than 30 g / 100 ml. .
また、本発明は、エチレン性不飽和二重結合を有する化合物(A)が酸価(固形分換算)30mgKOH/g以上200mgKOH/g未満の化合物を含むことを特徴とする、上記感光性組成物に関する。 Further, the present invention provides the photosensitive composition, wherein the compound (A) having an ethylenically unsaturated double bond includes a compound having an acid value (in terms of solid content) of 30 mgKOH / g or more and less than 200 mgKOH / g. About.
また、本発明は、さらに、テトラアルコキシシラン(E)を含有し、シラン化合物(B)の重量(b)とテトラアルコキシシラン(E)の重量(e)との比率(b/e)が、2以上20未満であることを特徴とする上記感光性組成物に関する。 The present invention further comprises a tetraalkoxysilane (E), and the ratio (b / e) of the weight (b) of the silane compound (B) to the weight (e) of the tetraalkoxysilane (E) is: It is related with the said photosensitive composition characterized by being 2-20.
また、本発明は、上記感光性組成物を用いてなる保護膜に関する。 Moreover, this invention relates to the protective film which uses the said photosensitive composition.
また、本発明は、上記感光性組成物を用いてなるタッチパネル用絶縁膜に関する。 Moreover, this invention relates to the insulating film for touchscreens which uses the said photosensitive composition.
本発明の感光性組成物により、基材や下地などとの密着性が良好であり、かつ経時安定性に優れ、鉛筆硬度、エッチャント耐性に優れる塗膜の形成が可能であり、優れた保護膜あるいはタッチパネル用絶縁膜の提供が可能となる。 With the photosensitive composition of the present invention, it is possible to form a coating film that has good adhesion to a substrate, a base, and the like, is excellent in stability over time, has excellent pencil hardness, and etchant resistance, and has an excellent protective film. Alternatively, an insulating film for a touch panel can be provided.
以下、本発明を詳細に説明する。
なお、本願では、「(メタ)アクリロイル」、「(メタ)アクリル」、「(メタ)アクリル酸」、又は「(メタ)アクリレート」と表記した場合には、特に説明がない限り、それぞれ、「アクリロイル及び/又はメタクリロイル」、「アクリル及び/又はメタクリル」、「アクリル酸及び/又はメタクリル酸」、又は「アクリレート及び/又はメタクリレート」を表すものとする。
Hereinafter, the present invention will be described in detail.
In the present application, when expressed as “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, or “(meth) acrylate”, unless otherwise specified, It shall represent "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid" or "acrylate and / or methacrylate".
まず本発明の感光性組成物の各種構成成分について説明する。
<エチレン性不飽和二重結合を有する化合物(A)>
本発明の感光性組成物は、エチレン性不飽和二重結合を有する化合物(A)を含むことを特徴とする。
エチレン性不飽和二重結合を有する化合物(A)としては、エチレン性不飽和二重結合を有する単量体(A1)、あるいは、側鎖にエチレン性不飽和二重結合を有する樹脂[A2]が挙げられる。
エチレン性不飽和二重結合を有する化合物(A)は、エチレン性不飽和二重結合を有する単量体(A1)と、側鎖にエチレン性不飽和二重結合を有する樹脂[A2]とのうちの、いずれか一方、あるいは両方を含んでいても良いが、エチレン性不飽和二重結合を有する単量体(A1)の含有量は、感光性組成物の固形分の合計100重量%中、5〜80重量%の量で用いることが好ましい。この場合、5重量%より単量体(A1)が少ないと、鉛筆硬度アップや耐溶剤性付与という効果が得られず、80重量%より多いと透過率の低下、基材密着性の低下が起こりやすい。より好ましくは、10〜50重量%である。
First, various components of the photosensitive composition of the present invention will be described.
<Compound (A) having an ethylenically unsaturated double bond>
The photosensitive composition of the present invention comprises a compound (A) having an ethylenically unsaturated double bond.
As the compound (A) having an ethylenically unsaturated double bond, a monomer (A1) having an ethylenically unsaturated double bond, or a resin having an ethylenically unsaturated double bond in the side chain [A2] Is mentioned.
The compound (A) having an ethylenically unsaturated double bond comprises a monomer (A1) having an ethylenically unsaturated double bond and a resin [A2] having an ethylenically unsaturated double bond in the side chain. Either or both of them may be contained, but the content of the monomer (A1) having an ethylenically unsaturated double bond is 100% by weight in total of the solid content of the photosensitive composition. , Preferably in an amount of 5 to 80% by weight. In this case, if the amount of the monomer (A1) is less than 5% by weight, the effect of increasing pencil hardness and imparting solvent resistance cannot be obtained. If the amount is more than 80% by weight, the transmittance and the substrate adhesion are decreased. It is easy to happen. More preferably, it is 10 to 50% by weight.
<エチレン性不飽和二重結合を有する単量体(A1)>
エチレン性不飽和二重結合を有する単量体(A1)としては、一般式(2)で表される化合物(a1)、酸基を有するエチレン性不飽和単量体(a2)、水酸基を有するエチレン性不飽和単量体(a3)、エポキシ基を有するエチレン性不飽和単量体(a4)、イソシアネート基を有するエチレン性不飽和単量体(a5)、および、(a1)〜(a5)以外のエチレン性不飽和単量体(a6)があげられる。
<Monomer (E1) having an ethylenically unsaturated double bond>
Examples of the monomer (A1) having an ethylenically unsaturated double bond include the compound (a1) represented by the general formula (2), the ethylenically unsaturated monomer (a2) having an acid group, and a hydroxyl group. Ethylenically unsaturated monomer (a3), ethylenically unsaturated monomer having epoxy group (a4), ethylenically unsaturated monomer having isocyanate group (a5), and (a1) to (a5) And ethylenically unsaturated monomers (a6) other than the above.
<一般式(2)で表される化合物(a1)>
一般式(2):
General formula (2):
一般式(2)中、R7およびR8で表される、置換基を有していてもよい炭素数1〜25の炭化水素基としては、特に制限はないが、例えば、メチル、エチル、n−プロピル、イソプロピル、n−ブチル、イソブチル、t−ブチル、t−アミル、ステアリル、ラウリル、2−エチルヘキシル等の直鎖状または分岐状のアルキル基;フェニル等のアリール基;シクロヘキシル、t−ブチルシクロヘキシル、ジシクロペンタジエニル、トリシクロデカニル、イソボルニル、アダマンチル、2−メチル−2−アダマンチル等の脂環式基;1−メトキシエチル、1−エトキシエチル等のアルコキシで置換されたアルキル基;ベンジル等のアリール基で置換されたアルキル基;等が挙げられる。これらの中でも特に、メチル、エチル、シクロヘキシル、ベンジル等のような酸や熱で脱離しにくい炭化水素基が耐熱性の点で好ましい。なお、R7およびR8は、同種の炭化水素基であってもよいし、異なる炭化水素基であってもよい。 In the general formula (2), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R 7 and R 8 is not particularly limited, and examples thereof include methyl, ethyl, linear or branched alkyl groups such as n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, t-butyl An alicyclic group such as cyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; an alkyl group substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like and a hydrocarbon group which is difficult to be removed by heat are preferable from the viewpoint of heat resistance. R 7 and R 8 may be the same type of hydrocarbon group or different hydrocarbon groups.
[化合物(a1)]
化合物(a1)の具体例としては、例えば、ジメチル−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジエチル−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジ(n−プロピル)−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジ(イソプロピル)−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジ(n−ブチル)−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジ(イソブチル)−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジ(t−ブチル)−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジ(t−アミル)−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジ(ステアリル)−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジ(ラウリル)−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジ(2−エチルヘキシル)−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジ(1−メトキシエチル)−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジ(1−エトキシエチル)−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジベンジル−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジフェニル−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジシクロヘキシル−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジ(t−ブチルシクロヘキシル)−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジ(ジシクロペンタジエニル)−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジ(トリシクロデカニル)−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジ(イソボルニル)−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジアダマンチル−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジ(2−メチル−2−アダマンチル)−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート等が挙げられる。これらの中でも特に、ジメチル−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジエチル−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジシクロヘキシル−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエート、ジベンジル−2,2′−[オキシビス(メチレン)]ビス−2−プロペノエートがあげられる。
これらの化合物(a1)は、1種を単独で、または必要に応じて任意の比率で2種以上混合して用いることができる。
[Compound (a1)]
Specific examples of the compound (a1) include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, Di (n-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n- Butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2 , 2 '-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propenoate Di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 '-[oxybis (methylene)] Bis-2-propenoate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, di (t-butyl Chlohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (tricyclo Decanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 ' -[Oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate and the like. Among these, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'- [Oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 '-[oxybis (methylene)] bis-2-propenoate.
These compounds (a1) can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.
<酸基を有するエチレン性不飽和単量体(a2)>
酸基を有するエチレン性不飽和単量体(a2)としては、例えば、(メタ)アクリル酸やイタコン酸、クロトン酸、o−、m−、p−ビニル安息香酸、(メタ)アクリル酸のα位ハロアルキル、アルコキシル、ハロゲン、ニトロ、シアノ置換体等のモノカルボン酸等のカルボキシル基を有するエチレン性不飽和単量体(不飽和一塩基酸(a2‘))、
N−ヒドロキシフェニルマレイミド等のフェノール性水酸基を有するエチレン性不飽和単量体、
テトラヒドロ無水フタル酸、無水フタル酸、ヘキサヒドロ無水フタル酸、無水コハク酸、無水マレイン酸等の多塩基酸無水物等が挙げられるが、これらの中でも特に、(メタ)アクリル酸が好ましい。
<Ethylenically unsaturated monomer having acid group (a2)>
Examples of the ethylenically unsaturated monomer (a2) having an acid group include (meth) acrylic acid, itaconic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α of (meth) acrylic acid. An ethylenically unsaturated monomer (unsaturated monobasic acid (a2 ′)) having a carboxyl group such as a monocarboxylic acid such as a substituted haloalkyl, alkoxyl, halogen, nitro, cyano substituent, etc.
An ethylenically unsaturated monomer having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide;
Examples thereof include polybasic acid anhydrides such as tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. Among them, (meth) acrylic acid is particularly preferable.
<水酸基を有するエチレン性不飽和単量体(a3)>
水酸基を有するエチレン性不飽和単量体(a3)としては、2−ヒドロキシエチル(メタ)アクリレート、2−若しくは3−ヒドロキシプロピル(メタ)アクリレート、2−若しくは3−若しくは4−ヒドロキシブチル(メタ)アクリレート、グリセロール(メタ)アクリレート、又はシクロヘキサンジメタノールモノ(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレート類が挙げられ、これらは、単独で用いても、2種類以上を併用して用いてもかまわない。
また、上記ヒドロキシアルキル(メタ)アクリレートに、エチレンオキシド、プロピレンオキシド、及び/又はブチレンオキシド等を付加重合させたポリエーテルモノ(メタ)アクリレートや、(ポリ)γ−バレロラクトン、(ポリ)ε−カプロラクトン、及び/又は(ポリ)12−ヒドロキシステアリン酸等を付加した(ポリ)エステルモノ(メタ)アクリレートも使用できる。
<Ethylenically unsaturated monomer having a hydroxyl group (a3)>
Examples of the ethylenically unsaturated monomer (a3) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth). Examples thereof include hydroxyalkyl (meth) acrylates such as acrylate, glycerol (meth) acrylate, or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Absent.
Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used.
<エポキシ基を有するエチレン性不飽和単量体(a4)>
エポキシ基を有するエチレン性不飽和単量体(a4)としては、例えば、グリシジル(メタ)アクリレート、メチルグリシジル(メタ)アクリレート、2−グリシドキシエチル(メタ)アクリレート、3,4エポキシブチル(メタ)アクリレート、及び3,4エポキシシクロヘキシル(メタ)アクリレートが挙げられ、これらは、単独で用いても、2種類以上を併用してもかまわない。
<Ethylenically unsaturated monomer (a4) having an epoxy group>
Examples of the ethylenically unsaturated monomer (a4) having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4 epoxybutyl (meth) ) Acrylate and 3,4 epoxy cyclohexyl (meth) acrylate, and these may be used alone or in combination of two or more.
<イソシアネート基を有するエチレン性不飽和単量体(a5)>
イソシアネート基を有するエチレン性不飽和単量体(a5)としては、2−(メタ)アクリロイルオキシエチルイソシアネート、又は1,1−ビス〔(メタ)アクリロイルオキシ〕エチルイソシアネート等が挙げられ、これらに限定することなく、2種類以上併用することもできる。
<An ethylenically unsaturated monomer having an isocyanate group (a5)>
Examples of the ethylenically unsaturated monomer (a5) having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. Two or more types can also be used together without doing.
<(a1)〜(a5)以外のエチレン性不飽和単量体(a6)>
(a1)〜(a5)以外のエチレン性不飽和単量体(a6)としては、メチル(メタ)メタアクリレート、エチル(メタ)アクリレート、n−プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、s−ブチル(メタ)アクリレート、t−ブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、イソペンチルアクリレート、ネオペンチル(メタ)アクリレート、t−ペンチル(メタ)アクリレート、1−メチルブチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、ヘプタ(メタ)アクリレート、オクチル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、ラウリル(メタ)アクリレート、セチル(メタ)アクリレート、ステアリル(メタ)アクリレート、イソステアリル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート等のアルキル(メタ)アクリレート、あるいは、(a6‘)として後述するアルキル(メタ)アクリレート、
アリル(メタ)アクリレート、又はオレイル(メタ)アクリレート、ビニル(メタ)アクリレート等のアルケニル(メタ)アクリレート、ベンジルメタクリレート等の置換されたアルキル(メタ)アクリレート、
スチレン、メチルスチレン、塩化ビニル、酢酸ビニル、ブタジエン、イソプレン、シクロペンタジエン、シクロヘキセン等のビニル化合物などの単官能単量体、
トリメチロールプロパンジアクリレート、トリメチロールプロパンジメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリメタクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールペンタメタクリレート等のモノヒドロキシオリゴアクリレートまたはモノヒドロキシオリゴメタクリレート類と、マロン酸、こはく酸、グルタル酸、テレフタル酸等のジカルボン酸類との遊離カルボキシル基含有モノエステル化物;プロパン−1,2,3−トリカルボン酸(トリカルバリル酸)、ブタン−1,2,4−トリカルボン酸、ベンゼン−1,2,3−トリカルボン酸、ベンゼン−1,3,4−トリカルボン酸、ベンゼン−1,3,5−トリカルボン酸等のトリカルボン酸類と、2−ヒドロキシエチルアクリレート、2−ヒドロキシエチルメタクリレート、2−ヒドロキシプロピルアクリレート、2−ヒドロキシプロピルメタクリレート等のモノヒドロキシモノアクリレートまたはモノヒドロキシモノメタクリレート類との遊離カルボキシル基含有オリゴエステル化物などの多官能単量体が挙げられるが、必ずしもこれらに限定されるものではない。
これらの光重合性単量体は、1種を単独で、または必要に応じて任意の比率で2種以上混合して用いることができる。
<Ethylenically unsaturated monomer (a6) other than (a1) to (a5)>
As ethylenically unsaturated monomers (a6) other than (a1) to (a5), methyl (meth) methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (Meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl acrylate, neopentyl (meth) acrylate, t-pentyl (meth) acrylate 1-methylbutyl (meth) acrylate, hexyl (meth) acrylate, hepta (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (Meth) acrylate, isostearyl (meth) acrylate, alkyl (meth) acrylate such as cyclohexyl (meth) acrylate, or alkyl (meth) acrylate described later as (a6 ′),
Allyl (meth) acrylate, oleyl (meth) acrylate, alkenyl (meth) acrylate such as vinyl (meth) acrylate, substituted alkyl (meth) acrylate such as benzyl methacrylate,
Monofunctional monomers such as vinyl compounds such as styrene, methylstyrene, vinyl chloride, vinyl acetate, butadiene, isoprene, cyclopentadiene, cyclohexene,
Monohydroxy oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, and malonic acid, Monoesterified products containing free carboxyl groups with dicarboxylic acids such as succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene Tricarboxylic acids such as -1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, and 2-hydride Polyfunctional monomers such as monohydroxy monoacrylates such as xylethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, or oligoesters containing free carboxyl groups with monohydroxy monomethacrylates Although it is mentioned, it is not necessarily limited to these.
These photopolymerizable monomers can be used singly or in combination of two or more at any ratio as required.
なかでも、1分子中に7個以上のエチレン性不飽和二重結合を有する多官能単量体を含むことが好ましい。これを含むことで、鉛筆硬度、エッチャント耐性に優れるものとなる。また透過率の維持、鉛筆硬度と基材密着性のバランスなどの観点から7〜16個のエチレン性不飽和二重結合を有する多官能単量体であることが好ましく、さらに7〜12個である場合、鉛筆硬度と基材密着性、さらにエッチャント耐性に優れるため、より好ましい。
このような多官能単量体として市販品では、例えば、ビスコート#802(トリペンタエリスリトールオクタアクリレート、テトラペンタエリスリトールデカアクリレート、およびペンタペンタエリスリトールドデカアクリレートの混合物、大阪有機化学工業株式会社製)を挙げることができる。
Especially, it is preferable that the polyfunctional monomer which has 7 or more ethylenically unsaturated double bonds in 1 molecule is included. By including this, it will be excellent in pencil hardness and etchant tolerance. Moreover, it is preferable that it is a polyfunctional monomer which has 7-16 ethylenically unsaturated double bonds from viewpoints, such as the maintenance of a transmittance | permeability, and pencil hardness and base-material adhesiveness, Furthermore, it is 7-12 pieces. In some cases, it is more preferable because it is excellent in pencil hardness, substrate adhesion, and etchant resistance.
As such a polyfunctional monomer, commercially available products include, for example, Biscoat # 802 (mixture of tripentaerythritol octaacrylate, tetrapentaerythritol decaacrylate, and pentapentaerythritol dodecaacrylate, manufactured by Osaka Organic Chemical Co., Ltd.). be able to.
<側鎖にエチレン性不飽和二重結合を有する樹脂の骨格となる樹脂[A2]>
側鎖にエチレン性不飽和二重結合を有する樹脂の骨格となる樹脂[A2]としては、熱可塑性樹脂[A2−1]、熱硬化性樹脂[A2−2]がある。
側鎖にエチレン性不飽和二重結合を有する樹脂の骨格となる樹脂[A2]は、可視光領域の400〜700nmの全波長領域において分光透過率が好ましくは80%以上、より好ましくは95%以上の樹脂である。また、それぞれの樹脂を単独に使用しても良いし、併用しても良い。
<Resin [A2] serving as a skeleton of a resin having an ethylenically unsaturated double bond in the side chain>
Examples of the resin [A2] serving as a skeleton of a resin having an ethylenically unsaturated double bond in the side chain include a thermoplastic resin [A2-1] and a thermosetting resin [A2-2].
The resin [A2] serving as a skeleton of a resin having an ethylenically unsaturated double bond in the side chain preferably has a spectral transmittance of 80% or more, more preferably 95% in the entire wavelength region of 400 to 700 nm in the visible light region. The above resin. Moreover, each resin may be used independently and may be used together.
熱硬化性樹脂[A2−2]は、例えば、ベンゾグアナミン樹脂、ロジン変性マレイン酸樹脂、ロジン変性フマル酸樹脂、メラミン樹脂、エポキシ樹脂、尿素樹脂、及びフェノール樹脂等が挙げられる。中でも、耐熱性向上の観点から、エポキシ樹脂、メラミン樹脂がより好適に用いられる。 Examples of the thermosetting resin [A2-2] include benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, epoxy resin, urea resin, and phenol resin. Especially, an epoxy resin and a melamine resin are used more suitably from a viewpoint of heat resistance improvement.
熱可塑性樹脂[A2−1]は、例えば、アクリル樹脂、ブチラール樹脂、スチレンーマレイン酸共重合体、塩素化ポリエチレン、塩素化ポリプロピレン、ポリ塩化ビニル、塩化ビニル−酢酸ビニル共重合体、ポリ酢酸ビニル、ポリウレタン系樹脂、ポリエステル樹脂、ビニル系樹脂、アルキッド樹脂、ポリスチレン樹脂、ポリアミド樹脂、ゴム系樹脂、環化ゴム系樹脂、セルロース類、ポリエチレン(HDPE、LDPE)、ポリブタジエン、及びポリイミド樹脂等が挙げられる。
熱可塑性樹脂[A2−1]としては、酸性基含有エチレン性不飽和単量体を共重合したアルカリ可溶性ビニル系樹脂がより好ましい。
The thermoplastic resin [A2-1] is, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate. , Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. .
As the thermoplastic resin [A2-1], an alkali-soluble vinyl resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer is more preferable.
酸性基含有エチレン性不飽和単量体(a2)を共重合したアルカリ可溶性ビニル系樹脂は、例えば、カルボキシル基、スルホン基、フェノール性水酸基、多塩基酸無水物基等の酸性基を有する樹脂が挙げられる。これら酸基は、1種のみであってもよいし、2種以上であってもよい。アルカリ可溶性樹脂として具体的には、酸性基を有するアクリル樹脂、α−オレフィン/(無水)マレイン酸共重合体、スチレン/スチレンスルホン酸共重合体、エチレン/(メタ)アクリル酸共重合体、又はイソブチレン/(無水)マレイン酸共重合体等が挙げられる。中でも、酸性基を有するアクリル樹脂、およびスチレン/スチレンスルホン酸共重合体から選ばれる少なくとも1種の樹脂、特に酸性基を有するアクリル樹脂は、耐熱性、透明性が高いため、好適に用いられる。 The alkali-soluble vinyl resin obtained by copolymerizing the acidic group-containing ethylenically unsaturated monomer (a2) is, for example, a resin having an acidic group such as a carboxyl group, a sulfone group, a phenolic hydroxyl group, or a polybasic acid anhydride group. Can be mentioned. These acid groups may be used alone or in combination of two or more. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.
樹脂に酸基を導入する方法としては、酸基を有するエチレン性不飽和単量体(a2)を用いる方法、あるいは重合後に酸基を付与しうるエチレン性不飽和単量体を、エチレン性不飽和単量体成分として重合する方法を用いても良い。 As a method for introducing an acid group into the resin, a method using an ethylenically unsaturated monomer (a2) having an acid group or an ethylenically unsaturated monomer capable of imparting an acid group after polymerization is used. A method of polymerizing as a saturated monomer component may be used.
酸基を有するエチレン性不飽和単量体(a2)を含む場合、その含有割合は、特に制限されないが、全エチレン性不飽和単量体成分の合計100重量%中5〜70重量%、好ましくは10〜60重量%であるのがよい。 When the ethylenically unsaturated monomer (a2) having an acid group is included, the content ratio is not particularly limited, but it is preferably 5 to 70% by weight in the total 100% by weight of all ethylenically unsaturated monomer components, preferably Is preferably 10 to 60% by weight.
重合後に酸基を付与しうるエチレン性不飽和単量体としては、例えば、2−ヒドロキシエチル(メタ)アクリレート等の水酸基を有するエチレン性不飽和単量体(a3)、グリシジル(メタ)アクリレート等のエポキシ基を有するエチレン性不飽和単量体(a4)等が挙げられる。
水酸基を有するエチレン性不飽和単量体(a3)を用いる場合には、例えば水酸基を有するエチレン性不飽和単量体(a3)と、共重合可能なその他のエチレン性不飽和単量体とを共重合することによって得られた共重合体の水酸基に、多塩基酸無水物を反応させ、酸基(カルボキシル基)を導入することが出来る。あるいは、エポキシ基を有するエチレン性不飽和単量体(a4)を用いる場合には、例えばエポキシ基を有するエチレン性不飽和単量体(a4)と、共重合可能なその他のエチレン性不飽和単量体とを共重合することによって得られた共重合体の側鎖エポキシ基に、カルボキシル基を有する不飽和一塩基酸(a2‘)を付加反応させ、更に、生成した水酸基に、多塩基酸無水物を反応させ、酸基(カルボキシル基)を導入することが出来る。この方法では、水酸基と多塩基酸無水物を過不足なく反応させると水酸基が消失する。一方、水酸基の一部と多塩基酸無水物を反応させることで、側鎖に水酸基を有し、かつカルボキシル基等の酸基およびエチレン性不飽和二重結合を有する樹脂が得られる。
Examples of the ethylenically unsaturated monomer capable of imparting an acid group after polymerization include, for example, an ethylenically unsaturated monomer (a3) having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and the like. And an ethylenically unsaturated monomer (a4) having an epoxy group.
When the ethylenically unsaturated monomer (a3) having a hydroxyl group is used, for example, the ethylenically unsaturated monomer (a3) having a hydroxyl group and another ethylenically unsaturated monomer that can be copolymerized are used. The hydroxyl group of the copolymer obtained by copolymerization can be reacted with a polybasic acid anhydride to introduce an acid group (carboxyl group). Or when using the ethylenically unsaturated monomer (a4) which has an epoxy group, for example, the ethylenically unsaturated monomer (a4) which has an epoxy group, and the other ethylenically unsaturated monomer which can be copolymerized An unsaturated monobasic acid (a2 ′) having a carboxyl group is added to the side chain epoxy group of the copolymer obtained by copolymerizing with a monomer, and a polybasic acid is added to the generated hydroxyl group. An anhydride can be reacted to introduce an acid group (carboxyl group). In this method, when the hydroxyl group and the polybasic acid anhydride are reacted without excess or deficiency, the hydroxyl group disappears. On the other hand, a resin having a hydroxyl group in the side chain and an acid group such as a carboxyl group and an ethylenically unsaturated double bond is obtained by reacting a part of the hydroxyl group with a polybasic acid anhydride.
重合後に酸基を付与するためのエチレン性不飽和単量体を含む場合、その含有割合は、特に制限されないが、全エチレン性不飽和単量体成分の合計100重量%中5〜70重量%、好ましくは10〜60重量%であるのがよい。 When an ethylenically unsaturated monomer for imparting an acid group after polymerization is included, the content ratio is not particularly limited, but is 5 to 70% by weight in a total of 100% by weight of all ethylenically unsaturated monomer components. Preferably, it is 10 to 60% by weight.
酸基を導入することにより、得られる感光性組成物は、酸基とエポキシ基あるいは水酸基が反応してエステル結合が生じることを利用した架橋反応が可能な感光性組成物、あるいは未硬化部をアルカリ現像液で現像可能な組成物、とすることができる。前記酸基としては、特に制限されないが、例えば、カルボキシル基、フェノール性水酸基、カルボン酸無水物基等が挙げられる。これら酸基は、1種のみであってもよいし、2種以上であってもよい。 By introducing an acid group, the resulting photosensitive composition is a photosensitive composition capable of a crosslinking reaction utilizing the fact that an ester bond is formed by the reaction of an acid group with an epoxy group or a hydroxyl group, or an uncured part. The composition can be developed with an alkali developer. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups may be used alone or in combination of two or more.
<樹脂にエチレン性不飽和二重結合を導入する方法>
樹脂の側鎖にエチレン性不飽和二重結合を有するためには、たとえば以下に示す(a)や(b)の方法が挙げられる。
<Method of introducing ethylenically unsaturated double bond into resin>
In order to have an ethylenically unsaturated double bond in the side chain of the resin, for example, the following methods (a) and (b) are exemplified.
[方法(a)]
方法(a)としては、例えば、エポキシ基を有するエチレン性不飽和単量体(a4)と、他の1種類以上の単量体とを共重合することによって得られた共重合体の側鎖エポキシ基に、エチレン性不飽和二重結合を有する不飽和一塩基酸のカルボキシル基を付加反応させ、更に、生成した水酸基に、多塩基酸無水物を反応させ、エチレン性不飽和二重結合およびカルボキシル基を導入する方法がある。
[Method (a)]
As the method (a), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer (a4) having an epoxy group and one or more other monomers. An epoxy group is allowed to undergo an addition reaction with a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and a polybasic acid anhydride is further reacted with the resulting hydroxyl group to produce an ethylenically unsaturated double bond and There is a method of introducing a carboxyl group.
エポキシ基を有するエチレン性不飽和単量体(a4)としては、(A1)で説明したものがあげられ、次工程の不飽和一塩基酸との反応性の観点で、グリシジル(メタ)アクリレートが好ましい。 Examples of the ethylenically unsaturated monomer (a4) having an epoxy group include those described in (A1). From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferable.
不飽和一塩基酸(a2‘)としては、(A1)で説明したものがあげられ、これらは、単独で用いても、2種類以上を併用してもかまわない。 As unsaturated monobasic acid (a2 '), what was demonstrated by (A1) is mention | raise | lifted, These may be used independently or may use 2 or more types together.
多塩基酸無水物としては、テトラヒドロ無水フタル酸、無水フタル酸、ヘキサヒドロ無水フタル酸、無水コハク酸、無水マレイン酸等が挙げられ、これらは単独で用いても、2種類以上を併用してもかまわない。カルボキシル基の数を増やす等、必要に応じて、トリメリット酸無水物等のトリカルボン酸無水物を用いたり、ピロメリット酸二無水物等のテトラカルボン酸二無水物を用いて、残った無水物基を加水分解したりすること等もできる。また、多塩基酸無水物として、エチレン性不飽和二重結合を有する、エトラヒドロ無水フタル酸、又は無水マレイン酸を用いると、更にエチレン性不飽和二重結合を増やすことができる。 Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.
方法(a)の類似の方法として、例えば、酸基を有するエチレン性不飽和単量体(a2)と、他の1種類以上の単量体とを共重合することによって得られた共重合体の側鎖カルボキシル基の一部に、エポキシ基を有するエチレン性不飽和単量体を付加反応させ、エチレン性不飽和二重結合およびカルボキシル基を導入する方法がある。 As a method similar to method (a), for example, a copolymer obtained by copolymerizing an ethylenically unsaturated monomer (a2) having an acid group and one or more other monomers There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of the side chain carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.
[方法(b)]
方法(b)としては、水酸基を有するエチレン性不飽和単量体(a3)を使用し、他のカルボキシル基を有する不飽和一塩基酸(a2‘)や、(a3)(a2’)以外の単量体とを共重合することによって得られた共重合体の側鎖水酸基に、イソシアネート基を有するエチレン性不飽和単量体(a5)のイソシアネート基を反応させる方法がある。
[Method (b)]
As the method (b), an ethylenically unsaturated monomer having a hydroxyl group (a3) is used, and other than the unsaturated monobasic acid having another carboxyl group (a2 ′) or (a3) (a2 ′) There is a method in which the isocyanate group of the ethylenically unsaturated monomer (a5) having an isocyanate group is reacted with the side chain hydroxyl group of the copolymer obtained by copolymerizing with the monomer.
水酸基を有するエチレン性不飽和単量体(a3)としては、(A1)で説明したものがあげられ、塗膜異物抑制の観点から、2−ヒドロキシエチル(メタ)アクリレート、又はグリセロール(メタ)アクリレートが好ましい。 Examples of the ethylenically unsaturated monomer (a3) having a hydroxyl group include those described in (A1), and 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate, from the viewpoint of suppressing foreign matter on the coating film. Is preferred.
イソシアネート基を有するエチレン性不飽和単量体(a5)としては、(A1)で説明したものがあげられる。 Examples of the ethylenically unsaturated monomer (a5) having an isocyanate group include those described in (A1).
特に、(メタ)アクリル酸、クロトン酸、若しくはα−クロルアクリル酸等の不飽和モノカルボン酸、又はマレイン酸、若しくはフマル酸等の不飽和ジカルボン酸等のカルボキシル基を含有しかつエチレン性不飽和二重結合を有する化合物等の酸基を有するエチレン性不飽和単量体(a2)からなる群と、(A1)で説明中(a6)として説明したアルキル(メタ)アクリレート類からなる群から選ばれ、それぞれ1種類以上使用することが好ましい。 In particular, it contains a carboxyl group such as an unsaturated monocarboxylic acid such as (meth) acrylic acid, crotonic acid, or α-chloroacrylic acid, or an unsaturated dicarboxylic acid such as maleic acid or fumaric acid, and is ethylenically unsaturated. Selected from the group consisting of an ethylenically unsaturated monomer (a2) having an acid group, such as a compound having a double bond, and the group consisting of alkyl (meth) acrylates described as (a6) in the description in (A1) It is preferable to use one or more of each.
樹脂[A2]は、二重結合当量が350g/mol以上1200g/mol未満であり、分子量Mwが500以上40000未満であることが好ましい。二重結合当量が350g/molより小さい場合は、樹脂の硬化収縮が大きくなるため基材密着性が低下することがあり、二重結合当量が1200g/molを超える場合は、十分な鉛筆硬度を満たすことができないことがあるため好ましくない。また、重量分子量Mwが500より小さい場合は、樹脂の硬化収縮が大きくなるため基材密着性が低下することがあり、重量分子量Mwが40000を超える場合は、鉛筆硬度が悪化することがあり好ましくない。
二重結合当量が350〜1200g/mol、重量分子量Mwが500以上40000未満であることで、優れた鉛筆硬度および基材密着性を引き出すことが可能である。
The resin [A2] preferably has a double bond equivalent of 350 g / mol or more and less than 1200 g / mol and a molecular weight Mw of 500 or more and less than 40000. When the double bond equivalent is less than 350 g / mol, the resin shrinkage increases and the substrate adhesion may decrease. When the double bond equivalent exceeds 1200 g / mol, sufficient pencil hardness is obtained. Since it may not be able to be satisfied, it is not preferable. Further, when the weight molecular weight Mw is smaller than 500, the curing shrinkage of the resin is increased, and thus the substrate adhesion may be decreased. When the weight molecular weight Mw exceeds 40000, the pencil hardness may be deteriorated. Absent.
When the double bond equivalent is 350 to 1200 g / mol and the weight molecular weight Mw is 500 or more and less than 40000, it is possible to draw out excellent pencil hardness and substrate adhesion.
また、樹脂[A2]の酸価が30mgKOH/g以上200mgKOH/g未満であることが、感光性組成物の現像性や経時安定性の面からより好ましい。酸価が30未満である場合は、感光性組成物の現像性が低下するため好ましくない。酸価が200以上である場合は、シラン化合物(B)の加水分解を促進し、感光性組成物が形成する塗膜の鉛筆硬度や基板密着性が経時経過とともに低下するため、好ましくない。 In addition, the acid value of the resin [A2] is more preferably 30 mgKOH / g or more and less than 200 mgKOH / g from the viewpoint of developability and temporal stability of the photosensitive composition. An acid value of less than 30 is not preferable because the developability of the photosensitive composition is lowered. When the acid value is 200 or more, hydrolysis of the silane compound (B) is promoted, and the pencil hardness and substrate adhesion of the coating film formed by the photosensitive composition are decreased with the passage of time.
[樹脂(A2−a)]
樹脂[A2]は、下記一般式(2)で表される化合物(a1)と、化合物(a1)と共重合可能な他の化合物とを共重合してなる樹脂(A2−a)であることが特に好ましい。
化合物(a1)の説明は、(A1)で説明した通りである。
[Resin (A2-a)]
The resin [A2] is a resin (A2-a) obtained by copolymerizing the compound (a1) represented by the following general formula (2) and another compound copolymerizable with the compound (a1). Is particularly preferred.
The description of the compound (a1) is as described in (A1).
化合物(a1)と共重合可能なその他のエチレン性不飽和単量体とを共重合して樹脂(A2−a)を得る際に、重合と同時に化合物(a1)の環化反応が進行してテトラヒドロピラン環構造が形成される。 When the resin (A2-a) is obtained by copolymerizing the compound (a1) with another ethylenically unsaturated monomer copolymerizable, the cyclization reaction of the compound (a1) proceeds simultaneously with the polymerization. A tetrahydropyran ring structure is formed.
樹脂(A2−a)を得る際のエチレン性不飽和単量体成分中における化合物(a1)の割合は、特に制限されないが、全エチレン性不飽和単量体成分中2〜50重量%、好ましくは5〜55重量%、さらに好ましくは5〜50重量%であるのがよい。化合物(a1)の量が多すぎると共重合の際、低分子量のものを得ることが困難になったり、あるいはゲル化し易くなったりするおそれがあり、一方、少なすぎると、透明性や耐熱性などの塗膜性能が不充分となるおそれがある。 The ratio of the compound (a1) in the ethylenically unsaturated monomer component in obtaining the resin (A2-a) is not particularly limited, but is preferably 2 to 50% by weight in the total ethylenically unsaturated monomer component, preferably Is 5 to 55% by weight, more preferably 5 to 50% by weight. If the amount of the compound (a1) is too large, it may be difficult to obtain a low molecular weight product during copolymerization or may be easily gelled. On the other hand, if the amount is too small, the transparency and heat resistance may be increased. There is a possibility that the performance of the coating film becomes insufficient.
[化合物(a1)と共重合可能な他の化合物]
化合物(a1)と共重合可能な他の化合物(a2)としては、化合物(a1)と共重合可能であればとくに制限は無く、(A1)で説明中、(a2)〜(a6)として説明したものがあげられるが、アルカリ可溶性を付与するために酸基を導入するための単量体を含むことが好ましく、その他、エチレン性不飽和二重結合を導入するための単量体、側鎖型環状エーテル含有単量体(a6‘)が好ましい。
樹脂(A2−a)に酸基、および、エチレン性不飽和二重結合を導入する方法については、すでに樹脂[a2]で説明した。
[Other compounds copolymerizable with compound (a1)]
The other compound (a2) copolymerizable with the compound (a1) is not particularly limited as long as it can be copolymerized with the compound (a1), and is described as (a2) to (a6) in the description in (A1). It is preferable to include a monomer for introducing an acid group to impart alkali solubility, and other monomers for introducing an ethylenically unsaturated double bond, side chain Type cyclic ether-containing monomer (a6 ′) is preferred.
The method for introducing an acid group and an ethylenically unsaturated double bond into the resin (A2-a) has already been described in the resin [a2].
<側鎖型環状エーテル含有単量体(a6‘)>
側鎖型環状エーテル含有単量体(a6‘)としては、たとえば、テトラヒドロフラン骨格、フラン骨格、テトラヒドロピラン骨格、ピラン骨格、ラクトン骨格の郡から選ばれる少なくとも1つの骨格を含有する不飽和化合物である。
テトラヒドロフラン骨格としては、テトラヒドロフルフリル(メタ)アクリレート、2−メタクリロイルオキシ−プロピオン酸テトラヒドロフルフリルエステル、(メタ)アクリル酸テトラヒドロフラン−3−イルエステルなど;
フラン骨格としては、2−メチル−5−(3−フリル)−1−ペンテン−3−オン、フルフリル(メタ)アクリレート、1−フラン−2−ブチル−3−エン−2−オン、1−フラン−2−ブチル−3−メトキシ−3−エン−2−オン、6−(2−フリル)−2−メチル−1−ヘキセン−3−オン、6−フラン−2−イル−ヘキシ−1−エン−3−オン、アクリル酸2−フラン−2−イル−1−メチル−エチルエステル、6−(2−フリル)−6−メチル−1−ヘプテン−3−オンなど;
テトラヒドロピラン骨格としては、(テトラヒドロピラン−2−イル)メチルメタクリレート、2,6−ジメチル−8−(テトラヒドロピラン−2−イルオキシ)−オクト−1−エン−3−オン、2−メタクリル酸テトラヒドロピラン−2−イルエステル、1−(テトラヒドロピラン−2−オキシ)−ブチル−3−エン−2−オンなど;
ピラン骨格としては、4−(1,4−ジオキサ−5−オキソ−6−ヘプテニル)−6−メチル−2−ピロン、4−(1,5−ジオキサ−6−オキソ−7−オクテニル)−6−メチル−2−ピロンなど;
ラクトン骨格としては、2−プロペン酸2−メチル−テトラヒドロ−2−オキソ−3−フラニルエステル、2−プロペン酸2−メチル−7−オキソ−6−オクサビシクロ[3.2.1]オクト−2−イルエステル、2−プロペン酸2−メチル−ヘキサヒドロ−2−オキソ−3,5−メタノ−2H−シクロペンタ[b]フラン−7−イルエステル、2−プロペン酸2−メチル−テトラヒドロ−2−オキソ−2H−ピラン−3−イルエステル、2−プロペン酸(テトラヒドロ−5−オキソ−2−フラニル)メチルエステル、2−プロペン酸ヘキサヒドロ−2−オキソ−2,6−メタノフロ[3,2−b]−6−イルエステル、2−プロペン酸2−メチル−2−(テトラヒドロ−5−オキソ−3−フラニル)エチルエステル、2−プロペン酸2−メチル−デカヒドロ−8−オキソ−5,9−メタノ−2H−フロ[3,4−g]−1−ベンゾピラン−2−イルエステル、2−プロペン酸2−メチル−2−[(ヘキサヒドロ−2−オキソ−3,5−メタノ−2H−シクロペンタ[b]フラン−6−イル)オキシ]エチルエステル、2−プロペン酸3−オキソ−3−[(テトラヒドロ−2−オキソ−3−フラニル)オキシ]プロピルエステル、2−プロペン酸2−メチル−2−オキシ−1−オクサスピロ[4.5]デク−8−イルエステルなどが挙げられる。
これらのうちテトラヒドロフルフリル(メタ)アクリレートが着色、入手性の点から好ましい。これら側鎖型環状エーテル含有単量体は単独で用いても2種以上を複合して用いても構わない。
<Side Chain Cyclic Ether-Containing Monomer (a6 ′)>
The side chain type cyclic ether-containing monomer (a6 ′) is, for example, an unsaturated compound containing at least one skeleton selected from the group consisting of a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, and a lactone skeleton. .
Examples of the tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, (meth) acrylic acid tetrahydrofuran-3-yl ester, and the like;
Examples of the furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-en-2-one, and 1-furan. 2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2-yl-hex-1-ene -3-one, 2-furan-2-yl-1-methyl-ethyl acrylate, 6- (2-furyl) -6-methyl-1-hepten-3-one, and the like;
Examples of the tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one, and tetrahydropyran 2-methacrylate. 2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, and the like;
Examples of the pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyrone and 4- (1,5-dioxa-6-oxo-7-octenyl) -6. -Methyl-2-pyrone and the like;
Examples of the lactone skeleton include 2-propenoic acid 2-methyl-tetrahydro-2-oxo-3-furanyl ester, 2-propenoic acid 2-methyl-7-oxo-6-oxabicyclo [3.2.1] oct-2- Yl ester, 2-propenoic acid 2-methyl-hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan-7-yl ester, 2-propenoic acid 2-methyl-tetrahydro-2-oxo- 2H-pyran-3-yl ester, 2-propenoic acid (tetrahydro-5-oxo-2-furanyl) methyl ester, 2-propenoic acid hexahydro-2-oxo-2,6-methanofuro [3,2-b]- 6-yl ester, 2-propenoic acid 2-methyl-2- (tetrahydro-5-oxo-3-furanyl) ethyl ester, 2-propenoic acid 2-methyl ester Ru-decahydro-8-oxo-5,9-methano-2H-furo [3,4-g] -1-benzopyran-2-yl ester, 2-propenoic acid 2-methyl-2-[(hexahydro-2- Oxo-3,5-methano-2H-cyclopenta [b] furan-6-yl) oxy] ethyl ester, 2-propenoic acid 3-oxo-3-[(tetrahydro-2-oxo-3-furanyl) oxy] propyl And 2-propenoic acid 2-methyl-2-oxy-1-oxaspiro [4.5] dec-8-yl ester.
Among these, tetrahydrofurfuryl (meth) acrylate is preferable from the viewpoint of coloring and availability. These side chain type cyclic ether-containing monomers may be used alone or in combination of two or more.
樹脂(A2−a)を得る際の単量体成分中における前記側鎖型環状エーテル含有単量体(a6‘)の割合は、特に制限されないが、全単量体成分中10〜80重量%、好ましくは20〜70重量%、さらに好ましくは30〜60重量%であるのがよい。側鎖型環状エーテル含有単量体の量が多すぎると、親水性が強くなりすぎてアルカリ現像時に表面が白化したり、パターンが欠けたり、ガラスへの密着性が低下し易くなったりするおそれがあり、一方、少なすぎると、耐熱性などの性能が不充分となる恐れがある。 The proportion of the side-chain cyclic ether-containing monomer (a6 ′) in the monomer component for obtaining the resin (A2-a) is not particularly limited, but is 10 to 80% by weight in the total monomer components. , Preferably 20 to 70% by weight, more preferably 30 to 60% by weight. If the amount of the side chain type cyclic ether-containing monomer is too large, the hydrophilicity becomes too strong and the surface may be whitened during alkali development, the pattern may be lost, or the adhesion to the glass may be reduced. On the other hand, if the amount is too small, performance such as heat resistance may be insufficient.
側鎖型環状エーテル含有単量体(a6‘)以外で、化合物(a1)と共重合可能な他の化合物として使用できるその他の共重合可能な単量体としては、(メタ)アクリル酸メチル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸ベンジル、スチレンが、透明性が良好で、耐熱性を損ないにくい点で好ましい。これら共重合可能な他の単量体は、1種のみ用いても2種以上を併用してもよい。 Other copolymerizable monomers that can be used as other compounds copolymerizable with the compound (a1) other than the side chain type cyclic ether-containing monomer (a6 ′) include methyl (meth) acrylate, Cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more.
前記単量体成分の重合反応の方法としては、特に制限はなく、従来公知の各種重合方法を採用することができるが、特に、溶液重合法によることが好ましい。なお、重合温度や重合濃度(重合濃度=[単量体成分の全重量/(単量体成分の全重量+溶媒重量)]×100とする)は、使用する単量体成分の種類や比率、目標とするポリマーの分子量によって異なるが、好ましくは、重合温度40〜150℃、重合濃度5〜50%とするのがよく、さらに好ましくは、重合温度60〜130℃、重合濃度10〜40%とするのがよい。
樹脂(A2−a)は、感光性組成物の固形分の合計100重量%中、10〜60重量%の量で用いることが好ましい。樹脂(A2−a)が10重量%より少ない場合、充分な基材密着性良化、高耐熱性の効果を得られず、60重量%より多い場合、光硬化成分量の含有量が少なくなり、充分な塗膜の鉛筆硬度を得る事が難しい。
The method for the polymerization reaction of the monomer component is not particularly limited, and various conventionally known polymerization methods can be employed, but the solution polymerization method is particularly preferable. The polymerization temperature and polymerization concentration (polymerization concentration = [total weight of monomer components / (total weight of monomer components + solvent weight)] × 100) are the types and ratios of the monomer components used. Depending on the molecular weight of the target polymer, the polymerization temperature is preferably 40 to 150 ° C. and the polymerization concentration is 5 to 50%, and more preferably, the polymerization temperature is 60 to 130 ° C. and the polymerization concentration is 10 to 40%. It is good to do.
The resin (A2-a) is preferably used in an amount of 10 to 60% by weight in a total of 100% by weight of the solid content of the photosensitive composition. When the amount of the resin (A2-a) is less than 10% by weight, sufficient substrate adhesion improvement and high heat resistance cannot be obtained. When the amount is more than 60% by weight, the content of the photocuring component is decreased. It is difficult to obtain a sufficient pencil hardness of the coating film.
(その他の樹脂(A2−b)
本発明の感光性組成物の樹脂[A2]は、樹脂(A2−a)に加えて、その他の樹脂(A2−b)を含んでいても良い。その他の樹脂(A2−b)が共重合体である場合は、樹脂(A2−a)の化合物(a1)を共重合成分として含まないものに相当し、なかでも前述した酸基を導入するための単量体あるいはラジカル重合性二重結合を導入するための単量体を共重合成分として含むものが好ましい。また、その他の樹脂(A2−b)は熱硬化性樹脂であっても良い。
(Other resins (A2-b)
Resin [A2] of the photosensitive composition of this invention may contain other resin (A2-b) in addition to resin (A2-a). When the other resin (A2-b) is a copolymer, it corresponds to a resin (A2-a) that does not contain the compound (a1) as a copolymerization component, and in particular, to introduce the acid group described above. And those containing a monomer for introducing a radical polymerizable double bond as a copolymerization component are preferred. Further, the other resin (A2-b) may be a thermosetting resin.
<シラン化合物(B)>
本発明の感光性組成物は、下記一般式(1)で表わされるシラン化合物(B)を含む。
一般式(1)
Xは炭素数1〜20のアルキレン基、炭素数1〜20のアリーレン基、または、炭素数1〜20のアルコキシレン基を表し、
R2、R3およびR4は互いに独立して、炭素数1〜20のアルコキシ基、炭素数6〜20のアリールオキシ基、炭素数1〜20のアルキル基、炭素数6〜20のアリール基、炭素数7〜30のアルアルキル基、炭素数7〜30のアルカリール基、置換基を有するシロキサン、ハロゲン、ヒドロキシおよび水素を表す。]
<Silane compound (B)>
The photosensitive composition of this invention contains the silane compound (B) represented by following General formula (1).
General formula (1)
X represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 1 to 20 carbon atoms, or an alkoxylene group having 1 to 20 carbon atoms,
R 2 , R 3 and R 4 are independently of each other an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Represents an aralkyl group having 7 to 30 carbon atoms, an alkaryl group having 7 to 30 carbon atoms, a siloxane having a substituent, halogen, hydroxy and hydrogen. ]
一般式(1)で表わされるシラン化合物(B)を含むことによりガラス基材、ITO、モリブデンなどのタッチパネルに用いられる部材との密着性が向上し、かつ鉛筆硬度が向上する。 By including the silane compound (B) represented by the general formula (1), adhesion to a member used for a touch panel such as a glass substrate, ITO, or molybdenum is improved, and pencil hardness is improved.
一般式(1)で表わされるシラン化合物(B)としては、例えば(3−カルバメートエチル)プロピルトリエトキシシラン、(3−カルバメートエチル)プロピルトリメトキシシラン、(3−カルバメートエチル)プロピルトリプロパキシシラン、(3−カルバメートプロピル)プロピルトリエトキシシラン、(3−カルバメートプロピル)プロピルトリメトキシシラン、(3−カルバメートプロピル)プロピルトリプロパキシシラン、(3−カルバメートブチル)プロピルトリエトキシシラン、(3−カルバメートブチル)プロピルトリメトキシシラン、(3−カルバメートブチル)プロピルトリプロパキシシラン、(3−カルバメートブチル)ブチルトリプロパキシシラン、(3−カルバメートブチル)プロピルメチルジエトキシシラン、(3−カルバメートペンチル)プロピルトリエトキシシラン、(3−カルバメートヘキシル)プロピルトリエトキシシラン、3−カルバメートオクチル)ペンチルトリブトキシシラン、
(3−カルバメートエチル)プロピルシリルトリクロライド、(3−カルバメートエチル)プロピルトリメチルシラン、3−カルバメートエチル)プロピルジメチルシラン、3−カルバメートエチル)プロピルトリブチルシラン、3−カルバメートエチル)エチル-p-キシレントリエトキシシラン、3−カルバメートエチル)-p-フェニレントリエトキシシランなどが挙げられるが、これらに限らない。また一般式(1)で表わされるシラン化合物(B)はその加水分解によるシラノール化合物であっても、それらが縮合したポリオルガノシロキサン化合物でも良い。
Examples of the silane compound (B) represented by the general formula (1) include (3-carbamateethyl) propyltriethoxysilane, (3-carbamateethyl) propyltrimethoxysilane, and (3-carbamateethyl) propyltripropoxysilane. , (3-carbamatepropyl) propyltriethoxysilane, (3-carbamatepropyl) propyltrimethoxysilane, (3-carbamatepropyl) propyltripropoxysilane, (3-carbamatebutyl) propyltriethoxysilane, (3-carbamate (Butyl) propyltrimethoxysilane, (3-carbamatebutyl) propyltripropoxysilane, (3-carbamatebutyl) butyltripropoxysilane, (3-carbamatebutyl) propylmethyldiethoxysilane, ( - carbamate pentyl) triethoxysilane, (3-carbamate-hexyl) triethoxysilane, 3-carbamate-octyl) pen tilt butoxy silane,
(3-carbamateethyl) propylsilyltrichloride, (3-carbamateethyl) propyltrimethylsilane, 3-carbamateethyl) propyldimethylsilane, 3-carbamateethyl) propyltributylsilane, 3-carbamateethyl) ethyl-p-xylenetri Examples include, but are not limited to, ethoxysilane, 3-carbamateethyl) -p-phenylenetriethoxysilane, and the like. Further, the silane compound (B) represented by the general formula (1) may be a silanol compound obtained by hydrolysis thereof, or a polyorganosiloxane compound in which they are condensed.
シラン化合物(B)の重量平均分子量(Mw)は100以上5000未満が好ましく、かつ感光性組成物の固形分合計100重量%中の該シラン化合物(B)の含有量が5重量%以上60重量%未満であることが好ましい。シラン化合物(B)の重量平均分子量(Mw)が100未満の場合基材密着性が悪化し、5000以上の場合鉛筆硬度が悪化するため好ましくない。また含有量が5重量%未満の場合鉛筆硬度が低下し、60重量%以上の場合基材密着性と透過率が低下するため好ましくない。
また、シラン化合物(B)の重量平均分子量(Mw)は200以上500未満であることが、鉛筆硬度と基材密着性の点からより好ましく、感光性組成物の固形分合計100重量%中の該シラン化合物(B)の含有量が10重量%以上50重量%未満であることが、基材密着性の点からより好ましい。
The weight average molecular weight (Mw) of the silane compound (B) is preferably 100 or more and less than 5000, and the content of the silane compound (B) in the total solid content of 100% by weight of the photosensitive composition is 5% by weight or more and 60% by weight. It is preferable that it is less than%. When the weight average molecular weight (Mw) of the silane compound (B) is less than 100, the substrate adhesion is deteriorated, and when it is 5000 or more, the pencil hardness is deteriorated. Further, when the content is less than 5% by weight, the pencil hardness is lowered, and when it is 60% by weight or more, the substrate adhesion and the transmittance are lowered, which is not preferable.
The weight average molecular weight (Mw) of the silane compound (B) is more preferably 200 or more and less than 500 from the viewpoint of pencil hardness and substrate adhesion, and the total solid content of the photosensitive composition is 100% by weight. The content of the silane compound (B) is more preferably 10% by weight or more and less than 50% by weight from the viewpoint of substrate adhesion.
イソシアネート基含有シラン化合物、例えば3−イソシアネートプロピルトリメトキシシラン、3−イソシアネートプロピルトリエトキシシラン、3−イソシアネートプロピルトリプロパキシシランは、感光性組成物中の溶剤、樹脂、単量体、水分と反応して白濁したり、ゲル化したりすることがある。またその硬化塗膜は安定して高い鉛筆硬度と基材密着性を発現できない。それと比較して一般式(1)で表わされるシラン化合物(B)は、イソシアネート基のような高い反応性を持つ部位を持たないため、熱的、化学的に安定である。そのため、シラン化合物(B)は感光性組成物中でも経時安定性に優れており、安定して高い鉛筆硬度と良好な基材密着性を示すことができる。 Isocyanate group-containing silane compounds such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-isocyanatepropyltripropoxysilane react with the solvent, resin, monomer, and moisture in the photosensitive composition. May become cloudy or gel. In addition, the cured coating cannot stably exhibit high pencil hardness and substrate adhesion. In comparison, the silane compound (B) represented by the general formula (1) is thermally and chemically stable because it does not have a highly reactive site such as an isocyanate group. Therefore, the silane compound (B) is excellent in stability over time even in the photosensitive composition, and can stably exhibit high pencil hardness and good substrate adhesion.
<酸化物微粒子(C)>
本発明の感光性組成物には酸化物微粒子(C)を含むことが好ましい。酸化物微粒子は表面処理されていても良く、得られる硬化性組成物の硬化被膜の無色性の観点から、ケイ素、アルミニウム、ジルコニウム、チタニウムおよび亜鉛よりなる群から選ばれる少なくとも一つの元素の酸化物粒子であることが好ましい。なかでも透過率の観点から、ケイ素、ジルコニウム、またはアルミニウムの酸化物粒子が好ましく、とくにケイ素の酸化物粒子が好ましい。
酸化物微粒子(C)を用いることで、さらに鉛筆硬度を高く、エッチャント耐性の高い塗膜を得ることができる。
<Oxide fine particles (C)>
The photosensitive composition of the present invention preferably contains fine oxide particles (C). The oxide fine particles may be surface-treated, and from the viewpoint of colorlessness of the cured film of the resulting curable composition, an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium and zinc Particles are preferred. Of these, from the viewpoint of transmittance, oxide particles of silicon, zirconium, or aluminum are preferable, and silicon oxide particles are particularly preferable.
By using the oxide fine particles (C), a coating film having higher pencil hardness and higher etchant resistance can be obtained.
酸化物微粒子(C)は、分散液中あるいは塗布液中で、分散安定化を図るために、あるいはバインダー成分との親和性、結合性を高めるために、プラズマ放電処理やコロナ放電処理のような物理的表面処理、界面活性剤やカップリング剤等による化学的表面処理がなされていても良い。 The oxide fine particles (C) are used in plasma dispersion treatment or corona discharge treatment in order to stabilize dispersion in the dispersion or coating solution, or to improve the affinity and binding properties with the binder component. A physical surface treatment or a chemical surface treatment with a surfactant or a coupling agent may be performed.
酸化物粒子(C)の平均一次粒子径は、1nm〜1000nmが好ましく、3nm〜100nmがさらに好ましく、5nm〜30nmが特に好ましい。平均一次粒子径が1000nmを超えると、硬化物としたときの透明性が低下したり、被膜としたときの表面状態が悪化する傾向がある。また、粒子の分散性を改良するために各種の界面活性剤やアミン類を添加してもよい。 The average primary particle diameter of the oxide particles (C) is preferably 1 nm to 1000 nm, more preferably 3 nm to 100 nm, and particularly preferably 5 nm to 30 nm. When the average primary particle diameter exceeds 1000 nm, the transparency when cured is reduced, or the surface state when coated is liable to deteriorate. Various surfactants and amines may be added to improve the dispersibility of the particles.
酸化物微粒子(C)の平均一次粒子径は、たとえばBET法を用いて測定される。具体的には、BET法にて得られた無機酸化物微粒子の比表面積を得、無機酸化物の比重を用いて体積と表面積の比を算出し、粒子を真球であると仮定して、これらの比から粒子径を求め、平均一次粒子径とする方法がある。 The average primary particle diameter of the oxide fine particles (C) is measured using, for example, the BET method. Specifically, the specific surface area of the inorganic oxide fine particles obtained by the BET method is obtained, the ratio of volume to surface area is calculated using the specific gravity of the inorganic oxide, and the particles are assumed to be true spheres. There is a method of obtaining the particle diameter from these ratios to obtain the average primary particle diameter.
酸化物粒子(C)は、有機溶媒分散物として用いるのが好ましい。有機溶媒分散物として用いる場合、他の成分との相溶性、分散性の観点から、分散媒は、有機溶剤が好ましい。このような有機溶剤としては、例えば、メタノール、エタノール、イソプロパノール、ブタノール、オクタノール等のアルコール系溶剤;アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤;酢酸エチル、酢酸ブチル、乳酸エチル、γ−ブチロラクトン、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等のエステル系溶剤;エチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル等のエーテル系溶剤;ベンゼン、トルエン、キシレン等の芳香族炭化水素系溶剤;ジメチルホルムアミド、ジメチルアセトアミド、N−メチルピロリドン等のアミド系溶剤等が挙げられる。
中でも、メタノール、イソプロパノール、ブタノール、メチルエチルケトン、メチルイソブチルケトン、酢酸エチル、酢酸ブチル、トルエン、キシレン、プロピレングリコールモノメチルエーテルアセテートが好ましい。
The oxide particles (C) are preferably used as an organic solvent dispersion. When used as an organic solvent dispersion, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such organic solvents include alcohol solvents such as methanol, ethanol, isopropanol, butanol, and octanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ -Ester solvents such as butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ether solvents such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbon solvents such as benzene, toluene and xylene; dimethyl Examples include amide solvents such as formamide, dimethylacetamide, and N-methylpyrrolidone.
Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, xylene, and propylene glycol monomethyl ether acetate are preferable.
本発明に特に好ましく用いられるケイ素の酸化物微粒子分散液として市販されている商品としては、日産化学工業(株)製MA−ST−MS、IPA−ST、IPA−ST−MS、IPA−ST−L、IPA−ST−ZL、IPA−ST−UP、EG−ST、NPC−ST−30、MEK−ST、MEK−ST−L、MIBK−ST、NBA−ST、XBA−ST、DMAC−ST、ST−UP、ST−OUP、ST−20、ST−40、ST−C、ST−N、ST−O、ST−50、ST−OL等、触媒化成工業(株)製中空シリカCS60−IPA等を挙げることができる。また粉体シリカとしては、日本アエロジル(株)製アエロジル130、アエロジル300、アエロジル380、アエロジルTT600、アエロジルOX50、旭硝子(株)製シルデックスH31、H32、H51、H52、H121、H122、日本シリカ工業(株)製E220A、E220、富士シリシア(株)製SYLYSIA470、日本板硝子(株)製SGフレ−ク等を挙げることができる。 Commercially available products as silicon oxide fine particle dispersions particularly preferably used in the present invention include MA-ST-MS, IPA-ST, IPA-ST-MS, and IPA-ST- manufactured by Nissan Chemical Industries, Ltd. L, IPA-ST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-L, MIBK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc., hollow silica CS60-IPA manufactured by Catalyst Kasei Kogyo Co., Ltd., etc. Can be mentioned. As the powdered silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Silex H31, H32, H51, H52, H121, H122, Asahi Glass Co., Ltd., Nippon Silica Industry, Nippon Aerosil Co., Ltd. Examples include E220A and E220 manufactured by Fuji Electric, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.
本発明に好ましく用いられるジルコニアの酸化物微粒子分散液として市販されている商品としては、日産化学工業(株)製ZR−40BL、ZR−30BS、ZR−30AL、ZR−30AH等、住友大阪セメント(株)製HXU−110JCを挙げることができる。 Examples of products that are commercially available as zirconia oxide fine particle dispersions preferably used in the present invention include ZR-40BL, ZR-30BS, ZR-30AL, ZR-30AH manufactured by Nissan Chemical Industries, Ltd., Sumitomo Osaka Cement ( HXU-110JC manufactured by Co., Ltd. can be mentioned.
本発明に好ましく用いられるアルミニウムの酸化物微粒子分散液として市販されている商品としては、日産化学工業(株)製アルミナゾル−100、アルミナゾル−200、アルミナゾル−520、住友大阪セメント(株)製AS−150I、AS−150Tが挙げられる。 Commercially available products as aluminum oxide fine particle dispersions preferably used in the present invention include alumina sol-100, alumina sol-200, alumina sol-520 manufactured by Nissan Chemical Industries, Ltd. and AS- manufactured by Sumitomo Osaka Cement Co., Ltd. 150I, AS-150T.
その他、本発明に好ましく用いられる酸化物微粒子分散液としては、チタニウム、亜鉛等の酸化物微粒子分散液が挙げられ、市販品としては、シーアイ化成(株)製ナノテック等を挙げることができる。 In addition, examples of the oxide fine particle dispersion preferably used in the present invention include oxide fine particle dispersions such as titanium and zinc, and examples of commercially available products include Nanotech manufactured by CI Kasei Co., Ltd.
酸化物微粒子(C)の添加量は感光性組成物における固形分合計100重量%中、5重量%以上50重量%未満が好ましく、10〜35重量%がさらに好ましい。添加量が5重量%未満である場合は鉛筆硬度、エッチャント耐性の向上などの効果が得られにくく、一方で50重量%を超える場合は、基材密着性が低下する、透過率が低下するなどの問題が生じることがある。
また、一般式(1)で表されるシラン化合物(B)の重量(b)と酸化物微粒子(C)の重量(c)との比率(b/c)が、0.4以上20.0未満であることが好ましく、1.0以上10.0未満がさらに好ましい。比率(b/c)が0.4未満である場合は基材密着性改善の効果が得られにくく、かつ絶縁性が低下するため好ましくない。比率(b/c)が20.0以上である場合は鉛筆硬度やエッチャント耐性が低下するため好ましくない。
The addition amount of the oxide fine particles (C) is preferably 5% by weight or more and less than 50% by weight, more preferably 10 to 35% by weight, in the total solid content of 100% by weight in the photosensitive composition. When the addition amount is less than 5% by weight, it is difficult to obtain effects such as improvement in pencil hardness and etchant resistance. On the other hand, when the addition amount exceeds 50% by weight, the adhesion to the substrate is lowered and the transmittance is lowered. Problems may occur.
The ratio (b / c) between the weight (b) of the silane compound (B) represented by the general formula (1) and the weight (c) of the oxide fine particles (C) is 0.4 or more and 20.0. Is preferably less than 1.0, and more preferably 1.0 or more and less than 10.0. When the ratio (b / c) is less than 0.4, the effect of improving the adhesion to the substrate is difficult to obtain, and the insulating property is lowered, which is not preferable. When the ratio (b / c) is 20.0 or more, the pencil hardness and the etchant resistance are lowered, which is not preferable.
<溶剤>
本発明の感光性組成物に用いる溶剤としては、1,2,3−トリクロロプロパン、1,3−ブタンジオール、1,3−ブチレングリコール、1,4−ジオキサン、2−ヘプタノン、2−メチル−1,3−プロパンジオール、3,5,5−トリメチル−2−シクロヘキセン−1−オン、3,3,5−トリメチルシクロヘキサノン、3−エトキシプロピオン酸エチル、3−メチル−1,3−ブタンジオール、3−メトキシ−3−メチル−1−ブタノール、3−メトキシ−3−メチルブチルアセテート、3−メトキシブタノール、3−メトキシブチルアセテート、4−ヘプタノン、m−キシレン、m−ジエチルベンゼン、m−ジクロロベンゼン、N,N−ジメチルアセトアミド、N,N−ジメチルホルムアミド、n−ブチルアルコール、n−ブチルベンゼン、n−プロピルアセテート、N−メチルピロリドン、o−キシレン、o−クロロトルエン、o−ジエチルベンゼン、o−ジクロロベンゼン、p−クロロトルエン、p−ジエチルベンゼン、sec−ブチルベンゼン、tert−ブチルベンゼン、γ―ブチロラクトン、イソブチルアルコール、イソホロン、エチレングリコールジエチルエーテル、エチレングリコールジブチルエーテル、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノターシャリーブチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノブチルエーテルアセテート、エチレングリコールモノプロピルエーテル、エチレングリコールモノヘキシルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテルアセテート、ジイソブチルケトン、ジエチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールモノイソプロピルエーテル、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノメチルエーテル、シクロヘキサノール、シクロペンタノン、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールメチルエーテルアセテート、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノブチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノメチルエーテル、ダイアセトンアルコール、トリアセチン、トリプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル、プロピレングリコールジアセテート、プロピレングリコールフェニルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノブチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルプロピオネート、ベンジルアルコール、メチルイソブチルケトン、メチルシクロヘキサノール、酢酸n−アミル、酢酸n−ブチル、酢酸イソアミル、酢酸イソブチル、酢酸プロピル、二塩基酸エステル等が挙げられ、これらを単独でもしくは混合して用いる。
<Solvent>
As the solvent used in the photosensitive composition of the present invention, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,4-dioxane, 2-heptanone, 2-methyl- 1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butyl N-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ -Butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene Glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol Recall monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, Cyclohexanol, cyclopentanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol Monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate , Propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, acetic acid Isobutyl, Propyl, dibasic acid esters, and the like, used alone or in combination.
特に溶剤の乾燥性を考慮し、ダイコートや印刷法などにおいては160℃以上の高沸点溶剤を含むことが好ましく、たとえば、3−メトキシ−3−メチル−1−ブタノール(bp174℃)、1,3−ブタンジオール(bp203℃)、3−メチル−1,3−ブタンジオール(bp203℃)、2−メチル−1,3−プロパンジオール(bp213℃)、ジイソブチルケトン(bp168.1℃)、エチレングリコールモノブチルエーテル(bp171.2℃)、エチレングリコールモノヘキシルエーテル(bp208.1℃)、エチレングリコールモノブチルエーテルアセテート(bp191.5℃)、エチレングリコールジブチルエーテル(bp203.3℃)、ジエチレングリコールモノメチルエーテル(bp194.0℃)、ジエチレングリコールモノエチルエーテル(bp202.0℃)、ジエチレングリコールジエチルエーテル(bp188.4℃)、ジエチレングリコールモノイソプロピルエーテル(bp207.3℃)、プロピレングリコールモノブチルエーテル(bp170.2℃)、プロピレングリコールジアセテート(bp190.0℃)、ジプロピレングリコールモノメチルエーテル(bp187.2℃)、ジプロピレングリコールモノエチルエーテル(bp197.8℃)、ジプロピレングリコールモノプロピルエーテル(bp212.0℃)、ジプロピレングリコールジメチルエーテル(bp175℃)、トリプロピレングリコールモノメチルエーテル(bp206.3℃)、3−エトキシプロピオン酸エチル(bp169.7℃)、3−メトキシブチルアセテート(bp172.5℃)、3−メトキシ−3−メチルブチルアセテート(bp188℃)、γ−ブチロラクトン(bp204℃)、N,N−ジメチルアセトアミド(bp166.1℃)、N−メチルピロリドン(bp202℃)、p−クロロトルエン(bp162.0℃)、o−ジエチルベンゼン(bp183.4℃)、m−ジエチルベンゼン(bp181.1℃)、p−ジエチルベンゼン(bp183.8℃)、o−ジクロロベンゼン(bp180.5℃)、m−ジクロロベンゼン(bp173.0℃)、n−ブチルベンゼン(bp183.3℃)、sec−ブチルベンゼン(bp178.3℃)、tert−ブチルベンゼン(bp169.1℃)、シクロヘキサノール(bp161.1℃)、シクロヘキシルアセテート(bp173℃)、メチルシクロヘキサノール(bp174℃)等が挙げられる。 In consideration of the drying property of the solvent, it is preferable to include a high boiling point solvent of 160 ° C. or higher in die coating or printing methods. For example, 3-methoxy-3-methyl-1-butanol (bp 174 ° C.), 1, 3 -Butanediol (bp 203 ° C.), 3-methyl-1,3-butanediol (bp 203 ° C.), 2-methyl-1,3-propanediol (bp 213 ° C.), diisobutyl ketone (bp 168.1 ° C.), ethylene glycol mono Butyl ether (bp 171.2 ° C.), ethylene glycol monohexyl ether (bp 208.1 ° C.), ethylene glycol monobutyl ether acetate (bp 191.5 ° C.), ethylene glycol dibutyl ether (bp 203.3 ° C.), diethylene glycol monomethyl ether (bp 194.0) ℃), Diechi Glycol monoethyl ether (bp 202.0 ° C.), diethylene glycol diethyl ether (bp 188.4 ° C.), diethylene glycol monoisopropyl ether (bp 207.3 ° C.), propylene glycol monobutyl ether (bp 170.2 ° C.), propylene glycol diacetate (bp 190 0.0 ° C.), dipropylene glycol monomethyl ether (bp 187.2 ° C.), dipropylene glycol monoethyl ether (bp 197.8 ° C.), dipropylene glycol monopropyl ether (bp 212.0 ° C.), dipropylene glycol dimethyl ether (bp 175 ° C.) ), Tripropylene glycol monomethyl ether (bp 206.3 ° C.), ethyl 3-ethoxypropionate (bp 169.7 ° C.), 3-methoxybutene Ruacetate (bp 172.5 ° C.), 3-methoxy-3-methylbutyl acetate (bp 188 ° C.), γ-butyrolactone (bp 204 ° C.), N, N-dimethylacetamide (bp 166.1 ° C.), N-methylpyrrolidone (bp 202 ° C), p-chlorotoluene (bp162.0 ° C), o-diethylbenzene (bp183.4 ° C), m-diethylbenzene (bp181.1 ° C), p-diethylbenzene (bp183.8 ° C), o-dichlorobenzene (bp180) .5 ° C), m-dichlorobenzene (bp 173.0 ° C), n-butylbenzene (bp183.3 ° C), sec-butylbenzene (bp178.3 ° C), tert-butylbenzene (bp169.1 ° C), cyclo Hexanol (bp 161.1 ° C), cyclohexyl acetate (bp 73 ° C.), and methyl cyclohexanol (bp174 ℃) and the like.
<溶剤(D)>
さらに本発明の感光性組成物は、20℃での水に対する溶解度が0.1g/100ml以上30g/100ml未満である溶剤(D)を含むことが好ましい。溶剤の水に対する溶解度が30g/100ml以上である場合、感光性組成物作製中に溶剤が水分を吸湿することでシラン化合物(B)が感光性組成物中で加水分解を起こし、感光性組成物が白濁化したり塗膜の基材密着性が低下したりする。また溶剤の水に対する溶解度が1g/100ml未満である場合、感光性組成物中の水分量が充分でなく加水分解によるシロキサン結合の形成などが起きにくくなり、塗膜の基材密着性が低下したりする場合がある。
溶剤(D)としては例えば、シクロヘキサノン(8.7g/100ml)、プロピレングリコールモノメチルエーテルアセテート(16.0g/100ml)、1,3−ブチレングリコールジアセテート(5.0g/100ml)、シクロヘキサノールアセテート(0.2g/100ml)などが挙げられるが、これらだけに限らない。
20℃での水に対する溶解度は、20℃の水100gに対し、20℃の溶剤100gを混合し、水層のみを分離して、水槽の重量と水の重量との差を求めることで得られる。
<Solvent (D)>
Furthermore, the photosensitive composition of the present invention preferably contains a solvent (D) having a solubility in water at 20 ° C. of 0.1 g / 100 ml or more and less than 30 g / 100 ml. When the solubility of the solvent in water is 30 g / 100 ml or more, the silane compound (B) is hydrolyzed in the photosensitive composition as the solvent absorbs moisture during production of the photosensitive composition, and the photosensitive composition Becomes cloudy or the base material adhesion of the coating film decreases. When the solubility of the solvent in water is less than 1 g / 100 ml, the amount of water in the photosensitive composition is not sufficient, and formation of siloxane bonds due to hydrolysis is difficult to occur, and the substrate adhesion of the coating film is reduced. Sometimes.
Examples of the solvent (D) include cyclohexanone (8.7 g / 100 ml), propylene glycol monomethyl ether acetate (16.0 g / 100 ml), 1,3-butylene glycol diacetate (5.0 g / 100 ml), cyclohexanol acetate ( 0.2g / 100ml), but is not limited thereto.
The solubility in water at 20 ° C. can be obtained by mixing 100 g of water at 20 ° C. with 100 g of solvent at 20 ° C., separating only the aqueous layer, and determining the difference between the weight of the water tank and the weight of water. .
溶剤(D)の含有量は、感光性組成物中の固形分合計100重量%に対して、25〜6000重量%の量で用いることができる。 The content of the solvent (D) can be used in an amount of 25 to 6000% by weight with respect to 100% by weight of the total solid content in the photosensitive composition.
<テトラアルコキシシラン(E)>
本発明の感光性組成物は、テトラアルコキシシラン(E)を含むことができる。
テトラアルコキシシラン(E)としては例えば、テトラメトキシシラン、テトラエトキシシラン、テトラプロパキシシラン、テトラブトキシシランなどが挙げられるが、これらだけに限らない。
感光性組成物中にテトラアルコキシシラン(E)を含有することで、感光性組成物中の水分による加水分解が優先的にテトラアルコキシシラン(E)にて行なわれ、シラン化合物(B)の加水分解を防ぐことができる。また、シラン化合物(B)の重量(b)とテトラアルコキシシラン(E)の重量(e)との比率(b/e)が、2以上20未満であることが好ましい。シラン化合物(B)の重量(b)とテトラアルコキシシラン(E)の重量(e)との比率(b/e)が2未満の場合、塗膜形成時にテトラアルコキシシラン(E)の加水分解が多くなされ、シラン化合物(B)の加水分解がされにくくなり、塗膜の鉛筆硬度や基材密着性が低下するため好ましくない。シラン化合物(B)の重量(b)とテトラアルコキシシラン(E)の重量(e)との比率(b/e)が20以上の場合、テトラアルコキシシラン(E)によるシラン化合物(B)の加水分解を防ぐ効果が少なくなり、好ましくない。
<Tetraalkoxysilane (E)>
The photosensitive composition of the present invention can contain tetraalkoxysilane (E).
Examples of tetraalkoxysilane (E) include, but are not limited to, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.
By containing tetraalkoxysilane (E) in the photosensitive composition, hydrolysis with moisture in the photosensitive composition is preferentially performed in tetraalkoxysilane (E), and the silane compound (B) is hydrolyzed. Decomposition can be prevented. The ratio (b / e) of the weight (b) of the silane compound (B) and the weight (e) of the tetraalkoxysilane (E) is preferably 2 or more and less than 20. When the ratio (b / e) of the weight (b) of the silane compound (B) to the weight (e) of the tetraalkoxysilane (E) is less than 2, the tetraalkoxysilane (E) is hydrolyzed during the formation of the coating film. This is not preferable because the silane compound (B) is hardly hydrolyzed and the pencil hardness and substrate adhesion of the coating film are lowered. When the ratio (b / e) of the weight (b) of the silane compound (B) to the weight (e) of the tetraalkoxysilane (E) is 20 or more, the hydrolysis of the silane compound (B) with the tetraalkoxysilane (E) The effect of preventing decomposition is reduced, which is not preferable.
<光重合開始剤>
本発明の感光性組成物には、該組成物を紫外線照射により硬化させ、フォトリソグラフィー法により塗膜を形成するために、光重合開始剤を加えて溶剤現像型あるいはアルカリ現像型の感光性組成物の形態で調製することができる。
<Photopolymerization initiator>
In the photosensitive composition of the present invention, in order to cure the composition by ultraviolet irradiation and form a coating film by a photolithography method, a photopolymerization initiator is added to the photosensitive composition of a solvent development type or an alkali development type. It can be prepared in the form of a product.
光重合開始剤としては、4−フェノキシジクロロアセトフェノン、4−t−ブチル−ジクロロアセトフェノン、ジエトキシアセトフェノン、1−(4−イソプロピルフェニル)−2−ヒドロキシ−2−メチルプロパン−1−オン、1−ヒドロキシシクロヘキシルフェニルケトン、2−ベンジル−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタン−1−オン、2−メチル−1−[4−(メチルチオ)フェニル]−2−モルフォリノプロパン−1−オン等のアセトフェノン系光重合開始剤、
1,2−オクタジオン−1−[4−(フェニルチオ)−,2−(o−ベンゾイルオキシム)]、エタノン,1−[9−エチル−6−(2−メチルベンゾイル)−9H−カルバゾール−3−イル]−,1−(o−アセチルオキシム)等のオキシムエステル系光重合開始剤、
ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンジルジメチルケタール等のベンゾイン系光重合開始剤、
ベンゾフェノン、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、4−フェニルベンゾフェノン、ヒドロキシベンゾフェノン、アクリル化ベンゾフェノン、4−ベンゾイル−4’−メチルジフェニルサルファイド等のベンゾフェノン系光重合開始剤、
チオキサンソン、2−クロルチオキサンソン、2−メチルチオキサンソン、イソプロピルチオキサンソン、2,4−ジイソプロピルチオキサンソン等のチオキサンソン系光重合開始剤、
2,4,6−トリクロロ−s−トリアジン、2−フェニル−4,6−ビス(トリクロロメチル)−s−トリアジン、2−(p−メトキシフェニル)−4,6−ビス(トリクロロメチル)−s−トリアジン、2−(p−トリル)−4,6−ビス(トリクロロメチル)−s−トリアジン、2−ピペロニル−4,6−ビス(トリクロロメチル)−s−トリアジン、2,4−ビス(トリクロロメチル)−6−スチリル−s−トリアジン、2−(ナフト−1−イル)−4,6−ビス(トリクロロメチル)−s−トリアジン、2−(4−メトキシ−ナフト−1−イル)−4,6−ビス(トリクロロメチル)−s−トリアジン、2,4−トリクロロメチル−(ピペロニル)−6−トリアジン、2,4−トリクロロメチル(4’−メトキシスチリル)−6−トリアジン等のトリアジン系光重合開始剤、
ボレート系光重合開始剤、カルバゾール系光重合開始剤、
イミダゾール系光重合開始剤等が用いられ、これらを単独で、あるいは2種以上混合して用いることができる。
Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- Acetophenone photopolymerization initiators such as 1-one,
1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- Yl]-, 1- (o-acetyloxime) and other oxime ester photopolymerization initiators,
Benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldimethyl ketal,
Benzophenone photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide,
Thioxanthone photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone,
2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloro) Methyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4′-methoxystyryl) -6-tri Triazine photopolymerization initiators such as azine,
Borate photopolymerization initiator, carbazole photopolymerization initiator,
Imidazole-based photopolymerization initiators and the like are used, and these can be used alone or in admixture of two or more.
なかでもアセトフェノン系光重合開始剤、オキシムエステル系光重合開始剤は感度が高く、添加量が少なくて良いため、透過率が高くなることから、好ましい。
また、アセトフェノン系光重合開始剤、オキシムエステル系光重合開始剤のなかでも、1−ヒドロキシシクロヘキシルフェニルケトン、2−メチル−1−(4−メチルチオフェニル)−2−モルホリノプロパン−1−オン、1,2−オクタジオン−1−[4−(フェニルチオ)−,2−(o−ベンゾイルオキシム)]、とりわけ、2−メチル−1−(4−メチルチオフェニル)−2−モルホリノプロパン−1−オン、1,2−オクタジオン−1−[4−(フェニルチオ)−,2−(o−ベンゾイルオキシム)]は、加熱工程時に黄変しないため、絶縁膜としての透過率が高く、特に波長400nm付近の透過率が高い感光性組成物を提供することができるため、より好ましい。これらはそれぞれを単独で用いても良く、ともに含んでいても良い。
光重合開始剤は、感光性組成物の固形分の合計100重量%中、1〜30重量%の量で用いることが好ましく、透過率の観点から1〜10重量%の量で用いることがより好ましい。
Among them, acetophenone photopolymerization initiators and oxime ester photopolymerization initiators are preferable because they have high sensitivity and can be added in a small amount, so that the transmittance increases.
Among acetophenone photopolymerization initiators and oxime ester photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1 , 2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], especially 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, , 2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)] has a high transmittance as an insulating film because it does not turn yellow during the heating step, and particularly has a transmittance around 400 nm. Is more preferable because it can provide a photosensitive composition having a high value. These may be used alone or in combination.
The photopolymerization initiator is preferably used in an amount of 1 to 30% by weight in a total of 100% by weight of the solid content of the photosensitive composition, and more preferably in an amount of 1 to 10% by weight from the viewpoint of transmittance. preferable.
本発明の感光性組成物は、さらに増感剤として、α−アシロキシエステル、アシルフォスフィンオキサイド、メチルフェニルグリオキシレート、ベンジル、9,10−フェナンスレンキノン、カンファーキノン、エチルアンスラキノン、4,4’−ジエチルイソフタロフェノン、3,3’,4,4’−テトラ(t−ブチルパーオキシカルボニル)ベンゾフェノン、4,4’−ジエチルアミノベンゾフェノン等の化合物を併用することもできる。
増感剤は、光重合開始剤100重量部に対して、0.1〜150重量部の量で用いることができる。
The photosensitive composition of the present invention further includes α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, as a sensitizer. Compounds such as 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone can be used in combination.
The sensitizer can be used in an amount of 0.1 to 150 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.
<酸化防止剤>
本発明の感光性組成物には酸化防止剤を含有することができる。酸化防止剤は、加熱工程を経ることによる黄変等による透過率の低下を抑制することができる。そのため、酸化防止剤を含むことで、加熱工程時の黄変を防止し、透過率の高い塗膜を得る事ができる。
<Antioxidant>
The photosensitive composition of the present invention can contain an antioxidant. The antioxidant can suppress a decrease in transmittance due to yellowing or the like due to the heating process. Therefore, by including an antioxidant, yellowing during the heating step can be prevented, and a coating film having a high transmittance can be obtained.
本発明における「酸化防止剤」とは、紫外線吸収機能、ラジカル補足機能、または、過酸化物分解機能を有する化合物であればよく、具体的には、酸化防止剤としてヒンダードフェノール系、ヒンダードアミン系、リン系、イオウ系、ベンゾトリアゾール系、ベンゾフェノン系、ヒドロキシルアミン系、サルチル酸エステル系、およびトリアジン系の化合物があげられ、公知の紫外線吸収剤、酸化防止剤等が使用できる。これらの酸化防止剤の中でも、塗膜の透過率と感度の両立の観点から、フェノール系酸化防止剤、リン系酸化防止剤およびイオウ系酸化防止剤が好ましい。フェノール系のなかでも特に、立体障害性の高いヒンダードフェノール系酸化防止剤がより好ましい。 The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. Among these antioxidants, phenol-based antioxidants, phosphorus-based antioxidants and sulfur-based antioxidants are preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Among phenol-based compounds, hindered phenol-based antioxidants having high steric hindrance are particularly preferable.
[フェノール系酸化防止剤]
例えば、2,6−ジ−t−ブチル−4−エチルフェノール、2,4−ビス−(n−オクチルチオ)−6−(4−ヒドロキシ−3,5−ジ−t−ブチルアニリノ)−1,3,5−トリアジン、2,2−チオ−ジエチレンビス{3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート}、N,N’−ヘキサメチレンビス(3,5−ジ−t−ブチル−4−ヒドロキシ−ヒドロシンナミド)、3,5−ジ−t−ブチル−4−ヒドロキシベンジルフォスフォネート−ジエチルエステル、トリス−(3,5−ジ−t−ブチル−4−ヒドロキシベンジル)−イソシアヌレート、2,6−ジ−t−ブチルフェノール、2,6−ジ−t−ブチル−p−クレゾール、2,6−ジ−t−ブチル−4−メトキシフェノール、トリエチレングリコール−ビス{3−(3−t−ブチル−5−メチル−4−ヒドロキシフェニル)プロピオネート}、1,6−ヘキサンジオール−ビス{3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート}、ペンタエリスリチル−テトラキス{3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート}、オクタデシル−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート、1,3,5−トリメチル−2,4,6−トリス(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)ベンゼンなどが挙げられ、単独又は2種以上を使用してもよい。
[Phenolic antioxidant]
For example, 2,6-di-t-butyl-4-ethylphenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3 , 5-triazine, 2,2-thio-diethylenebis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, N, N'-hexamethylenebis (3,5-di- t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -Isocyanurate, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-methoxyphenol, triethylene glycol- Bis {3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis {3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate}, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Examples include propionate and 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxyphenyl) benzene. .
なかでも、2,4−ビス−(n−オクチルチオ)−6−(4−ヒドロキシ−3,5−ジ−t−ブチルアニリノ)−1,3,5−トリアジン、ペンタエリスリトールテトラキス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート]、N,N'−ヘキサメチレンビス(3,5−ジ−t−ブチル−4−ヒドロキシ−ヒドロシンナミド)、3,5−ジ−t−ブチル−4−ヒドロキシベンジルフォスフォネート−ジエチルエステル、及びトリス−(3,5−ジ−t−ブチル−4−ヒドロキシベンジル)−イソシアヌレートからなる群から選ばれるヒンダードフェノール系酸化防止剤は、光硬化性の面から好ましい。 Among them, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t- A hindered phenolic antioxidant selected from the group consisting of butyl-4-hydroxybenzylphosphonate-diethyl ester and tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate is: It is preferable from the viewpoint of photocurability.
[リン系酸化防止剤]
リン系酸化防止剤としては、市販されているものを使用できるが、トリス[2,4−ジ−(tert)−ブチルフェニル]ホスフィントリス[2−[[2,4,8,10−テトラキス(1,1−ジメチルエチル)ジベンゾ[d,f][1,3,2]ジオキサホスフェピン−6−イル]オキシ]エチル]アミン、トリス[2−[(4,6,9,11−テトラ−tert−ブチルジベンゾ[d,f][1,3,2]ジオキサホスフェピン−2−イル)オキシ]エチル]アミン、亜りん酸エチルビス(2,4−ジtert−ブチル−6−メチルフェニル) が挙げられ、 これらからなる群から選ばれる少なくとも1種の化合物であることが好ましく、これらは1種又は2種以上を使用することができる。
[Phosphorus antioxidant]
Although what is marketed can be used as phosphorus antioxidant, Tris [2,4-di- (tert) -butylphenyl] phosphinetris [2-[[2,4,8,10-tetrakis ( 1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11- Tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2-yl) oxy] ethyl] amine, ethylbisphosphite (2,4-ditert-butyl-6-) It is preferable that it is at least one compound selected from the group consisting of these, and these may be used alone or in combination of two or more.
[イオウ系酸化防止剤]
イオウ系酸化防止剤は分子中にイオウを含む酸化防止剤である。このような含イオウ系酸化防止剤としては市販されているものを使用できるが、3,3'−チオジプロパン酸ジオクタデシル、ジミリスチル−3,3’−チオジプロピオネート、ジパルミチル−3,3’−チオジプロピオネート、ジステアリル−3,3’−チオジプロピオネート、4,4’−チオビス−3−メチル−6−tert−ブチルフェノール、チオジエチレンビス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート]が挙げられ、これらからなる群から選ばれる少なくとも1種の化合物であることが好ましく、これらは1種又は2種以上を使用することができる。
[Sulfur antioxidants]
A sulfur-based antioxidant is an antioxidant containing sulfur in the molecule. As such a sulfur-containing antioxidant, commercially available ones can be used, but dioctadecyl 3,3′-thiodipropanoate, dimyristyl-3,3′-thiodipropionate, dipalmityl-3,3′- Thiodipropionate, distearyl-3,3′-thiodipropionate, 4,4′-thiobis-3-methyl-6-tert-butylphenol, thiodiethylenebis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate], and is preferably at least one compound selected from the group consisting of these, and one or more of these may be used.
これらの酸化防止剤は、1種を単独で、または必要に応じて任意の比率で2種以上混合して用いることができる。 These antioxidants can be used singly or in combination of two or more at any ratio as required.
酸化防止剤の含有量は、感光性組成物の固形分合計100重量%中、0.1重量%以上4重量%未満であることが好ましい。0.1重量%より少ない場合は、酸化防止剤が不足するため黄変防止効果が得られにくく、4重量%より多い場合には紫外線露光時に発生するラジカルを補足してしまうため、感光性組成物の硬化が不十分となることがある。 The content of the antioxidant is preferably 0.1% by weight or more and less than 4% by weight in a total solid content of 100% by weight of the photosensitive composition. If the amount is less than 0.1% by weight, it is difficult to obtain the yellowing prevention effect due to insufficient antioxidant, and if it is more than 4% by weight, the radicals generated at the time of UV exposure are captured. Curing of the product may be insufficient.
<その他の成分>
本発明の感光性組成物には、その他必要に応じて単官能単量体、界面活性剤、貯蔵安定剤、レベリング剤、光安定剤などを使用することもできる。
<Other ingredients>
In the photosensitive composition of the present invention, a monofunctional monomer, a surfactant, a storage stabilizer, a leveling agent, a light stabilizer and the like can be used as necessary.
《貯蔵安定剤》
貯蔵安定剤としては、例えばベンジルトリメチルクロライド、ジエチルヒドロキシアミンなどの4級アンモニウムクロライド、乳酸、シュウ酸などの有機酸およびそのメチルエーテル、t−ブチルピロカテコール、トリエチルホスフィン、トリフェニルフォスフィンなどの有機ホスフィン、亜リン酸塩等が挙げられる。貯蔵安定剤は、感光性組成物の合計100重量%中、0.1〜5重量%の量で用いることができる。
<Storage stabilizer>
Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, triethylphosphine, and triphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 5% by weight in a total of 100% by weight of the photosensitive composition.
《レベリング剤》
本発明の着色組成物には、透明基板上での組成物のレベリング性をよくするため、レベリング剤を添加することが好ましい。レベリング剤としては、主鎖にポリエーテル構造又はポリエステル構造を有するジメチルシロキサンが好ましい。主鎖にポリエーテル構造を有するジメチルシロキサンの具体例としては、東レ・ダウコーニング社製FZ−2122、ビックケミー社製BYK−330などが挙げられる。主鎖にポリエステル構造を有するジメチルシロキサンの具体例としては、ビックケミー社製BYK−310、BYK−370などが挙げられる。主鎖にポリエーテル構造を有するジメチルシロキサンと、主鎖にポリエステル構造を有するジメチルシロキサンとは、併用することもできる。レベリング剤の含有量は通常、感光性組成物の合計100重量%中、0.003〜0.5重量%用いることが好ましい。
《Leveling agent》
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-330 manufactured by BYK Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent is preferably used in an amount of 0.003 to 0.5% by weight in a total of 100% by weight of the photosensitive composition.
レベリング剤として特に好ましいものとしては、分子内に疎水基と親水基を有するいわゆる界面活性剤の一種で、親水基を有しながらも水に対する溶解性が小さく、着色組成物に添加した場合、その表面張力低下能が低いという特徴を有し、さらに表面張力低下能が低いにも拘らずガラス板への濡れ性が良好なものが有用であり、泡立ちによる塗膜の欠陥が出現しない添加量において十分に帯電性を抑止できるものが好ましく使用できる。このような好ましい特性を有するレベリング剤として、ポリアルキレンオキサイド単位を有するジメチルポリシロキサンが好ましく使用できる。ポリアルキレンオキサイド単位としては、ポリエチレンオキサイド単位、ポリプロピレンオキサイド単位があり、ジメチルポリシロキサンは、ポリエチレンオキサイド単位とポリプロピレンオキサイド単位とを共に有していてもよい。 Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.
また、ポリアルキレンオキサイド単位のジメチルポリシロキサンとの結合形態は、ポリアルキレンオキサイド単位がジメチルポリシロキサンの繰り返し単位中に結合したペンダント型、ジメチルポリシロキサンの末端に結合した末端変性型、ジメチルポリシロキサンと交互に繰り返し結合した直鎖状のブロックコポリマー型のいずれであってもよい。ポリアルキレンオキサイド単位を有するジメチルポリシロキサンは、東レ・ダウコーニング株式会社から市販されており、例えば、FZ−2110、FZ−2122、FZ−2130、FZ−2166、FZ−2191、FZ−2203、FZ−2207が挙げられるが、これらに限定されるものではない。 In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.
レベリング剤には、アニオン性、カチオン性、ノニオン性、または両性の界面活性剤を補助的に加えることも可能である。界面活性剤は、2種以上混合して使用しても構わない。
レベリング剤に補助的に加えるアニオン性界面活性剤としては、ポリオキシエチレンアルキルエーテル硫酸塩、ドデシルベンゼンスルホン酸ナトリウム、スチレン−アクリル酸共重合体のアルカリ塩、アルキルナフタリンスルホン酸ナトリウム、アルキルジフェニルエーテルジスルホン酸ナトリウム、ラウリル硫酸モノエタノールアミン、ラウリル硫酸トリエタノールアミン、ラウリル硫酸アンモニウム、ステアリン酸モノエタノールアミン、ステアリン酸ナトリウム、ラウリル硫酸ナトリウム、スチレン−アクリル酸共重合体のモノエタノールアミン、ポリオキシエチレンアルキルエーテルリン酸エステルなどが挙げられる。
An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.
レベリング剤に補助的に加えるカオチン性界面活性剤としては、アルキル4級アンモニウム塩やそれらのエチレンオキサイド付加物が挙げられる。レベリング剤に補助的に加えるノニオン性界面活性剤としては、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンアルキルエーテルリン酸エステル、ポリオキシエチレンソルビタンモノステアレート、ポリエチレングリコールモノラウレートなどの;アルキルジメチルアミノ酢酸ベタインなどのアルキルベタイン、アルキルイミダゾリンなどの両性界面活性剤、また、フッ素系やシリコーン系の界面活性剤が挙げられる。 Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.
<感光性組成物の製法>
本発明の感光性組成物は、エチレン性不飽和二重結合を有する化合物(A)、前記一般式(1)で表わされるシラン化合物(B)、および必要に応じて酸化物微粒子(C)および必要に応じて溶剤(D)、および必要に応じてテトラアルコキシシラン(E)等を攪拌・混合して得ることが出来る。
本発明の感光性組成物は、遠心分離、焼結フィルタ、メンブレンフィルタ等の手段にて、5μm以上の粗大粒子、好ましくは1μm以上の粗大粒子、さらに好ましくは0.5μm以上の粗大粒子および混入した塵、異物の除去を行うことが好ましい。
<Production method of photosensitive composition>
The photosensitive composition of the present invention comprises a compound (A) having an ethylenically unsaturated double bond, a silane compound (B) represented by the general formula (1), and, if necessary, oxide fine particles (C) and It can be obtained by stirring and mixing the solvent (D) and, if necessary, the tetraalkoxysilane (E) if necessary.
The photosensitive composition of the present invention may be mixed with coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more by using means such as centrifugation, sintered filter, membrane filter and the like. It is preferable to remove dust and foreign matters.
<塗膜>
本発明による感光性組成物をガラス基材、ITO上、モリブデン上、その他の金属膜上、有機膜上などにスピンコートなどの回転塗布、ダイコートなどの流延塗布、ロールコートによる塗布、ロール転写法による塗布などにより塗膜を形成する。
また、本発明の感光性組成物は、保護膜用途、平坦膜用途、タッチパネル用絶縁膜用途、のいずれで使用されても良く、さらに各々の用途において、印刷法によりパターン形成されていても構わないが、特にフォリソソグラフィによるパターン形成が好ましい。
<Coating film>
The photosensitive composition according to the present invention is applied to a glass substrate, ITO, molybdenum, other metal film, organic film, etc. by spin coating such as spin coating, casting coating such as die coating, coating by roll coating, roll transfer. A coating film is formed by application by a method.
Moreover, the photosensitive composition of the present invention may be used for any of protective film applications, flat film applications, touch panel insulating film applications, and in each application, a pattern may be formed by a printing method. Although there is no, pattern formation by lithography is particularly preferable.
以下に、実施例により本発明を説明する。なお、実施例中の「部」および「%」とは、それぞれ「重量部」および「重量%」を表す。
実施例に先立ち、エチレン性不飽和二重結合を有する化合物(A)、シラン化合物(B)の重量平均分子量、エチレン性不飽和二重結合を有する化合物(A)の二重結合当量、およびエチレン性不飽和二重結合を有する化合物(A)の酸価の測定方法について説明する。
Hereinafter, the present invention will be described by way of examples. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
Prior to Examples, the compound (A) having an ethylenically unsaturated double bond, the weight average molecular weight of the silane compound (B), the double bond equivalent of the compound (A) having an ethylenically unsaturated double bond, and ethylene A method for measuring the acid value of the compound (A) having a polymerizable unsaturated double bond will be described.
(エチレン性不飽和二重結合を有する化合物(A)の重量平均分子量(Mw))
エチレン性不飽和二重結合を有する化合物(A)の重量平均分子量(Mw)は、装置としてHLC−8220GPC(東ソー株式会社製)を用い、カラムとしてTSK−GEL SUPER HZM−Nを2連でつなげて使用し、溶媒としてTHFを用いて測定したポリスチレン換算分子量である。
(シラン化合物(B)の重量平均分子量(Mw))
シラン化合物(B)の重量平均分子量(Mw)は、ゲルパーミュエ−ションクロマトグラフィー(GPC)分析装置(昭和電工株式会社製 Shodex GPC system)で分子量分布を分析し算出した。
(Weight average molecular weight (Mw) of compound (A) having an ethylenically unsaturated double bond)
The weight average molecular weight (Mw) of the compound (A) having an ethylenically unsaturated double bond is HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus and TSK-GEL SUPER HZM-N is connected in series as a column. It is a polystyrene conversion molecular weight measured using THF as a solvent.
(Weight average molecular weight (Mw) of silane compound (B))
The weight average molecular weight (Mw) of the silane compound (B) was calculated by analyzing the molecular weight distribution with a gel permeation chromatography (GPC) analyzer (Shodex GPC system manufactured by Showa Denko KK).
(エチレン性不飽和二重結合を有する化合物(A)の二重結合当量)
二重結合当量とは、分子中に含まれる二重結合量の尺度となるものであり、同じ分子量の化合物であれば、二重結合当量の数値が小さいほど二重結合の導入量が多くなる。
二重結合当量は下記式により算出した。
[二重結合当量]=[二重結合を持つモノマー成分の分子量]/[二重結合を持つモノマー成分の樹脂中の組成比]
(Double bond equivalent of the compound (A) having an ethylenically unsaturated double bond)
Double bond equivalent is a measure of the amount of double bonds contained in a molecule. If the compounds have the same molecular weight, the amount of double bonds introduced increases as the double bond equivalent value decreases. .
The double bond equivalent was calculated by the following formula.
[Double bond equivalent] = [Molecular weight of monomer component having double bond] / [Composition ratio of monomer component having double bond in resin]
(エチレン性不飽和二重結合を有する化合物(A)の酸価)
エチレン性不飽和二重結合を有する化合物(A)の酸価(JIS酸価)は、以下の方法により求めることができる。
酸価とは試料1gをキシレンとジメチルホルムアミド(1+1)を混合した滴定溶剤に溶かし、電位差滴定法により0.1mol/L水酸化カリウム・エタノール溶液で滴定し、滴定曲線上の変曲点を終点とし、水酸化カリウム溶液の終点までの滴定量から、酸価を算出する。
酸価の算出
得られた結果を下記式に代入して、酸価を算出する。
A=(B−C)×f×D/S
(A:酸価(mgKOH/g)、B:本試験の水酸化カリウム溶液の添加量(mL)、C:空試験(測定試料を用いないで測定)の水酸化カリウム溶液の添加量(mL)、f:水酸化カリウム溶液のファクター、D:濃度換算値5.611mg/mL(0.1mol/LKOH 1mLの水酸化カリウム相当量)、S:試料(g))
(Acid value of compound (A) having an ethylenically unsaturated double bond)
The acid value (JIS acid value) of the compound (A) having an ethylenically unsaturated double bond can be determined by the following method.
The acid value is obtained by dissolving 1 g of a sample in a titration solvent mixed with xylene and dimethylformamide (1 + 1), titrating with a 0.1 mol / L potassium hydroxide / ethanol solution by potentiometric titration, and setting the inflection point on the titration curve as the end point. The acid value is calculated from the titration amount until the end point of the potassium hydroxide solution.
Calculation of acid value The obtained result is substituted into the following formula to calculate the acid value.
A = (BC) × f × D / S
(A: Acid value (mgKOH / g), B: Addition amount of potassium hydroxide solution in this test (mL), C: Addition amount of potassium hydroxide solution in blank test (measured without using measurement sample) (mL ), F: factor of potassium hydroxide solution, D: concentration converted value 5.611 mg / mL (0.1 mol / LKOH 1 mL of potassium hydroxide equivalent), S: sample (g))
続いて、樹脂(A2−a)溶液、その他の樹脂(A2−b)溶液の製造方法について説明する。
<その他の樹脂(A2−b)溶液の製造方法>
(樹脂溶液(A−1))
攪拌機、温度計、滴下装置、還流冷却器、ガス導入管を備えた反応容器にPGMEA100部を入れ、容器に窒素ガスを注入しながら70℃に加熱して、同温度でスチレン30.0部、2−ヒドロキシエチルメタクリレート23.4部、シクロヘキシルメタクリレート43.5部、メタクリル酸3.1部、2,2’−アゾビスイソブチロニトリル1部の混合物を1時間かけて滴下して重合反応を行った。滴下終了後、さらに70℃で3時間反応させた後、アゾビスイソブチロニトリル0.2部をPGMEA50部に溶解させたものを添加し、その後3時間、同じ温度で攪拌を続け共重合体を得た。室温に冷却後、PGMEAで希釈することにより、固形分40重量%の表1に示す通りの重量平均分子量、酸価を有する樹脂溶液(A−1)を得た。
Then, the manufacturing method of resin (A2-a) solution and other resin (A2-b) solutions is demonstrated.
<Method for producing other resin (A2-b) solution>
(Resin solution (A-1))
In a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, and gas introduction tube, 100 parts of PGMEA was charged, heated to 70 ° C. while injecting nitrogen gas into the vessel, 30.0 parts of styrene at the same temperature, A mixture of 23.4 parts of 2-hydroxyethyl methacrylate, 43.5 parts of cyclohexyl methacrylate, 3.1 parts of methacrylic acid and 1 part of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. went. After completion of the dropwise addition, the mixture was further reacted at 70 ° C. for 3 hours, then 0.2 parts of azobisisobutyronitrile dissolved in 50 parts of PGMEA was added, and then the copolymer was continuously stirred for 3 hours at the same temperature. Got. After cooling to room temperature, a resin solution (A-1) having a weight average molecular weight and an acid value as shown in Table 1 having a solid content of 40% by weight was obtained by diluting with PGMEA.
<樹脂(A2−a)溶液の製造方法>
(樹脂溶液(A−2−2))
工程1
攪拌機、温度計、滴下装置、還流冷却器、ガス導入管を備えた反応容器にPGMEA100部を入れ、容器に窒素ガスを注入しながら70℃に加熱して、同温度でスチレン5.0部、シクロヘキシルメタクリレート15.9部、メタクリル酸31.7部、2,2’−アゾビスイソブチロニトリル1部の混合物を1時間かけて滴下して重合反応を行った。滴下終了後、さらに70℃で3時間反応させた後、アゾビスイソブチロニトリル0.2部をPGMEA40部に溶解させたものを添加し、その後3時間、同じ温度で攪拌を続け共重合体を得た。
工程2
次いで、反応容器内に乾燥空気を導入し、グリシジルメタクリレート50.0部、PGMEA37.0部、ジメチルベンジルアミン0.3部、メトキノン0.1部を仕込み、その後10時間、同じ温度で攪拌を続けた。室温に冷却後、PGMEAで希釈することにより、固形分40重量%の表1に示す通りの重量平均分子量、酸価、二重結合当量を有する樹脂溶液(A−2−2)を得た。
<Method for Producing Resin (A2-a) Solution>
(Resin solution (A-2-2))
Process 1
PGMEA 100 parts in a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, gas introduction pipe, heated to 70 ° C. while injecting nitrogen gas into the vessel, 5.0 parts of styrene at the same temperature, A mixture of 15.9 parts of cyclohexyl methacrylate, 31.7 parts of methacrylic acid, and 1 part of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 70 ° C. for 3 hours, and then 0.2 parts of azobisisobutyronitrile dissolved in 40 parts of PGMEA was added, followed by stirring at the same temperature for 3 hours. Got.
Process 2
Next, dry air was introduced into the reaction vessel, charged with 50.0 parts of glycidyl methacrylate, 37.0 parts of PGMEA, 0.3 part of dimethylbenzylamine, and 0.1 part of methoquinone, and then continued stirring at the same temperature for 10 hours. It was. After cooling to room temperature, the resin solution (A-2-2) having a weight average molecular weight, an acid value, and a double bond equivalent as shown in Table 1 having a solid content of 40% by weight was obtained by diluting with PGMEA.
(樹脂溶液(A−2−3〜A−2−9))
表1に記載の組成、および配合量(重量部)、反応温度にそれぞれ変更した以外は、樹脂溶液(A−2−2)と同様の方法で調整し、表1に示す通りの重量平均分子量、酸価、二重結合当量を有する樹脂溶液(A−2−3、A−2−4、A−2−5、A−2−6、A−2−7、A−2−8、A−2−9)をそれぞれ得た。
(Resin solution (A-2-3 to A-2-9))
The weight average molecular weight as shown in Table 1 was adjusted by the same method as in the resin solution (A-2-2) except that the composition, blending amount (parts by weight) and reaction temperature were changed respectively. , A resin solution having an acid value and a double bond equivalent (A-2-3, A-2-4, A-2-5, A-2-6, A-2-7, A-2-8, A -2-9) were obtained respectively.
PGMEA:プロピレングリコールモノメチルエーテルアセテート
St:スチレン
HEMA:2−ヒドロキシエチルメタクリレート
CHMA:シクロヘキシルメタクリレート
MAA:メタクリル酸
GMA:グリシジルメタクリレート
PGMEA: propylene glycol monomethyl ether acetate St: styrene HEMA: 2-hydroxyethyl methacrylate CHMA: cyclohexyl methacrylate MAA: methacrylic acid GMA: glycidyl methacrylate
<シラン化合物(B)の製造方法>
(シラン化合物(B−1))
反応槽として冷却管を付けたフラスコを準備し、3−イソシアネートプロピルトリエトキシシラン(信越化学工業製「KBE−9007」)100g、エタノール(キシダ化学社製)50gをよく攪拌混合したものを準備し、窒素置換した後、攪拌しながらオイルバスで加熱して反応槽の温度を60℃まで昇温した。反応槽の温度が60℃に安定してから、8時間攪拌した。FT−IRスペクトルにより反応が終了したことを確認し、反応槽の温度を常温まで下げ、固形分79重量%の(3−カルバメートエチル)プロピルトリエトキシシランのエタノール溶液130gを得た。
ジムロート式冷却凝縮器、ディーンスターク、撹拌機、温度計を備えた100mLの四つ口フラスコを十分窒素置換したものを準備し、次いで前記(3−カルバメートエチル)プロピルトリエトキシシランのエタノール溶液100g、エタノール25mL、酢酸ナトリウム0.06gを仕込み、水1.3gをゆっくりと添加した。常圧下、30〜40℃で1時間熟成した後、還流下で3時間熟成した。熟成後常圧で徐々に溶媒を抜き出し、釜温が105℃に達した所で加熱を止め、冷却した。得られた溶液をろ過し、減圧下、120℃で1時間乾燥することで透明なオイル状生成物であるシロキサンオリゴマーが35g得られた。ゲルパーミュエ−ションクロマトグラフィー(GPC)分析装置(昭和電工株式会社製 Shodex GPC system)で分子量分布を分析した結果、重量平均分子量(Mw)が約5,500であった。
<Method for producing silane compound (B)>
(Silane compound (B-1))
Prepare a flask equipped with a cooling tube as a reaction tank, and mix well with 100 g of 3-isocyanatopropyltriethoxysilane (“KBE-9007” manufactured by Shin-Etsu Chemical Co., Ltd.) and 50 g of ethanol (manufactured by Kishida Chemical Co., Ltd.). After substituting with nitrogen, the temperature of the reaction vessel was raised to 60 ° C. by heating in an oil bath while stirring. After the temperature of the reaction vessel was stabilized at 60 ° C., the mixture was stirred for 8 hours. After confirming the completion of the reaction by FT-IR spectrum, the temperature of the reaction vessel was lowered to room temperature to obtain 130 g of an ethanol solution of (3-carbamateethyl) propyltriethoxysilane having a solid content of 79% by weight.
A 100 mL four-necked flask equipped with a Dimroth-type cooling condenser, a Dean Stark, a stirrer, and a thermometer was prepared by sufficiently substituting with nitrogen, and then 100 g of the ethanol solution of (3-carbamateethyl) propyltriethoxysilane, Ethanol (25 mL) and sodium acetate (0.06 g) were charged, and water (1.3 g) was slowly added. The mixture was aged at 30 to 40 ° C. for 1 hour under normal pressure and then aged for 3 hours under reflux. After aging, the solvent was gradually extracted at normal pressure, and when the kettle temperature reached 105 ° C., the heating was stopped and the system was cooled. The obtained solution was filtered, and dried under reduced pressure at 120 ° C. for 1 hour to obtain 35 g of a siloxane oligomer that was a transparent oily product. As a result of analyzing the molecular weight distribution with a gel permeation chromatography (GPC) analyzer (Shodex GPC system manufactured by Showa Denko KK), the weight average molecular weight (Mw) was about 5,500.
(シラン化合物(B−2))
反応槽として冷却管を付けたフラスコを準備し、3−イソシアネートプロピルトリエトキシシラン(信越化学工業製「KBE−9007」)100g、2,8−エチル−1−テトラデカノール100g部をよく攪拌混合したものを準備し、窒素置換した後、攪拌しながらオイルバスで加熱して反応槽の温度を60℃まで昇温した。反応槽の温度が60℃に安定してから、10時間攪拌した。IRスペクトルにより反応が終了したことを確認し、反応槽の温度を常温まで下げ、試料を窒素置換した容器に取り出し保管した。ゲルパーミュエ−ションクロマトグラフィー(GPC)分析装置(昭和電工株式会社製 Shodex GPC system)で分子量分布を分析した結果、重量平均分子量(Mw)が約520であった。
(Silane compound (B-2))
Prepare a flask equipped with a cooling tube as a reaction vessel, and stir and mix 100 g of 3-isocyanatopropyltriethoxysilane (“KBE-9007” manufactured by Shin-Etsu Chemical Co., Ltd.) and 100 g of 2,8-ethyl-1-tetradecanol well. The prepared product was purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 60 ° C. After the temperature of the reaction vessel was stabilized at 60 ° C., the mixture was stirred for 10 hours. After confirming the completion of the reaction by IR spectrum, the temperature of the reaction vessel was lowered to room temperature, and the sample was taken out and stored in a container purged with nitrogen. As a result of analyzing the molecular weight distribution with a gel permeation chromatography (GPC) analyzer (Shodex GPC system manufactured by Showa Denko KK), the weight average molecular weight (Mw) was about 520.
(シラン化合物(B−3))
反応槽として冷却管を付けたフラスコを準備し、3−イソシアネートプロピルトリエトキシシラン(信越化学工業製「KBE−9007」)100g、エタノール(キシダ化学社製)100gをよく攪拌混合したものを準備し、窒素置換した後、攪拌しながらオイルバスで加熱して反応槽の温度を60℃まで昇温した。反応槽の温度が60℃に安定してから、6時間攪拌した。FT−IRスペクトルにより反応が終了したことを確認し、反応槽の温度を常温まで下げ、試料を窒素置換した容器に取り出し保管した。
(Silane compound (B-3))
Prepare a flask equipped with a cooling tube as a reaction tank, and thoroughly stir and mix 100 g of 3-isocyanatopropyltriethoxysilane (“KBE-9007” manufactured by Shin-Etsu Chemical Co., Ltd.) and 100 g of ethanol (manufactured by Kishida Chemical Co., Ltd.). After substituting with nitrogen, the temperature of the reaction vessel was raised to 60 ° C. by heating in an oil bath while stirring. After the temperature of the reaction vessel was stabilized at 60 ° C., the mixture was stirred for 6 hours. After confirming the completion of the reaction by FT-IR spectrum, the temperature of the reaction vessel was lowered to room temperature, and the sample was taken out and stored in a container purged with nitrogen.
[実施例1]
(感光性組成物1(R1))
下記組成の混合物を均一になるように攪拌混合した後、1μmのフィルタで濾過して、感光性組成物1を得た。
樹脂溶液A−1 35.24部
多官能単量体
(V#802「ビスコート#802」(大阪有機化学社製)) 4.00部
シラン化合物B−1
(シロキサンオリゴマー 分子量約5,500) 0.60部
光重合開始剤
(IRGACURE OXE−01(BASF社製);1,2−オクタジオン−1−[4−(フェニルチオ)−,2−(o−ベンゾイルオキシム)]) 1.30部
レベリング剤
(BYK−330 2%(ビックケミー社製);ポリエーテル構造含有ジメチルシロキサンのPGMEA溶液(固型分1%に調整))) 1.00部
プロピレングリコールモノメチルエーテルアセテート 37.87部
エタノール(キシダ化学社製) 20.00部
[Example 1]
(Photosensitive composition 1 (R1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a photosensitive composition 1.
Resin solution A-1 35.24 parts Polyfunctional monomer (V # 802 “Biscoat # 802” (manufactured by Osaka Organic Chemical Co., Ltd.)) 4.00 parts Silane compound B-1
(Siloxane oligomer molecular weight: about 5,500) 0.60 parts Photopolymerization initiator (IRGACURE OXE-01 (manufactured by BASF); 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyl) Oxime)]) 1.30 parts Leveling agent (BYK-330 2% (by Big Chemie); PGMEA solution of polyether structure-containing dimethylsiloxane (adjusted to 1% solid content))) 1.00 parts propylene glycol monomethyl ether Acetate 37.87 parts Ethanol (Kishida Chemical Co., Ltd.) 20.00 parts
[実施例2〜19、比較例1〜4]
(感光性組成物2〜23(R2〜R23))
表2〜5に示した組成、および配合量(重量部)の混合物を均一になるように攪拌混合した後、1μmのフィルタで濾過し、感光性組成物1と同様の方法で、実施例2〜19、比較例1〜4にそれぞれ相当する感光性組成物2〜23(R2〜R23)を得た。
[Examples 2 to 19, Comparative Examples 1 to 4]
(Photosensitive composition 2-23 (R2-R23))
A mixture of the compositions shown in Tables 2 to 5 and the blending amount (parts by weight) was stirred and mixed so as to be uniform, then filtered through a 1 μm filter, and in the same manner as in photosensitive composition 1, Example 2 To 19, and photosensitive compositions 2 to 23 (R2 to R23) corresponding to Comparative Examples 1 to 4, respectively.
《酸化物微粒子(C)》
・ZR−40BL(日産化学社製);ジルコニアの酸化物微粒子の水酸化テトラメチルアンモニウム分散液(固型分40%)
・PMA−ST(日産化学社製);ケイ素の酸化物微粒子のPGMEA分散液(固型分30%)
《エチレン性不飽和二重結合を有する単量体(A1)》
・V#802;ビスコート#802(大阪有機化学社製)
トリペンタエリスリトールオクタアクリレートとテトラペンタエリスリトールデカアクリレートペンタペンタエリスリトールドデカアクリレートの混合物
・トリペンタエリスリトールオクタアクリレート
DPCA30;カヤキュア DPCA30(日本化薬社製)
《テトラアルコキシシラン(E)》
TEOS:テトラエトキシシラン(和光純薬工業社製)
《シラン化合物》
KBM−573:N−フェニル−3−アミノプロピルトリメトキシシラン(信越化学工業社製)
KBE−9007:3−イソシアネートプロピルトリエトキシシラン(信越化学工業社製)
《光重合開始剤》
・OXE−01;IRGACURE OXE−01(BASF社製);1,2−オクタジオン−1−[4−(フェニルチオ)−,2−(o−ベンゾイルオキシム) ]
・Irg.907;IRGACURE907(BASF社製);2−メチル−1−(4−メチルチオフェニル)−2−モルホリノプロパン−1−オン
<< Oxide fine particles (C) >>
ZR-40BL (Nissan Chemical Co., Ltd.); tetramethylammonium hydroxide dispersion of fine zirconia oxide particles (solid content 40%)
PMA-ST (manufactured by Nissan Chemical Co., Ltd.); PGMEA dispersion of silicon oxide fine particles (solid content 30%)
<< Monomer having an ethylenically unsaturated double bond (A1) >>
・ V # 802; Biscote # 802 (Osaka Organic Chemical Co., Ltd.)
Mixture of tripentaerythritol octaacrylate and tetrapentaerythritol decaacrylate pentapentaerythritol dodecaacrylate, tripentaerythritol octaacrylate DPCA30; Kayacure DPCA30 (manufactured by Nippon Kayaku Co., Ltd.)
<< Tetraalkoxysilane (E) >>
TEOS: Tetraethoxysilane (manufactured by Wako Pure Chemical Industries)
<< Silane compound >>
KBM-573: N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBE-9007: 3-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
<< Photopolymerization initiator >>
OXE-01; IRGACURE OX-01 (manufactured by BASF); 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)]
・ Irg. 907; IRGACURE907 (manufactured by BASF); 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one
《レベリング剤》
・BYK−330 2%(ビックケミー社製);ポリエーテル構造含有ジメチルシロキサンのPGMEA溶液(固型分1%に調整)
《溶剤》
・PGMEA;プロピレングリコールモノメチルエーテルアセテート
・エタノール(キシダ化学社製)
・1,3−BGDA(ダイセル化学工業社製);1,3−ブチレングリコールジアセテート
《Leveling agent》
-BYK-330 2% (manufactured by Big Chemie); polyether structure-containing dimethylsiloxane PGMEA solution (adjusted to 1% solids)
"solvent"
・ PGMEA: Propylene glycol monomethyl ether acetate ・ Ethanol (Kishida Chemical Co., Ltd.)
・ 1,3-BGDA (manufactured by Daicel Chemical Industries); 1,3-butylene glycol diacetate
<感光性組成物の評価>
以下に示す評価方法にて感光性組成物(R1〜R23)をそれぞれ評価した。結果を表6〜8に示す。
(透過率の測定)
感光性組成物(R1〜R23)を、100mm×100mm、0.7mm厚のガラス基板(コーニング社製ガラス イーグル2000)に、スピンコーターを用いて230℃20分加熱後の仕上がり膜厚が2.0μmとなるように塗布した基板を得た。次に、110℃に加熱したホットプレート上で2分間保持した後、超高圧水銀ランプを用いて、照度20mW/cm2、露光量50mJ/cm2で紫外線露光を行った。塗布基板を230℃で20分加熱、放冷後、顕微分光光度計(オリンパス光学社製「OSP−SP100」)を用いて、得られた塗膜の波長400nmにおける透過率を液浸法にて求めた。膜厚は、アルバック社製の触針式膜厚計DECTAC−3で測定した。
透過率 97%以上 :良好なレベル(判定◎)
透過率 95%以上97%未満 :実用可能なレベル(判定○)
透過率 95%未満 :実用には適さないレベル(判定×)
<Evaluation of photosensitive composition>
The photosensitive compositions (R1 to R23) were evaluated by the evaluation methods shown below. The results are shown in Tables 6-8.
(Measurement of transmittance)
The finished film thickness after heating the photosensitive composition (R1 to R23) on a glass substrate (Corning Glass Eagle 2000) of 100 mm × 100 mm and 0.7 mm thickness at 230 ° C. for 20 minutes using a spin coater is 2. A substrate coated so as to be 0 μm was obtained. Next, after holding for 2 minutes on a hot plate heated to 110 ° C., ultraviolet exposure was performed using an ultrahigh pressure mercury lamp at an illuminance of 20 mW / cm 2 and an exposure amount of 50 mJ / cm 2 . The coated substrate was heated at 230 ° C. for 20 minutes and allowed to cool, and then the transmittance at a wavelength of 400 nm of the obtained coating film was measured by an immersion method using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). Asked. The film thickness was measured with a stylus type film thickness meter DECTAC-3 manufactured by ULVAC.
Transmittance 97% or higher: Good level (Judgment ◎)
Transmittance 95% or more and less than 97%: Practical level (judgment ○)
Transmittance <95%: Level not suitable for practical use (judgment x)
(耐熱性;追加ベーク後の透過率の測定)
透過率の測定用に作製したものと同じ方法で得た感光性組成物塗布基板を300℃20分加熱、放冷後、顕微分光光度計(オリンパス光学社製「OSP−SP100」)を用いて、得られた塗膜の波長400nmにおける透過率を液浸法にて求めた。
透過率 95%以上 :良好なレベル(判定◎)
透過率 90%以上95%未満 :実用可能なレベル(判定○)
透過率 90%未満 :実用には適さないレベル(判定×)
(Heat resistance; measurement of transmittance after additional baking)
A photosensitive composition-coated substrate obtained by the same method as that prepared for transmittance measurement was heated at 300 ° C. for 20 minutes, allowed to cool, and then using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). The transmittance of the obtained coating film at a wavelength of 400 nm was determined by a liquid immersion method.
Transmittance 95% or higher: Good level (Judgment ◎)
Transmittance 90% or more and less than 95%: Practical level (judgment ○)
Transmittance less than 90%: Level not suitable for practical use (judgment ×)
(鉛筆硬度の測定)
透過率の測定用に作製したものと同じ方法で得た感光性組成物塗布基板について、JIS K5600−5−4に準じた引っかき硬度(鉛筆法)試験により絶縁膜の表面硬度を測定した。この値が5Hまたはそれより硬いとき、表面硬度は良好といえる。鉛筆硬度が7Hの場合非常に良好、6Hの場合は良好、5Hの場合実用上優れる硬度、鉛筆硬度が4Hの場合実用可能な最低限の硬度、3H以下の場合実用には適さない鉛筆硬度である。
(Measurement of pencil hardness)
About the photosensitive composition application | coating board | substrate obtained by the same method as what was produced for the measurement of the transmittance | permeability, the surface hardness of the insulating film was measured by the scratch hardness (pencil method) test according to JISK5600-5-4. When this value is 5H or higher, the surface hardness is good. When pencil hardness is 7H, it is very good, when 6H is good, when 5H is practically excellent, when pencil hardness is 4H, the minimum practical hardness is 3H or less. is there.
(ガラス、ITOおよびMoに対する密着性の測定)
透過率の測定用に作製したものと同じ方法で得た感光性組成物塗布基板をJIS K5600−5−6に準じた付着性(クロスカット法)試験により塗膜の基材密着性を評価し、碁盤目25個中の剥離個数を数えた。
基材はコーニング社製ガラス イーグル2000、ジオマテック社製 ITO膜、東邦化研社製Mo膜を使用した。
碁盤目の剥離個数 0個 →非常に優れているレベル(判定◎)
碁盤目の剥離個数 1個未満(フチハガレ;碁盤目のフチが剥がれるレベル)→実用上優れているレベル(判定○)
碁盤目の剥離個数 1個以上3個以下 →実用上問題ないレベル(判定△)
碁盤目の剥離個数 3個より多い →実用上支障のあるレベル(判定×)
(Measurement of adhesion to glass, ITO and Mo)
The substrate adhesion of the coating film was evaluated by an adhesion (cross-cut method) test according to JIS K5600-5-6 for the photosensitive composition coated substrate obtained by the same method as that prepared for the measurement of transmittance. The number of peels in 25 grids was counted.
As the substrate, Corning Glass Eagle 2000, Geomatek ITO film, and Toho Kaken Mo film were used.
Number of cross-cuts peeled off 0 → Excellent level (judgment ◎)
Number of cross-cuts less than 1 (edge peel; level at which cross-cuts are peeled off) → Practical level (Judgment ○)
Number of peeled grids: 1 or more and 3 or less → Practical level (judgment △)
Number of peeled grids greater than 3 → Levels that impede practical use (judgment ×)
(ITOエッチャント耐性)
透過率の測定用に作製したものと同じ方法でITO基材上に塗布した後、ITOエッチャント;硝酸/塩酸/水=0.1/1/1に40℃で5分間浸漬し、純水にて洗浄後、24時間放置した。得られた基板をJIS K5600−5−6に準じた付着性(クロスカット法)試験により塗膜の基材密着性を評価し、碁盤目25個中の剥離個数を数えた。
碁盤目の剥離個数 0個 →非常に優れているレベル(判定◎)
碁盤目の剥離個数 1個以上3個未満 →実用上優れているレベル(判定○)
碁盤目の剥離個数 3個以上12個以下 →実用上問題ないレベル(判定△)
碁盤目の剥離個数 12個より多い →実用上支障のあるレベル(判定×)
(ITO etchant resistance)
After coating on the ITO substrate by the same method as that prepared for the measurement of transmittance, it was immersed in ITO etchant; nitric acid / hydrochloric acid / water = 0.1 / 1/1 for 5 minutes at 40 ° C. And washed for 24 hours. The obtained substrate was evaluated for substrate adhesion of the coating film by an adhesion (cross-cut method) test according to JIS K5600-5-6, and the number of peels in 25 grids was counted.
Number of cross-cuts peeled off 0 → Excellent level (judgment ◎)
Number of peeled grids 1 or more and less than 3 → Practical level (Judgment ○)
Number of peeled grids 3 or more and 12 or less → Practical level (judgment △)
The number of peeled grids is more than 12 → Levels that impede practical use (judgment ×)
(Moエッチャント耐性)
透過率の測定用に作製したものと同じ方法でMo基材上に塗布した後、Moエッチャント;リン酸/酢酸/硝酸/水=80/5/5/10に40℃で5分間浸漬し、純水にて洗浄後、24時間放置した。得られた基板をJIS K5600−5−6に準じた付着性(クロスカット法)試験により塗膜の基材密着性を評価し、碁盤目25個中の剥離個数を数えた。
碁盤目の剥離個数 0個 →非常に優れているレベル(判定◎)
碁盤目の剥離個数 1個以上3個未満 →実用上優れているレベル(判定○)
碁盤目の剥離個数 3個以上12個以下 →実用上問題ないレベル(判定△)
碁盤目の剥離個数 12個より多い →実用上支障のあるレベル(判定×)
(Mo etchant resistance)
After being coated on the Mo substrate by the same method as that prepared for the measurement of transmittance, it was immersed in Mo etchant; phosphoric acid / acetic acid / nitric acid / water = 80/5/5/10 at 40 ° C. for 5 minutes, After washing with pure water, it was left for 24 hours. The obtained substrate was evaluated for substrate adhesion of the coating film by an adhesion (cross-cut method) test according to JIS K5600-5-6, and the number of peels in 25 grids was counted.
Number of cross-cuts peeled off 0 → Excellent level (judgment ◎)
Number of peeled grids 1 or more and less than 3 → Practical level (Judgment ○)
Number of peeled grids 3 or more and 12 or less → Practical level (judgment △)
The number of peeled grids is more than 12 → Levels that impede practical use (judgment ×)
(経時安定性)
感光性組成物を5℃1ヶ月間静置し、ITOに対する密着性を前記した方法にて測定し、サンプル作製直後の碁盤目25個中の剥離個数との差を測定した。
直後と5℃1ヶ月後の碁盤目の剥離個数の差 0個 (判定◎)
直後と5℃1ヶ月後の碁盤目の剥離個数の差 1個以上3個以下(判定○)
直後と5℃1ヶ月後の碁盤目の剥離個数の差 3個以上10個以下(判定△)
直後と5℃1ヶ月後の碁盤目の剥離個数の差 10個より多い (判定×)
(Stability over time)
The photosensitive composition was allowed to stand at 5 ° C. for 1 month, and the adhesion to ITO was measured by the method described above, and the difference from the number of peels in 25 grids immediately after sample preparation was measured.
The difference in the number of peeling of the grids immediately after and 5 months after 1 month 0 (Judgment ◎)
The difference in the number of peeling of the grids immediately after and 1 month after 5 ° C 1 or more and 3 or less (Judgment ○)
The difference in the number of peeling of the grids immediately after and 5 months after 1 month 3 to 10 (Decision △)
The difference in the number of peeling of the grids immediately after and 5 months after 1 month More than 10 (judgment ×)
(比誘電率)
透過率の測定用に作製したものと同じ方法で、電極用にアルミ蒸着した100mm×100mm、0.7mm厚のガラス基板上に塗布し塗布基板を得た。塗膜上に面積3.464×10-4m2の電極用のアルミを蒸着し、硬化塗膜をアルミ電極で挟んだサンプルを作製した。得られたサンプルの10Hz〜1MHzまでの誘電正接を、インピーダンスアナライザー(ソーラトロン社製「1260型」)を用いて得て、印過電圧100mVで比誘電率を得た。
比誘電率(@1kHz):3.5未満 →非常に優れているレベル(判定◎)
比誘電率(@1kHz):3.5以上3.7未満 →実用上優れているレベル(判定○)
比誘電率(@1kHz):3.7以上 →実用上支障のあるレベル(判定×)
(Relative permittivity)
By the same method as that prepared for the measurement of transmittance, it was applied onto a 100 mm × 100 mm, 0.7 mm thick glass substrate deposited with aluminum for electrodes to obtain a coated substrate. Aluminum for electrodes having an area of 3.464 × 10 −4 m 2 was vapor-deposited on the coating film to prepare a sample in which the cured coating film was sandwiched between aluminum electrodes. A dielectric loss tangent of 10 Hz to 1 MHz of the obtained sample was obtained using an impedance analyzer (“1260 type” manufactured by Solartron), and a relative dielectric constant was obtained at an imprint voltage of 100 mV.
Dielectric constant (@ 1 kHz): less than 3.5 → very good level (judgment ◎)
Relative permittivity (@ 1 kHz): 3.5 or more and less than 3.7 → Practically superior level (Judgment ○)
Relative permittivity (@ 1 kHz): 3.7 or higher → Practical hindrance level (judgment x)
(現像速度)
感光性組成物を、乾燥膜厚が2.0μmとなるようにガラス基板にスピンコート法により塗布し、この塗布基板に対し高圧水銀灯によりマスクパターンを通して60mJ/cm2で露光した後、0.04重量%水酸化カリウム水溶液(現像液温度26℃)を使用して圧力0.25MPaのスプレー現像を行い、塗膜が溶解し基板面が露出するまでの時間(現像溶解時間)を測定した。
現像時間:20秒未満 (判定◎)
現像時間:20秒以上、60秒未満(判定○)
現像時間:60秒以上(判定×)
(Development speed)
The photosensitive composition was applied to a glass substrate by a spin coat method so that the dry film thickness was 2.0 μm, and the coated substrate was exposed at 60 mJ / cm 2 through a mask pattern with a high-pressure mercury lamp, and then 0.04 weight Spray development was performed at a pressure of 0.25 MPa using a% potassium hydroxide aqueous solution (developer temperature: 26 ° C.), and the time until the coating film was dissolved and the substrate surface was exposed (development dissolution time) was measured.
Development time: less than 20 seconds (Judgment ◎)
Development time: 20 seconds or more and less than 60 seconds (Judgment ○)
Development time: 60 seconds or more (judgment x)
比較例1〜4のようにエチレン性不飽和二重結合を有する化合物(A)を含まなかったり、シラン化合物(B)を含まないことで、鉛筆硬度が悪かったり、基材密着性が悪かったり、経時安定性が悪いという不具合が生じたのに対して、表6の実施例1〜10に示すように、本発明の特徴であるエチレン性不飽和二重結合を有する化合物(A)と、前記一般式(1)で表わされるシラン化合物(B)を含むことにより、感光性組成物の鉛筆硬度、ガラス、ITO、Moといった基材への密着性、エッチャント耐性、透過率、耐熱性、経時安定性、現像性などにおいていずれも良好な結果となった。 By not including the compound (A) having an ethylenically unsaturated double bond as in Comparative Examples 1 to 4 or not including the silane compound (B), the pencil hardness is poor or the substrate adhesion is poor. In contrast to the problem of poor stability over time, as shown in Examples 1 to 10 in Table 6, the compound (A) having an ethylenically unsaturated double bond, which is a feature of the present invention, By including the silane compound (B) represented by the general formula (1), the pencil hardness of the photosensitive composition, adhesion to a substrate such as glass, ITO, Mo, etchant resistance, transmittance, heat resistance, aging Good results were obtained in both stability and developability.
なかでも、重量平均分子量(Mw)が100以上5000未満であるシラン化合物(B)を用い、かつ感光性組成物の固形分合計100重量%中の該シラン化合物(B)の含有量が5重量%以上60重量%未満である場合において、特に基材密着性、エッチャント耐性が良好であった。
また、二重結合当量350g/mol以上1200g/mol未満であり、かつ重量分子量Mw500以上40000未満であるエチレン性不飽和二重結合を有する化合物(A)を用いた場合、鉛筆硬度が高く基材密着性も良好な、バランスの取れた塗膜を得る事が出来た。
Among these, the silane compound (B) having a weight average molecular weight (Mw) of 100 or more and less than 5000 is used, and the content of the silane compound (B) in the total solid content of 100% by weight of the photosensitive composition is 5%. % And less than 60% by weight, the substrate adhesion and etchant resistance were particularly good.
Further, when a compound (A) having an ethylenically unsaturated double bond having a double bond equivalent of 350 g / mol or more and less than 1200 g / mol and having a weight molecular weight Mw of 500 or more and less than 40000 is used, the substrate has a high pencil hardness. A well-balanced coating film with good adhesion could be obtained.
また、表7の実施例11〜14に示すように、酸化物微粒子(C)を用い、かつ感光性組成物の固形分合計100重量%中、5重量%以上50重量%未満であり、シラン化合物(B)の重量(b)と酸化物微粒子(C)の重量(c)との比率(b/c)が、0.4以上20.0未満である場合、より鉛筆硬度が高い塗膜を得る事が出来た。 Further, as shown in Examples 11 to 14 in Table 7, the oxide fine particles (C) were used, and the total solid content of the photosensitive composition was 100% by weight or more and less than 5% by weight and less than 50% by weight. When the ratio (b / c) between the weight (b) of the compound (B) and the weight (c) of the fine oxide particles (C) is 0.4 or more and less than 20.0, the coating film has a higher pencil hardness. I was able to get.
また、表8の実施例15〜19に示すように、20℃での水に対する溶解度が1g/100ml以上30g/100ml未満である溶剤(D)を用いる、あるいは酸価(固形分換算)が30mgKOH/g以上200mgKOH/g未満であるエチレン性不飽和二重結合を有する化合物(A)を用い、テトラアルコキシシラン(E)を用いることで、経時安定性に優れた感光性組成物を得る事が出来た。 Moreover, as shown in Examples 15 to 19 in Table 8, the solvent (D) having a solubility in water at 20 ° C. of 1 g / 100 ml or more and less than 30 g / 100 ml is used, or the acid value (solid content conversion) is 30 mg KOH. Using a compound (A) having an ethylenically unsaturated double bond that is not less than 200 mgKOH / g and using tetraalkoxysilane (E), a photosensitive composition having excellent temporal stability can be obtained. done.
Claims (9)
エチレン性不飽和二重結合を有する化合物(A)が酸価(固形分換算)30mgKOH/g以上200mgKOH/g未満である化合物を含み、
光重合開始剤が、アセトフェノン系光重合開始剤、オキシムエステル系光重合開始剤、チオキサントン系光重合開始剤、ベンゾイン系光重合開始剤、ベンゾフェノン系光重合開始剤、トリアジン系光重合開始剤、ボレート系光重合開始剤、カルバゾール系光重合開始剤、およびイミダゾール系光重合開始剤からなる群から選ばれる少なくとも1種を含むことを特徴とする感光性組成物。
一般式(1):
[一般式(1)中、R1は炭素数1〜20のアルコキシ基、炭素数6〜20のアリールオキシ基、炭素数1〜20のアルキル基、炭素数6〜20のアリール基、炭素数7〜30のアルアルキル基、または、炭素数7〜30のアルカリール基を表し、
Xは炭素数1〜20のアルキレン基、炭素数1〜20のアリーレン基、または、炭素数1〜20のアルコキシレン基を表し、
R2、R3およびR4は互いに独立して、炭素数1〜20のアルコキシ基、炭素数6〜20のアリールオキシ基、炭素数1〜20のアルキル基、炭素数6〜20のアリール基、炭素数7〜30のアルアルキル基、炭素数7〜30のアルカリール基、置換基を有するシロキサン、ハロゲン、ヒドロキシおよび水素を表す。] A photosensitive composition comprising at least a compound (A) having an ethylenically unsaturated double bond, a silane compound (B) represented by the following general formula (1), and a photopolymerization initiator,
The compound (A) having an ethylenically unsaturated double bond includes a compound having an acid value (in terms of solid content) of 30 mgKOH / g or more and less than 200 mgKOH / g,
Photopolymerization initiator is acetophenone photopolymerization initiator, oxime ester photopolymerization initiator, thioxanthone photopolymerization initiator, benzoin photopolymerization initiator, benzophenone photopolymerization initiator, triazine photopolymerization initiator, borate A photosensitive composition comprising at least one selected from the group consisting of a photopolymerization initiator, a carbazole photopolymerization initiator, and an imidazole photopolymerization initiator.
General formula (1):
[In General Formula (1), R 1 is an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and the number of carbon atoms. Represents an aralkyl group having 7 to 30 carbon atoms or an alkaryl group having 7 to 30 carbon atoms,
X represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 1 to 20 carbon atoms, or an alkoxylene group having 1 to 20 carbon atoms,
R 2 , R 3 and R 4 are independently of each other an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Represents an aralkyl group having 7 to 30 carbon atoms, an alkaryl group having 7 to 30 carbon atoms, a siloxane having a substituent, halogen, hydroxy and hydrogen. ]
感光性組成物の固形分合計100重量%中の該シラン化合物(B)の含有量が5重量%以上60重量%未満であることを特徴とする請求項1または2に記載の感光性組成物。 The weight average molecular weight (Mw) of the silane compound (B) is 100 or more and less than 5000, and the content of the silane compound (B) in the total solid content of 100% by weight of the photosensitive composition is 5% by weight or more and 60% by weight. The photosensitive composition according to claim 1, wherein the composition is less than%.
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