JP6518243B2 - Photosensitive composition and cured film thereof - Google Patents

Description

  The present invention relates to adhesion to a substrate even at low temperature processing, which is suitable as a panel material such as a photosensitive composition, more specifically, an insulating film, retardation film, optical property film, etc. used for optical / electronic parts etc. Photosensitive composition and its cured film.

  In recent years, in the field of electronic and optical materials, high definition, wide viewing angle, high image quality, high brightness of light sources using light semiconductors such as light emitting diodes (LEDs) have been achieved for flat panel displays using liquid crystals and organic EL. Improvement studies are underway to improve the wavelength and wavelength, to whiten, to increase the frequency of electronic circuits, and to improve the performance of optical and electronic components such as circuits and communications using light. In addition, in the field of semiconductor technology, miniaturization, weight reduction, high performance and multifunctionalization of electronic devices are rapidly advancing. In addition, an optical circuit using an optical waveguide or the like which enables high-speed processing has also been studied. In response to these, high density and high wiring of the wiring substrate are required.

  In addition, cured films such as an insulating film, a retardation film, and an optical characteristic film are provided on optical / electronic components such as a liquid crystal display device, an organic EL display device, and an integrated circuit device. Although various materials have been developed for these cured films, for example, when a photosensitive composition is used, the photosensitive composition is coated on a substrate, exposed and developed in a predetermined pattern, and post-baked. It is formed by doing. With regard to the materials of these cured films, materials having high photosensitivity, high heat resistance, chemical resistance, and high transparency are also required in response to high performance of optical / electronic parts, high densification of wiring boards, etc. It is done.

  Moreover, in the touch-panel type display, the use of the electrostatic capacitance type touch panel is increasing in recent years. The capacitive touch panel captures a change in electrostatic capacitance between the fingertip and the conductive film to search for a position. A capacitive touch panel can not be provided with a layer for alleviating external impact like a resistive touch panel. For this reason, high hardness is required for the surface protective layer.

  As described above, in order to obtain a product meeting the above requirements, in addition to the material used in the cured film having such properties as high photosensitivity, high heat resistance, chemical resistance, hardness and high transparency, High adhesion to a substrate or the like is required. However, it is difficult to simultaneously achieve high hardness and good adhesion to a substrate, and as a means for improvement, it is practiced to add a silane coupling agent to a film material to improve the adhesion (for example, Patent Document 1).

International Publication No. 2011/114995

  However, in the conventional technique of adding a silane coupling agent, a necessary film material is applied in the case of using a plastic as a base material or in a state in which other parts, circuits and the like are already incorporated, In the case of film formation, the treatment has to be carried out at a low temperature, but there is a problem that such low temperature treatment can not obtain sufficient adhesion to the substrate.

  Then, an object of this invention is to provide the photosensitive composition which has sufficient adhesiveness with respect to a base material, and its cured film, even when a process is performed at low temperature.

  As a result of intensive studies to solve the above problems, the inventors of the present invention used an acrylic resin as a binder polymer, and reacted a specific silicon compound having an isocyanate newly found above with a silicon compound having a specific block group. The photosensitive composition containing the silane compound, which is a cured product, has sufficient adhesion to the substrate even if it is subjected to curing treatment such as post-baking at a temperature lower than 200.degree. C., for example, a low temperature of 180.degree. It has been found that it retains its desired properties as a membrane material and is stable, completing the present invention.

（式中、Ｒ¹〜Ｒ³は、同一または異なっていてもよく、全部または少なくとも１つは炭素数１〜５のアルコキシ基、好ましくはメトキシ基またはエトキシ基であり、他は炭素数１〜５のアルキル基、好ましくはメチル基またはエチル基である。Ａは、置換または非置換の炭素数２〜１８、好ましくは炭素数２〜１２、さらに好ましくは炭素数２〜６の直鎖または分岐鎖のアルキレン基であり、２価または３価の連結基を含んでいてもよい。ｑは、１〜３の整数であり、好ましくは１である。ｒは、１〜３の整数であり、好ましくは１のである。）

（式中、Ｒ⁴〜Ｒ⁶は、同一または異なっていてもよく、炭素数１〜５のアルコキシ基、好ましくはメトキシ基またはエトキシ基、または炭素数１〜５のアルキル基、好ましくはメチル基またはエチル基である。Ｂは、置換または非置換の炭素数２〜１５、好ましくは炭素数２〜１０、より好ましくは炭素数２〜６の直鎖または分岐鎖のアルキレン基であり、２価の連結基を含んでいてもよい。ｐは、０または１の整数である。Ｘは、Ｏ、ＮＨ、ＮＨ−ＣＯ−ＮＨ、Ｓであり、好ましくはＯ、ＮＨまたはＮＨ−ＣＯ−ＮＨである。ｓは、１〜３の整数であり、好ましくは１である。ｔは、１〜３の整数であり、好ましくは１である。ただし、ｐ＝０の場合は、ｓ＝１、ｔ＝１である。）、
［２］（Ａ）アクリル樹脂が、脂環式単位、エポキシ単位およびカルボン酸単位を有する上記［１］に記載の感光性組成物、
［３］（Ｂ）シランカップリング剤が、さらに下記一般式（３）で表されるシラン化合物、好ましくはトリメトキシシリルプロピル無水コハク酸を含む上記［１］または［２］に記載の感光性組成物

［式中、Ｒ¹²〜Ｒ¹⁴は、同一または異なってもよく、ヒドロキシまたは炭素数１〜５のアルコキシ基、好ましくはメトキシ基またはエトキシ基であり、Ｒ¹⁵は、無水カルボン酸基、−ＣＨＲ¹⁶（ＣＨ₂）_uＣＯＯＨまたは−ＣＨ（ＣＯＯＨ）（ＣＨ₂）_uＲ¹⁶（式中Ｒ¹⁶は、カルボン酸基またはカルボン酸エステル基であり、ｕは０〜３の整数、好ましくは０または１の整数である）であり、好ましくは無水カルボン酸基であり、さらに好ましくは無水コハク酸基であり、Ｄは、置換または非置換の炭素数２〜１０、好ましくは炭素数２〜５、より好ましくは炭素数２または３の直鎖または分岐鎖のアルキレン基、または置換または非置換の炭素数２〜１０、好ましくは炭素数２〜５、より好ましくは炭素数２または３の直鎖または分岐鎖の少なくとも１つの二重結合を有するアルキレン基である。］
［４］上記一般式（１）で表される化合物と、上記一般式（２）で表される化合物との反応物であるシラン化合物が、下記式（４）または（５）で表される化合物、好ましくは下記式（６）〜（１０）のいずれかで表される化合物である上記［１］〜［３］のいずれかに記載の感光性組成物、

（式中、Ｒ¹〜Ｒ³は、同一または異なっていてもよく、全部または少なくとも１つは炭素数１〜５のアルコキシ基、好ましくはメトキシ基またはエトキシ基であり、他は炭素数１〜５のアルキル基、好ましくはメチル基またはエチル基である。Ｒ⁴〜Ｒ⁶は、同一または異なっていてもよく、炭素数１〜５のアルコキシ基、好ましくはメトキシ基またはエトキシ基、または炭素数１〜５のアルキル基、好ましくはメチル基またはエチル基である。Ａは、置換または非置換の炭素数２〜１８、好ましくは炭素数２〜１２、より好ましくは炭素数２〜６の直鎖または分岐鎖のアルキレン基であり、２価または３価の連結基を含んでいてもよい。Ｂは、置換または非置換の炭素数２〜１５、好ましくは炭素数２〜１０、より好ましくは炭素数２〜６の直鎖または分岐鎖のアルキレン基であり、２価の連結基を含んでいてもよい。Ｘは、Ｏ、ＮＨ、ＮＨ−ＣＯ−ＮＨまたはＳであり、好ましくはＯ、ＮＨまたはＮＨ−ＣＯ−ＮＨである。ｐは、０または１の整数である。ｑは、１〜３の整数、好ましくは１である。ｒは、１〜３の整数、好ましくは１である。ｓは、１〜３の整数、好ましくは１である。ｔは、１〜３の整数、好ましくは１である。）

（式中、Ｒ¹〜Ｒ³は、上記化学式（１）で示したものと同様である。Ｒ⁴〜Ｒ⁶は、同一または異なっていてもよく、１〜５のアルキル基である。炭素数１〜５のアルキル基は、上記と同様である。ｍは、２〜１８の整数であり、好ましくは２〜８、特に好ましくは２〜４の整数である。）

（式中、Ｒ¹〜Ｒ³、Ｒ⁴〜Ｒ⁶は、上記化学式（１）、（２）で示したものと同様である。ｍは、上記と同様である。ｎは、２〜１５の整数であり、好ましくは２〜８、特に好ましくは２〜４の整数である。）

（式中、Ｒ¹〜Ｒ³、Ｒ⁴〜Ｒ⁶、ｍ、ｎは、上記一般式（７）と同様である。）

（式中、Ｒ¹〜Ｒ³、Ｒ⁴〜Ｒ⁶、ｍ、ｎは、上記一般式（７）と同様である。）

（式中、Ｒ¹〜Ｒ³、Ｒ⁴〜Ｒ⁶、ｍ、ｎは、上記一般式（７）と同様である。）、
［５］式（４）のＡで表される、連結基を有する炭素数２〜１８の直鎖または分岐鎖のアルキレン基において、２価または３価の連結基は、下記式［Ａ１］からなる群より選択される少なくとも１個であり、式（５）のＢで表される、連結基を有する炭素数２〜１５の直鎖または分岐鎖のアルキレン基において、２価の連結基は、下記式［Ｂ１］からなる群より選択される少なくとも１個である上記［１］〜［４］のいずれかに記載の感光性組成物

［Ｒ⁷、Ｒ⁸は、同一または異なっていてもよい、水素原子、炭素数１〜５のアルキル基、炭素数６〜１２のアリール基、−ＣＨ＝、

（Ｒ⁹、Ｒ¹⁰は、炭素数１〜５のアルキル基、ｍ３は、１〜５の整数）、

（ｍ４は、１〜５の整数）、

（Ｒ¹¹は、炭素数１〜５のアルキル基）、または、置換基を有していてもよい炭素数３〜６のシクロアルカンで表される、１価または２価の基である。Ｒ⁷またはＲ⁸のいずれか一方が２価の基である場合、他方は、水素原子または１価の基である。］、

結合手を少なくとも２ヶ所有する、置換または非置換の炭素数３〜６のシクロアルカン、

、および
［６］上記［１］〜［５］のいずれかに記載の感光性組成物を硬化させてなる硬化膜
に関する。 That is, the present invention
[1] (A) Acrylic resin, (B) Silane coupling agent, and (C) photopolymerizable compound, (B) Silane coupling agent has isocyanate represented by the following general formula (1) A photosensitive composition characterized in that it is a silane compound which is a reaction product of a silicon compound and a silicon compound represented by the following general formula (2)

(Wherein, R ^{1 to} R ³ may be the same or different, and all or at least one is an alkoxy group of 1 to 5 carbon atoms, preferably a methoxy group or an ethoxy group, and the others are 1 to 4 carbon atoms A is preferably a substituted or unsubstituted C2 to C18, preferably C2 to C12, more preferably C2 to C6 linear or branched, substituted or unsubstituted. And is a chain alkylene group, which may contain a divalent or trivalent linking group, q is an integer of 1 to 3, preferably 1. r is an integer of 1 to 3, Preferably it is 1.)

(Wherein, R ^{4 to} R ⁶ may be the same or different, and are an alkoxy group having 1 to 5 carbon atoms, preferably a methoxy group or an ethoxy group, or an alkyl group having 1 to 5 carbon atoms, preferably a methyl group And B is a linear or branched alkylene group having 2 to 15 carbon atoms, preferably 2 to 10 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms, which is substituted or unsubstituted; And P may be an integer of 0 or 1. X is O, NH, NH-CO-NH, S, preferably O, NH or NH-CO-NH. S is an integer of 1 to 3 and is preferably 1. t is an integer of 1 to 3 and preferably 1. However, in the case of p = 0, s = 1 and t = 1),
[2] The photosensitive composition according to the above [1], wherein the (A) acrylic resin has an alicyclic unit, an epoxy unit and a carboxylic acid unit,
[3] (B) The photosensitivity according to the above [1] or [2], wherein the silane coupling agent further contains a silane compound represented by the following general formula (3), preferably trimethoxysilylpropyl succinic anhydride Composition

[Wherein, R ^{12 to} R ¹⁴ may be the same or different and are hydroxy or an alkoxy group having 1 to 5 carbon atoms, preferably a methoxy group or an ethoxy group, and R ¹⁵ is a carboxylic anhydride group, —CHR ¹⁶ (CH ₂ ) _u COOH or —CH (COOH) (CH ₂ ) _u R ¹⁶ (wherein, R ¹⁶ is a carboxylic acid group or a carboxylic acid ester group, u is an integer of 0 to 3, preferably 0 or 1), preferably a carboxylic anhydride group, more preferably a succinic anhydride group, and D is a substituted or unsubstituted carbon number of 2 to 10, preferably 2 to 5 carbon atoms, More preferably, it is a linear or branched alkylene group having 2 or 3 carbon atoms, or a substituted or unsubstituted 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms Branched chain An alkylene group having at least one double bond. ]
[4] The silane compound which is a reaction product of the compound represented by the above general formula (1) and the compound represented by the above general formula (2) is represented by the following formula (4) or (5) The photosensitive composition according to any one of the above [1] to [3], which is a compound, preferably a compound represented by any one of the following formulas (6) to (10),

(Wherein, R ^{1 to} R ³ may be the same or different, and all or at least one is an alkoxy group of 1 to 5 carbon atoms, preferably a methoxy group or an ethoxy group, and the others are 1 to 4 carbon atoms R ^{4 to} R ^{6, which} may be the same or different, are each an alkoxy group having 1 to 5 carbon atoms, preferably a methoxy group or an ethoxy group, or a carbon number A substituted or unsubstituted alkyl group having 2 to 18 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms Or a branched alkylene group, which may contain a divalent or trivalent linking group B is a substituted or unsubstituted carbon number of 2 to 15, preferably 2 to 10, more preferably carbon 2 to 6 Is a linear or branched alkylene group which may contain a divalent linking group, and X is O, NH, NH-CO-NH or S, preferably O, NH or NH-CO. P is an integer of 0 or 1. q is an integer of 1 to 3, preferably 1. r is an integer of 1 to 3, preferably 1. s is 1 It is an integer of ~ 3, preferably 1. t is an integer of 1 to 3, preferably 1.

(Wherein, R ^{1 to} R ³ are the same as those shown in the above chemical formula (1). R ^{4 to} R ⁶ may be the same or different and are an alkyl group of 1 to 5. Carbon The alkyl group of the formulas 1 to 5 is the same as above, m is an integer of 2 to 18, preferably 2 to 8, particularly preferably 2 to 4.)

(Wherein, R ^{1 to} R ³ and R ^{4 to} R ⁶ are the same as those shown in the above chemical formulas (1) and (2). M is the same as the above. N is 2 to 15) And preferably 2 to 8, particularly preferably 2 to 4.)

(Wherein, R ^{1 to} R ³ , R ^{4 to} R ⁶ , m and n are the same as in the above general formula (7)).

(Wherein, R ^{1 to} R ³ , R ^{4 to} R ⁶ , m and n are the same as in the above general formula (7)).

(Wherein, R ^{1 to} R ³ , R ^{4 to} R ⁶ , m and n are the same as in the above general formula (7)),
[5] In the linear or branched alkylene group having 2 to 18 carbon atoms having a linking group, represented by A in the formula (4), the divalent or trivalent linking group is selected from the following formula [A1] In the linear or branched alkylene group having 2 to 15 carbon atoms having a linking group, which is at least one member selected from the group consisting of and represented by B in the formula (5), the divalent linking group is The photosensitive composition according to any one of the above [1] to [4], which is at least one selected from the group consisting of the following formula [B1]

[R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an aryl group of 6 to 12 carbon atoms, -CH =,

(R ⁹ and R ^{10 each} represent an alkyl group of 1 to 5 carbon atoms, m 3 is an integer of 1 to 5),

(M4 is an integer of 1 to 5),

(R ¹¹ is an alkyl group of 1 to 5 carbon atoms) or a monovalent or divalent group represented by a cycloalkane of 3 to 6 carbon atoms which may have a substituent. When one of R ^{7 and} R ⁸ is a divalent group, the other is a hydrogen atom or a monovalent group. ],

A substituted or unsubstituted cycloalkane having 3 to 6 carbon atoms, having at least two bonds

And [6] a cured film obtained by curing the photosensitive composition according to any one of the above [1] to [5].

  The photosensitive composition of the present invention exhibits sufficient adhesion to the substrate even when the film formation treatment is performed at a low temperature on the substrate. As a result, it can be used also for a substrate that can not be subjected to high temperature processing, and it becomes possible to perform film formation on cell in the manufacturing process of parts.

FIG. 1 is a chart of IR chart confirming the completion of the reaction of Synthesis Example 1. FIG. 2 is a chart of NMR of the reaction product of Synthesis Example 1.

((A) Acrylic resin)
The photosensitive composition of the present invention contains (A) an acrylic resin, and as the acrylic resin, one obtained by radical polymerization of (meth) acrylic acid and / or (meth) acrylic acid ester can be used. . Further, the acrylic resin in the present invention preferably contains an alicyclic unit from the viewpoint of chemical resistance and transparency, preferably contains an epoxy unit from the viewpoint of chemical resistance and adhesion, and is further preferably alkali-developed. It is preferable to contain a carboxylic acid unit from the viewpoint of properties. The acrylic resin containing these units is, for example, a general radical polymerization in which a polymerizable monomer having an alicyclic group, an epoxy group or a carboxyl group and other monomers are dissolved in a general solvent. It can be produced by radical polymerization using an initiator. It is preferable that all of these units be included in combination, because the adhesion improvement effect of the present invention can be effectively obtained. Moreover, as such a solvent, the same thing as what is used for the photosensitive composition of this invention mentioned later can be mentioned. As such a polymerization initiator, as an azo initiator, AIBN: 2,2'-azobisisobutyronitrile, ADVN: 2,2'-azobis (2,4-dimethyl valeronitrile), 2,2 '-Azobis (4-methoxy-2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd., V-70), dimethyl-2,2'-azobis (2-methylpropinato) (Wako Pure Chemical Industries, Ltd. (V-601), 2,2'-azobis (2-methylbutyronitrile) (Wako Pure Chemical Industries, Ltd., V-59), 1,1'-azobis (cyclohexane-1-carbonitrile) (Wako Pure Chemical Industries, Ltd., V-40), 4,4′-azobis (4-cyanopentanoic acid) (Otsuka Chemical Co., Ltd., ACVA) and the like, and as a peroxide initiator, Peroxyneodecanoate-t-butyl (NOF (stock Manufactured by Perbutyl ND), t-hexylperoxypivalate (manufactured by NOF Corporation, Perhexyl PV), t-butylperoxypivalate (manufactured by NOF Corporation, perbutyl PV), peroxy-2-ethyl Hexanoic acid-t-hexyl (manufactured by NOF Corporation, perhexyl O), peroxy-2-ethylhexanoate-t-butyl (manufactured by NOF Corporation, perbutyl O), etc. may be mentioned.

As a polymerizable monomer having an alicyclic group, a C _3-10 monocyclic or polycyclic alicyclic hydrocarbon group is ester bonded directly or via an alkyl group to (meth) acrylic acid (Meth) acrylic acid ester having an alicyclic hydrocarbon. Specifically, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) Tricyclodecanyl acrylate, Tricyclodecanylmethyl (meth) acrylate, Tetracyclodecanyl (meth) acrylate, Tricyclodecanyl di (meth) acrylate, Tricyclodecanylmethyl di (meth) acrylate And adamantyl (meth) acrylate, adamantyl methyl (meth) acrylate, 1-methyladamantyl (meth) acrylate, adamantyl ethyl (meth) acrylate, 1-ethyladamantyl (meth) acrylate and the like. These monomers can be used singly or in combination of two or more. In addition, dicyclopentanyl acrylate is commercially available as FA-513AS (manufactured by Hitachi Chemical Co., Ltd., trade name), and dicyclopentanyl methacrylate is commercially available as FA-513M (manufactured by Hitachi Chemical Co., Ltd., trade name) It is available. Adamantyl methacrylate (ADMA) is commercially available as Adamantate M-104 (trade name, manufactured by Idemitsu Kosan Co., Ltd.).

  Although the compounding quantity of the polymerizable monomer which has an alicyclic group in an acrylic resin is not specifically limited, Assuming that all the monomers are 100 mass parts, Preferably it is 10 mass parts or more, More preferably, 20 It is not less than mass part, preferably not more than 80 parts by mass, more preferably not more than 70 parts by mass. If the amount is less than 10 parts by mass, the chemical resistance tends to be poor, and if the amount is more than 80 parts by mass, the shape and the developability tend to be inferior.

  As a polymerizable monomer having an epoxy group, (meth) acrylic acid glycidyl, (meth) acrylic acid α-ethyl glycidyl, (meth) acrylic acid α-n-propyl glycidyl, (meth) acrylic acid α-n- Butyl glycidyl, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxyheptyl (meth) acrylate, α-ethyl-6,7-epoxyheptyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether (4-HBAGE), 3,4-epoxycyclohexylmethyl methacrylate (trade name: Cyclomer M-100, manufactured by Daicel Corporation), epoxidized cyclohexyl polylactone methacrylate (trade name: Cyclomer M-101, Inc.) Daicel), 3,4-epoxycyclohexyl methyl acrylate Product Name: CYCLOMER A-200, (Ltd.) manufactured by Daicel), and the like. These monomers can be used singly or in combination of two or more.

  Although the compounding quantity of the polymerizable monomer which has an epoxy group in an acrylic resin is not specifically limited, Assuming that all the monomers are 100 mass parts, Preferably it is 5 mass parts or more, More preferably, 10 mass parts The amount is preferably 70 parts by mass or less, more preferably 50 parts by mass or less. When the amount is less than 5 parts by mass, the chemical resistance tends to be poor, and when the amount is more than 70 parts by mass, the shape tends to be inferior.

  As a polymerizable monomer having a carboxylic acid group, (meth) acrylic acid, caprolactone adduct of (meth) acrylic acid, (meth) acryloylethyl monophthalate, (meth) acryloylethyl monohexahydrophthalate, (meth) Acryloyl ethyl monotetrahydro phthalate is preferable, and methacrylic acid is more preferable among them. These monomers can be used singly or in combination of two or more.

  Although the compounding quantity of the polymerizable monomer which has a carboxylic acid group in an acrylic resin is not specifically limited, When all the monomers are 100 mass parts, Preferably it is 5 mass parts or more, More preferably, 10 mass It is not less than 50 parts by mass, more preferably not more than 25 parts by mass. When the amount is less than 5 parts by mass, the chemical resistance and the developability tend to be inferior, and when the amount is more than 50 parts by mass, the shape tends to be inferior.

  As another monomer, for example, methyl (meth) acrylate, t-butyl (meth) acrylate, stearyl (meth) acrylate, ethoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, phenyl (meth) acrylate, (Meth) acrylic monomers such as N, N-dimethyl acrylamide; styrene, α-methylstyrene, ethyl vinyl ether, N-vinyl imidazole, vinyl acetate, vinyl pyridine, 2-vinyl naphthalene, vinyl chloride, vinyl fluoride, N-vinyl Vinyl-based monomers such as carbazole, vinylamine, vinylphenol and N-vinyl-2-pyrrolidone; allyl-based monomers such as 4-allyl-1,2-dimethoxybenzene, 4-allylphenol and 4-methoxyallylbenzene; E alkenyl maleimides, maleimide such as cyclohexyl maleimide can be used. These can be used alone or in combination of two or more.

  Moreover, the acrylic resin in the present invention can contain a hydroxyl group from the viewpoint of the patterning property. The acrylic resin containing a hydroxyl group can be produced, for example, by radically polymerizing a polymerizable monomer having a hydroxyl group and another polymerizable monomer. As the polymerizable monomer having a hydroxyl group, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like are preferable, and in particular, 2-hydroxyethyl methacrylate is more preferable.

  These acrylic resins are used alone or in combination of two or more. As an acrylic resin in the case of using in combination of 2 or more types, for example, 2 or more types of acrylic resin consisting of different copolymerization components, 2 or more types of acrylic resin of different weight average molecular weight, 2 or more types of different dispersion degree Acrylic resin etc. are mentioned.

  The polymerization average molecular weight (Mw) of the (A) acrylic resin is not particularly limited, but is preferably 2,000 or more, more preferably 3,000 or more, preferably 100,000 or less, in terms of polystyrene. More preferably, it is 20,000 or less. When the polymerization average molecular weight (Mw) is less than 2,000, peeling of the formed pattern tends to occur, and when it is more than 100,000, the developability may be deteriorated, which tends to lead to a reduction in resolution. There is.

  The acid value of the acrylic resin (A) is not particularly limited, but is preferably 20 or more, more preferably 30 or more, and preferably 200 or less, more preferably 150 or less. When the acid value is less than 20, developability may be deteriorated, which tends to lead to a reduction in resolution, and when it is more than 200, peeling of the formed pattern tends to occur.

（式中、Ｒ¹〜Ｒ³は、同一または異なっていてもよく、全部または少なくとも１つは炭素数１〜５のアルコキシ基であり、他は炭素数１〜５のアルキル基である。Ａは、置換または非置換の炭素数２〜１８の直鎖または分岐鎖のアルキレン基であり、２価または３価の連結基を含んでいてもよい。ｑは、１〜３の整数である。ｒは、１〜３の整数である。）((B) Silane coupling agent)
The photosensitive composition of the present invention is a reaction of a silicon compound having an isocyanate represented by the following general formula (1) as a silane coupling agent (B) and a silicon compound represented by the following general formula (2) Containing silane compounds.

(Wherein, R ^{1 to} R ³ may be the same or different, all or at least one is an alkoxy group having 1 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms). Is a substituted or unsubstituted linear or branched alkylene group having 2 to 18 carbon atoms, and may contain a divalent or trivalent linking group, and q is an integer of 1 to 3. r is an integer of 1 to 3.)

  As the alkoxy group having 1 to 5 carbon atoms, for example, methoxy group, ethoxy group, 1-propoxy group, 2-propoxy group, 1-butoxy group, 2-methylpropoxy group, 2-butoxy group, 1,1-dimethylethoxy A group, 1-pentoxy group, 3-methylbutoxy group, 2,2-dimethylpropoxy group, 1,1-dimethylpropoxy group and the like are preferably used, and a methoxy group or an ethoxy group is more preferable.

  As an alkyl group of 1 to 5 carbon atoms, for example, methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-methylpropyl group, 2-butyl group, 1,1-dimethylethyl A group, 1-pentyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, 1,1-dimethylpropyl group and the like are preferably used, and a methyl group or an ethyl group is more preferable.

［Ｒ⁷、Ｒ⁸は、同一または異なっていてもよい、水素原子、炭素数１〜５のアルキル基、炭素数６〜１２のアリール基、−ＣＨ＝、

（Ｒ⁹、Ｒ¹⁰は、炭素数１〜５のアルキル基、ｍ３は、１〜５の整数）、

（ｍ４は、１〜５の整数）、

（Ｒ¹¹は、炭素数１〜５のアルキル基）、または、置換基を有していてもよい炭素数３〜６のシクロアルカンで表される、１価または２価の基である。Ｒ⁷またはＲ⁸のいずれか一方が２価の基である場合、他方は、水素原子または１価の基である。］、

結合手を少なくとも２ヶ所有する、置換または非置換の炭素数３〜６のシクロアルカン、

A is a substituted or unsubstituted linear or branched alkylene group having 2 to 18 carbon atoms. The carbon number of the linear or branched alkylene group is preferably 2 to 12, more preferably 2 to 6. As a substituent of a C2-C18 linear or branched alkylene group, the ester group etc. which the C1-C5 alkyl group couple | bonded are mentioned. A may contain at least one divalent or trivalent linking group. Examples of the divalent or trivalent linking group include those represented by the following formula [A1]. The substituted or unsubstituted linear or branched alkylene group having 2 to 18 carbon atoms includes a trivalent linking group to obtain a compound in which q and r are integers larger than 1 in the formula (1). Be

[R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an aryl group of 6 to 12 carbon atoms, -CH =,

(R ⁹ and R ^{10 each} represent an alkyl group of 1 to 5 carbon atoms, m 3 is an integer of 1 to 5),

(M4 is an integer of 1 to 5),

(R ¹¹ is an alkyl group of 1 to 5 carbon atoms) or a monovalent or divalent group represented by a cycloalkane of 3 to 6 carbon atoms which may have a substituent. When one of R ^{7 and} R ⁸ is a divalent group, the other is a hydrogen atom or a monovalent group. ],

A substituted or unsubstituted cycloalkane having 3 to 6 carbon atoms, having at least two bonds

  In said [A1], a C1-C5 alkyl group is the same as that of what was illustrated by the said General formula (1). Moreover, as a C6-C12 aryl group, a phenyl group, a benzyl group, a tolyl group etc. are mentioned. Examples of the C3-C6 cycloalkane include cyclopropane, cyclobutane, cyclopentane and cyclohexane.

  The isocyanate group or silicon atom is attached to A. When A contains one or more trivalent linking groups [A1], it can be a compound having a plurality of isocyanate groups in the molecule or a compound having a plurality of silicon atoms in the molecule. In addition, even when a trivalent linking group is contained, a group not involved in the reaction such as a methyl group or a cyano group is bonded to the end of one of the linking groups to form a divalent linking group. In some cases.

  q is an integer of 1 to 3, preferably 1. r is an integer of 1 to 3, preferably 1.

（式中、Ｒ⁴〜Ｒ⁶は、同一または異なっていてもよく、炭素数１〜５のアルコキシ基または炭素数１〜５のアルキル基である。Ｂは、置換または非置換の炭素数２〜１５の直鎖または分岐鎖のアルキレン基であり、２価の連結基を含んでいてもよい。ｐは、０または１の整数である。Ｘは、Ｏ、ＮＨ、ＮＨ−ＣＯ−ＮＨ、Ｓである。ｓは、１〜３の整数である。ｔは、１〜３の整数である。ただし、ｐ＝０の場合は、ｓ＝１、ｔ＝１である。）

(Wherein, R ^{4 to} R ⁶ may be the same or different, and are an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms. B is a substituted or unsubstituted carbon number 2 A linear or branched alkylene group, which may contain a divalent linking group, p is an integer of 0 or 1. X is O, NH, NH-CO-NH, It is S. s is an integer of 1 to 3. t is an integer of 1 to 3. However, in the case of p = 0, s = 1 and t = 1.)

R ^{4 to} R ^{6, which} may be the same or different, are an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms. Examples of the alkoxy group having 1 to 5 carbon atoms or the alkyl group having 1 to 5 carbon atoms can be the same as those exemplified for the above R ^{1 to} R ³ .

  B is a substituted or unsubstituted linear or branched alkylene group having 2 to 15 carbon atoms. The carbon number of the linear or branched alkylene group is preferably 2 to 10, more preferably 2 to 6. B may contain at least one divalent linking group. As a bivalent coupling group, what is shown to following formula [B1] is mentioned.

  X is O, NH, NH-CO-NH, S. Preferably, X is O, NH or NH-CO-NH.

  The X group or the silicon atom is bonded to B or the X group and the silicon atom are directly bonded. In the molecule having a plurality of X groups, the second or more X groups are bonded to the above [B1], or the substituent [B1] itself is an NH-CO-NH group. In the molecule having a plurality of silicon atoms in the molecule, the second or more silicon atoms are bonded to the above [B1], or a linear or branched alkylene group substituent.

  p is an integer of 0 or 1. s is an integer of 1 to 3, preferably 1. t is an integer of 1 to 3, preferably 1.

  The reaction between the compound represented by the general formula (1) and the compound represented by the general formula (2) is the reaction of the general formula (2) to the isocyanate group of the compound represented by the general formula (1) The nucleophilic addition reaction of the X group of the compound represented by In the present invention, in the reactants, all isocyanate groups may be blocked by X groups. That is, the reaction product of a silicon compound having a plurality of isocyanate groups and a silicon compound having a plurality of X groups may be used.

  This reaction can be carried out without catalyst. The solvent may or may not be used, and is not particularly limited. When a solvent is used, for example, ethers such as diethyl ether, ethyl methyl ether, tetrahydrofuran and dioxane, halogenated hydrocarbons such as chloroform and dichloromethane, amides such as dimethylformamide, ethyl acetate, methyl acetate, butyl acetate and the like Esters, N-methyl pyrrolidone and the like can be used.

  The ratio of the compound represented by the general formula (1) to the compound represented by the general formula (2) is the same as that of the compound in which the isocyanate group of the compound of the general formula (1) is represented by the general formula (2) There is no particular limitation as long as it completely reacts with X. The amount of X used may be large or small with respect to 1 mole of isocyanate. When the amount of X used is large with respect to 1 mol of isocyanate, the compound represented by Formula (4) or (5) is obtained. When the amount of X used is small with respect to 1 mol of isocyanate, active hydrogen in the silicon compound represented by the general formula (4) or (5) remains in the reaction system, so that this is further substituted with an isocyanate group By reaction, a compound having a structure in which the isocyanate group has disappeared is obtained.

  The use ratio of the compound represented by the general formula (1) to the compound represented by the general formula (2) is not particularly limited as long as the isocyanate completely reacts with X of the silicon compound. For example, X is 1.00 to 6.00 mol, preferably 1.00 to 1.50 mol, more preferably 1.00 to 1.20 mol with respect to 1 mol of isocyanate. If X is less than 1.00 mol with respect to 1 mol of isocyanate, it is not preferable because the reaction between the isocyanate and X can not be performed completely. When X is more than 6.00 mol with respect to 1 mol of isocyanate, an unreacted silicon compound represented by the general formula (2) remains, which is not preferable.

  The reaction temperature is 30 to 90 ° C, preferably 40 to 80 ° C, and more preferably 50 to 70 ° C. The reaction time is usually 1 minute to 2 days, particularly 30 minutes to 3 hours.

The completion of the reaction is carried out by confirming disappearance of the isocyanate peak (2200 to 2300 cm ⁻¹ ) using infrared spectroscopy (hereinafter referred to as “IR”) or the like.

  The silane compound which is a reaction product of the compound represented by the general formula (1) and the compound represented by the general formula (2) is, for example, a compound represented by the following formula (4) or (5) Is preferable.

The silane compound represented by the following general formula (4) is a silicon compound having an isocyanate represented by the above general formula (1), having r number of isocyanates (integer of r = 1 to 3), and the above general formula The silicon compound represented by (2) is a reactant having one X, that is, t = 1.

In the formula, R ^{1 to} R ³ , R ^{4 to} R ⁶ , A, B, X, p, q, r and s are the same as those shown in the general formulas (1) and (2).

The silane compound represented by the above general formula (4) is obtained by the following reaction formula.

式中、Ｒ¹〜Ｒ³、Ｒ⁴〜Ｒ⁶、Ａ、Ｂ、Ｘ、ｐ、ｑ、ｓ、ｔは、上記一般式（１）、（２）で示したものと、同じである。The silane compound represented by the following general formula (5) is a silicon compound having an isocyanate represented by the above general formula (1) and has one isocyanate (r = 1), and is represented by the above general formula (2) It is a reactant in the case where the silicon compound to be represented has t (t is an integer of 1 to 3) X.

In the formula, R ^{1 to} R ³ , R ^{4 to} R ⁶ , A, B, X, p, q, s and t are the same as those shown in the general formulas (1) and (2).

The silane compound represented by the above general formula (5) is obtained by the following reaction formula.

式中、Ｒ¹〜Ｒ³は、上記化学式（１）で示したものと同様である。Ｒ⁴〜Ｒ⁶は、同一または異なっていてもよく、１〜５のアルキル基である。炭素数１〜５のアルキル基は、上記と同様である。ｍは、２〜１８の整数であり、好ましくは２〜８、特に好ましくは２〜４の整数である。It is still more preferable that the said silane compound is a silane compound represented by the formula in any one of following formula (6)-(10).

In formula, R < ¹ > -R < ³ > is the same as that shown by said Chemical formula (1). R ^{4 to} R ^{6, which} may be the same or different, are an alkyl group of 1 to 5; The C1-C5 alkyl group is the same as the above. m is an integer of 2 to 18, preferably 2 to 8, particularly preferably 2 to 4.

式中、Ｒ¹〜Ｒ³、Ｒ⁴〜Ｒ⁶は、上記化学式（１）、（２）で示したものと同様である。ｍは、上記と同様である。ｎは、２〜１５の整数であり、好ましくは２〜８、特に好ましくは２〜４の整数である。

In the formula, R ^{1 to} R ³ and R ^{4 to} R ⁶ are the same as those shown in the above chemical formulas (1) and (2). m is the same as above. n is an integer of 2 to 15, preferably 2 to 8, particularly preferably 2 to 4.

式中、Ｒ¹〜Ｒ³、Ｒ⁴〜Ｒ⁶、ｍ、ｎは、上記一般式（７）と同様である。

In the formula, R ^{1 to} R ³ , R ^{4 to} R ⁶ , m and n are the same as in the above general formula (7).

式中、Ｒ¹〜Ｒ³、Ｒ⁴〜Ｒ⁶、ｍ、ｎは、上記一般式（７）と同様である。

In the formula, R ^{1 to} R ³ , R ^{4 to} R ⁶ , m and n are the same as in the above general formula (7).

式中、Ｒ¹〜Ｒ³、Ｒ⁴〜Ｒ⁶、ｍ、ｎは、上記一般式（７）と同様である。

In the formula, R ^{1 to} R ³ , R ^{4 to} R ⁶ , m and n are the same as in the above general formula (7).

［式中、Ｒ¹²〜Ｒ¹⁴は、同一または異なってもよく、ヒドロキシまたは炭素数１〜５のアルコキシ基であり、Ｒ¹⁵は、無水カルボン酸基、−ＣＨＲ¹⁶（ＣＨ₂）_uＣＯＯＨまたは−ＣＨ（ＣＯＯＨ）（ＣＨ₂）_uＲ¹⁶（式中Ｒ¹⁶は、カルボン酸基またはカルボン酸エステル基であり、ｕは０〜３の整数である）であり、Ｄは、置換または非置換の炭素数２〜１０の直鎖または分岐鎖のアルキレン基、または置換または非置換の炭素数２〜１０の直鎖または分岐鎖の少なくとも１つの二重結合を有するアルキレン基である。］As a (B) silane coupling agent in the photosensitive composition of this invention, the silane compound which is a reaction product of the compound represented by the said General formula (1), and the compound represented by the said General formula (2) Preferably, a silane compound of the above formula (4) or (5), more preferably a silane compound of the above formulas (6) to (10) can be used singly or in combination of two or more. In addition, at least one of the silane compounds represented by the following general formula (3) is used in combination as component (B) to further improve the adhesion, particularly to improve adhesion to various substrates at low temperature processing. It is preferable because it can be obtained effectively.

[Wherein, R ^{12 to} R ¹⁴ may be the same or different and are hydroxy or an alkoxy group having 1 to 5 carbon atoms, and R ¹⁵ is a carboxylic acid anhydride group, —CHR ¹⁶ (CH ₂ ) _u COOH or -CH (COOH) (CH ₂ ) _u R ¹⁶ (wherein, R ¹⁶ is a carboxylic acid group or a carboxylic acid ester group, u is an integer of 0 to 3), and D is a substituted or unsubstituted Is a linear or branched alkylene group having 2 to 10 carbon atoms, or a substituted or unsubstituted alkylene group having at least one double bond of a linear or branched chain having 2 to 10 carbon atoms. ]

In the above formula (3), R ¹² ~R ¹⁴ may be the same or different, it is a hydroxy or alkoxy group having 1 to 5 carbon atoms.

  In said Formula (3), a C1-C5 alkoxy group is the same as what was shown by said Formula (1), and a methoxy group or an ethoxy group is preferable.

In the above formula (3), R ¹⁵ is a carboxylic acid anhydride group, —CHR ¹⁶ (CH ₂ ) _u COOH or —CH (COOH) (CH ₂ ) _u R ¹⁶ (wherein R ¹⁶ is a carboxylic acid group or a carboxylic acid group An acid ester group, u is an integer of 0 to 3, preferably 0 or 1, and a carboxylic acid anhydride group is preferred.

  As carboxylic acid anhydride which constitutes a carboxylic acid anhydride group in the above-mentioned formula (3), succinic anhydride, maleic anhydride, glutaric anhydride etc. are mentioned, and succinic anhydride is preferable.

The carboxylic acid ester group of R ¹⁶ is not particularly limited, and examples thereof include an ester group with a linear or branched alcohol having 1 to 5 carbon atoms, and an ester group having a polyethylene chain or a polypropylene chain And may have reactive groups such as (meth) acryloyloxy group and (meth) acrylamide group.

In the above formula (3), D is at least one of a substituted or unsubstituted linear or branched alkylene group having 2 to 10 carbon atoms, or a substituted or unsubstituted linear or branched chain having 2 to 10 carbon atoms It is an alkylene group having one double bond, and the carbon number of the alkylene chain is preferably 2 to 5, and more preferably 2 or 3. Examples _include- (CH ₂ ) ₂ -7-, -CH ₂ -CH (CH ₃ ) -CH _2- , -CH ₂ -CH = CH- (CH ₂ ) _3-7- and the like. As these substituents, a methyl group, an ethyl group, a carboxyl group etc. are mentioned.

  Specific examples of the general formula (3) include trimethoxysilylpropyl succinic anhydride, triethoxysilyl propyl succinic anhydride, trimethoxysilyl butyl succinic anhydride, triethoxy silyl butyl succinic anhydride, 3- [6- (tri (3-) Trimethoxysilylhexynyl succinic anhydride such as methoxysilyl) -2-hexen-1-yl] succinic anhydride, 2-methyl-3- (triethoxysilyl) propyl succinic anhydride, 3- [10- (trimethoxy) Silyl) -2-decen-1-yl] succinic anhydride, tetrahydro-2,5-dioxo-α- [2- (triethoxysilyl) ethyl] -3-furanacetic acid, 3-trimethoxysilylpropyl glutaric anhydride 3-triethoxysilylpropyl glutaric acid, and their hydrolysates, etc. Shi silyl propyl succinic anhydride are preferable.

（式中、Ｒ¹⁷は、ヒドロキシル基または炭素数１〜５のアルコキシ基を示し、炭素数１〜５のアルコキシ基は、上記式（１）で示したものと同じである。）When the compound of the general formula (3) has an acid anhydride group, the ring is opened by water etc. in the system to form a carboxyl group. The following shows Scheme 1 in the case where the acid anhydride group is succinic anhydride, but the same applies to other acid anhydride groups. In the formula, the R ¹⁷ group is a hydroxyl group derived from a carboxyl group generated by hydrolysis, or an alkoxy group formed by alcoholysis with an alcohol generated within the reaction system by hydrolysis, for example, an alcohol having 1 to 5 carbon atoms Show. The product thus ring-opened is also included in the compound of the general formula (3), and the mixture resulting from the reaction can be used as it is as the silane coupling agent of the present invention.

(Wherein, R ¹⁷ represents a hydroxyl group or an alkoxy group having 1 to 5 carbon atoms, and the alkoxy group having 1 to 5 carbon atoms is the same as that shown in the above formula (1)).

  In the photosensitive composition of the present invention, the content of the (B) silane coupling agent is not particularly limited, but preferably 2 parts by mass or more, more preferably 100 parts by mass of the acrylic resin (A). Is 5 parts by mass or more, particularly preferably 8 parts by mass or more, preferably 50 parts by mass or less, more preferably 30 parts by mass or less. If the amount is less than 2 parts by mass, the effect of improving the adhesion tends to not be sufficiently obtained. If the amount is more than 50 parts by mass, the curability tends to be reduced, and hardening may be difficult.

((C) polymerizable compound)
The photosensitive composition of the present invention contains, as a polymerizable compound, at least one polyfunctional polymerizable compound (monomer or oligomer) having at least two ethylenically unsaturated bonds. The polyfunctional polymerizable compound having at least two ethylenically unsaturated bonds is not particularly limited as long as it is radically polymerizable. For example, a compound having two ethylenically unsaturated bonds in the molecule, an intramolecular And any of compounds having three or more ethylenically unsaturated bonds may be used, and a plurality of them may be used in combination.

  Specific examples of the compound having two ethylenic unsaturated bonds in the molecule include a bisenol A-based di (meth) acrylate compound, a hydrogenated bisphenol A-based di (meth) acrylate compound, and a di- (meth) acrylate having a fluorene skeleton. ) Acrylate, di (meth) acrylate compound having urethane bond in molecule, polyalkylene glycol di (meth) acrylate compound, trimethylolpropane di (meth) acrylate, 1,6-hexanediol diacrylate; tricyclodecane dimethanol Examples include di (meth) acrylate compounds having an alicyclic hydrocarbon group in the molecule such as di (meth) acrylate.

  2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane, a compound having two ethylenic unsaturated bonds in its molecule, is BPE-500 (trade name of Shin-Nakamura Chemical Co., Ltd.) Alternatively, as FA-321M (trade name, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is BPE-1300 (manufactured by Shin-Nakamura Chemical Co., Ltd.) As a trade name), 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane is 9,9-bis [4 as a biscoat # 700 (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.). -(2-acryloyloxyethoxy) phenyl] fluorene is a tricyclodecanedimethanol diacrylate as A-BP (Shin-Nakamura Chemical Co., Ltd. product, trade name). Tricyclodecanedimethanol dimethacrylate as A-DCP (Shin-Nakamura Chemical Co., Ltd. product name) or Kayarad R-684 (Nippon Kayaku Co., Ltd. product name) is DCP (Shin-Nakamura Chemical Chemical Commercially available as Co., Ltd., trade name).

  The compounds having two ethylenic unsaturated bonds in the molecule may be used alone or in combination of two or more.

  As the compound having three or more ethylenic unsaturated bonds in the molecule, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate (the total number of oxyethylene groups is 1 to 5) ), PO-modified trimethylolpropane tri (meth) acrylate, EO and PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) ) Triacrylic cyanurates such as acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tris (2-acryloxyethyl) isocyanurate Etc. The. These can be used alone or in combination of two or more.

  The content of the polymerizable compound (C) in the photosensitive composition of the present invention is not particularly limited, but is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, with respect to 100 parts by mass of (A) acrylic resin. The amount is particularly preferably 30 parts by mass or more, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and particularly preferably 150 parts by mass or less. When the content is 10 parts by mass or more, sufficient sensitivity and resolution tend to be obtained, and when the content is 300 parts by mass or less, the formability of the film tends to be good, and a good film shape is obtained. It tends to be easy to

(Photopolymerization initiator)
The photopolymerization initiator is a compound which is activated by various actinic rays such as ultraviolet rays to initiate polymerization. Although not particularly limited, for example, the following can be used. That is, 2-methyl-4'-methylthio-2-morpholinopropiophenone (IRGACURE 907: manufactured by Ciba Specialty Chemicals), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone- 1 (Irgacure 369: manufactured by Ciba Specialty Chemicals), 1- [4- (phenylthio) -2- (O-benzoyloxime)] (Irgacure OXE-01: manufactured by Ciba Specialty Chemicals), 1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyl oxime) (IRGACURE OXE-02: manufactured by Ciba Specialty Chemicals) can be used.

  Other photopolymerization initiators include quinones such as 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, aromatic ketones such as benzophenone, benzoin, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether Acridine compounds, such as 9-phenylacridine, benzyl dimethyl ketal, benzyl diethyl ketal, 2,4-trichloromethyl- (4 ′ ′-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4′-methoxy) Triazines such as naphthyl) -6-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl- (4′-methoxystyryl) -6-triazine, 2-methyl-1 -(4-methylthiophenyl 2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2- Ndidyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphos And fin oxide, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyl oxime)] and the like.

  For example, there is also a combination of thioxanthones such as thioxanthone, 2,4-diethyl thioxanthone, 2-chlorothioxanthone and the like, and a tertiary amine compound such as a dimethylaminobenzoic acid alkyl ester compound. There are also oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime.

  These photopolymerization initiators can be used in combination of 2 or more types. In particular, 2-methyl-4'-methylthio-2-morpholinopropiophenone (IRGACURE 907: manufactured by Ciba Specialty Chemicals), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone- 1 (Irgacure 369: manufactured by Ciba Specialty Chemicals), 1- [4- (phenylthio) -2- (O-benzoyloxime)] (Irgacure OXE-01: manufactured by Ciba Specialty Chemicals), 1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (IRGACURE OXE-02: manufactured by Ciba Specialty Chemicals) alone or other photopolymerization initiator It is particularly preferred to use in combination with

  The proportion of the photopolymerization initiator contained in the photosensitive composition of the present invention is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, with respect to 100 parts by mass of (A) acrylic resin, preferably Is 40 parts by mass or less, more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less. If this content is less than 2 parts by mass, it tends to be difficult to obtain sufficient sensitivity. In addition, if this proportion exceeds 40 parts by mass, fog due to diffraction of light passing through the photomask at the time of exposure tends to be generated, and as a result, resolution may be deteriorated.

(Other additives)
The photosensitive composition of the present invention can further contain various additives. Additives include dyes, light color formers, thermal color formation inhibitors, plasticizers, hydrogen donors, color formers, pigments, fillers, antifoaming agents, flame retardants, adhesion promoters, leveling agents, peeling accelerators, Antioxidants, perfumes, imaging agents, thermal crosslinking agents and the like can be mentioned.

(solvent)
The photosensitive composition of the present invention can optionally contain a solvent. The solvent is not particularly limited, and can be appropriately selected from commonly used solvents. Specifically, for example, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, glycol acetates such as methyl cellosolve and ethyl cellosolve, hydrocarbons such as toluene, and aprotons such as N, N-dimethylformamide Polar solvents, ether acetates such as propylene glycol monomethyl ether 2-acetate, methyl methoxypropionate and the like, cyclic ketones such as cyclohexanenone and the like can be mentioned.

  These solvents are used alone or as a mixed solvent of two or more kinds. Although content of a solvent is suitably selected according to the objective, it can be set as the solution of about 30-60 mass% as solid content, for example. In addition, solid content is the total amount of the non-volatile component of a photosensitive composition.

  The photosensitive composition of the present invention can be applied to the surface of a support film, a treated substrate such as ITO or metal wiring, a substrate such as a metal plate or glass, and cured to form a cured film. . Of course, it is also possible as general method to pattern by exposure-development using a photomask etc.

  As the support film, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used. Examples of the metal plate include silver, aluminum, molybdenum, copper, a copper-based alloy, an iron-based alloy such as nickel, chromium, iron, and stainless steel.

  The photosensitive composition of the present invention is, as described above, usually applied to a substrate, prebaked if necessary, dried, exposed and cured, optionally patterned, optionally developed. Curing can be completed by post-baking to form a cured film more closely attached to the substrate. In such a film forming process, post-baking usually needs to be performed at 200 ° C. or higher when adhering to a conventional base material, and below 200 ° C., for example, peeling from the base material is observed in the cross-cut peeling test Adhesion to the substrate is not sufficient. However, the photosensitive composition of the present invention can be post-baked at 180 ° C. or less, for example, 150 ° C. or less, and if it is 120 ° C. or more, sufficient adhesion to the substrate can be obtained.

  For example, when using a polymer film with low heat resistance as the substrate, or when performing film formation treatment in an on-cell manner, post-baking is preferably performed at 180 ° C. or less, more preferably 150 ° C. or less.

  Although the thickness of the cured film formed changes with the uses, it is preferable that it is about 0.1 micrometer-100 micrometers in thickness after drying. The surface (surface) opposite to the surface facing the support of the cured film may be covered with a protective film. As a protective film, polymer films, such as polyethylene and a polypropylene, etc. are mentioned.

  Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the examples.

Synthesis Example 1: Synthesis of Silane Compound B-1 100 parts by mass of isocyanate propyltriethoxysilane (KBM 9007, manufactured by Shin-Etsu Chemical Co., Ltd.) in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer To a liquid mixture containing 485 parts by mass of N-methylpyrrolidone (NMP), 108 parts by mass of ureidopropyltrimethoxysilane (T1915, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise with stirring. The mixture was then raised to 65 ° C. and allowed to react for 2 days while maintaining this temperature. Completion of the reaction confirmed the disappearance of the isocyanate peak using IR.
The solid content concentration of the obtained solution was 30.0 mass%.

By the above reaction, a compound B-1 represented by the following formula was obtained. FIG. 1 is a chart of IR chart confirming the completion of the reaction of Synthesis Example 1. Thereby, it was confirmed that the isocyanate group disappeared. FIG. 2 is a chart of NMR of the reaction product of Synthesis Example 1.

Synthesis Example 2 Synthesis of Silane Compound B-2 In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 100 parts by mass of isocyanate propyltriethoxysilane (KBM 9007, manufactured by Shin-Etsu Chemical Co., Ltd.) To a liquid mixture containing 336 parts by mass of N-methylpyrrolidone (NMP), 44 parts by mass of trimethylsilanol (LS-310, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise with stirring. The mixture was then raised to 65 ° C. and allowed to react for 2 hours while maintaining this temperature. Completion of the reaction confirmed the disappearance of the isocyanate peak using IR.
The solid content concentration of the obtained solution was 30% by mass.

By the above reaction, a compound B-2 represented by the following formula was obtained.

Synthesis Example 3 Synthesis of Silane Compound B-3 100 parts by mass of isocyanate propyltriethoxysilane (KBM 9007, manufactured by Shin-Etsu Chemical Co., Ltd.) in a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer To a liquid mixture containing 445 parts by mass of N-methylpyrrolidone (NMP), 91 parts by mass of ureidopropyltrimethoxysilane (T1915, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise with stirring. The mixture was then raised to 65 ° C. and allowed to react for 2 days while maintaining this temperature. Completion of the reaction confirmed the disappearance of the isocyanate peak using IR.
The solid content concentration of the obtained solution was 30% by mass.

By the above reaction, a compound B-3 represented by the following formula was obtained.

Synthesis Example 4 Synthesis of Acrylic Resin A-1 Adamantyl methacrylate (ADMA) (adamantate M-104, manufactured by Idemitsu Kosan Co., Ltd.) in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen blow-in pipe, and a thermometer. 30 parts by mass, 50 parts by mass of glycidyl methacrylate, 20 parts by mass of methacrylic acid, and 300 parts by mass of cyclohexanone were charged and dissolved while blowing in nitrogen. After heating to 65 ° C., 5 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) (ADVN) was added, and polymerization was maintained at 65 ° C. for 8 hours. The obtained copolymer (acrylic resin A-1) was measured by gel permeation chromatography, and the weight average molecular weight was 12,000 in terms of polystyrene, and the solid content acid value was 82.

Synthesis Example 5 Synthesis of Acrylic Resin A-2 A copolymer was prepared in the same manner as in Synthesis Example 4 except that glycidyl methacrylate was changed to 3,4-epoxycyclohexylmethyl methacrylate (Cyclomer M-100, manufactured by Daicel Co., Ltd.) A united body (acrylic resin A-2) was obtained. The polymerization average molecular weight by gel permeation chromatography of the obtained acrylic resin A-2 was 12,000 in terms of polystyrene, and the solid content acid value was 80.

Synthesis Example 6 Synthesis of Acrylic Resin A-3 A copolymer (acrylic resin) was prepared in the same manner as in Synthesis Example 4 except that ADMA was changed to dicyclopentanyl methacrylate (FA-513M, manufactured by Hitachi Chemical Co., Ltd.). A-3) was obtained. The polymerization average molecular weight by gel permeation chromatography of the obtained acrylic resin A-3 was 10,000 in terms of polystyrene, and the solid content acid value was 83.

Synthesis Example 7 Synthesis of Acrylic Resin A-4 The same as Synthesis Example 4 except that ADMA was changed to FA-513M, glycidyl methacrylate was changed to 40 parts by mass, and 10 parts by mass of 2-hydroxyethyl methacrylate was added. Thus, a copolymer (acrylic resin A-4) was obtained. The polymerization average molecular weight by gel permeation chromatography of the obtained acrylic resin A-4 was 12,000 in terms of polystyrene, and the solid content acid value was 81.

Examples 1 to 9 and Comparative Example 1
In the composition described in Table 1, using cyclohexanone as a solvent, an acrylic resin, a silane coupling agent, a polymerizable compound, a photopolymerization initiator, and a surface control agent were mixed to obtain a photosensitive composition.

The details of each component used are as follows.
<(A) Acrylic resin>
A-1 to A-4 are those obtained in Synthesis Examples 4 to 7, respectively.
<(B) Silane coupling agent>
B-1: Compound obtained in Synthesis Example 1 B-4: trimethoxysilylpropylsuccinic anhydride (trade name: X-12967C, manufactured by Shin-Etsu Chemical Co., Ltd.)
<(C) polymerizable compound>
DPHA: dipentaerythritol hexaacrylate (trade name: ALONIX M-402, manufactured by Toagosei Co., Ltd.)
-V # 700: Viscote # 700 (Osaka Organic Chemical Industry Co., Ltd. product name)
V # 802: Viscote # 802 (Osaka Organic Chemical Industry Co., Ltd. product name)
A9300: A9300 (Shin-Nakamura Chemical Co., Ltd. product name): Ethoxylated isocyanuric acid triacrylate <photoinitiator>
OXE-01: 1- [4- (phenylthio) -2- (O-benzoyloxime)] (IRGACURE OXE-01: manufactured by Ciba Specialty Chemicals)
<Surface modifier>
-FZ-2122 (made by Toray Dow Corning, trade name): silicone oil-KF-351A (made by Shin-Etsu Chemical Co., Ltd., trade name): modified silicone oil

Examples 10 to 18 and Comparative Example 2
As Examples 10 to 18 and Comparative Example 2, the photosensitive compositions of Examples 1 to 9 and Comparative Example 1 are respectively spin coated on each substrate to a final film thickness of approximately 2 μm, Prebaked on a hot plate at 90 ° C. for 120 seconds. The test substrate was exposed to ultraviolet light throughout. The exposure dose was about 100 mJ / cm ² . Next, it developed for 60 seconds using the developing solution of 0.1 mass% potassium hydroxide aqueous solution. Further, post-baking was carried out on a hot plate at 150 ° C. for 30 minutes to obtain a cured film in close contact with the substrate. The hardness of each of the obtained cured films was good at a pencil hardness of H to 3H.

Test Example 1
Using the substrates to which the cured films obtained in Examples 10 to 18 and Comparative Example 2 in close contact as test substrates, the transparency, the adhesion to the substrate, and the high temperature and high humidity adhesion were measured. Transparency, substrate adhesion and high temperature / high humidity adhesion were measured under the following conditions.

(A) Evaluation of Transparency The transmittance at 380 to 780 nm of the obtained film was measured using a UV-visible spectrophotometer (V-660, manufactured by JASCO Corporation). Evaluation of transparency was judged as follows.
○: transmittance 98% or more Δ: transmittance 95 to 97%
X: Transmittance of 94% or less The results are shown in Table 2.

(B) Evaluation of Substrate Adhesion The evaluation test of the substrate adhesion was conducted according to JIS K5600-5-6. Specifically, the surface of the coating film of the obtained substrate is cut with a cutter at intervals of 1 mm with a cutter, a cellophane tape is attached to this surface, strongly rubbed with a nail and brought into close contact, and then the cellophane tape is peeled off at once. The adhesion was observed with The evaluation of adhesion was judged as follows.
◎: no tape peeling (adhesion ratio 100%).
○: Tape peeling at a small part (adhesion rate 90 to 99%)
Δ: Partial tape peeling (adhesion ratio 30 to 89%).
X: Tape peeling occurred in most parts (adhesion ratio 0 to 29%).
The results are shown in Table 2.

(C) Evaluation of high temperature and high humidity adhesion (pressure cooker (PCT) test)
The obtained test substrate was placed in a pressure cooker tester with the cured film surface facing up, and maintained at 120 ° C. for 2 minutes at 2 atm. Then, the board | substrate adhesiveness test was done according to JISK5600-5-6 like evaluation of the said (b) board | substrate adhesiveness.
◎: no tape peeling (adhesion ratio 100%).
○: Tape peeling at a small part (adhesion rate 90 to 99%)
Δ: Partial tape peeling (adhesion ratio 30 to 89%).
X: Tape peeling occurred in most parts (adhesion ratio 0 to 29%).
The results are shown in Table 2.

  In all of the tested Examples and Comparative Examples, a cured film having high transparency was obtained, and the adhesion to the substrate was also good. On the other hand, with respect to the adhesion after the high temperature and high humidity treatment, sufficient adhesion to various substrates was obtained in the example, but in the comparative example 2, the result was very poor to the glass substrate. Thereby, the photosensitive composition of the present invention can obtain sufficient adhesion to various substrates after the high temperature and high humidity treatment even when the film forming treatment is performed on the substrate at a low temperature. In the case where a silane coupling agent which is essential in the present invention is not used, it is understood that sufficient adhesion to a substrate after high temperature and high humidity treatment can not be obtained.

Test example 2
The adhesion after the drug resistance test was evaluated using the substrates to which the cured films obtained in Examples 10 to 18 and Comparative Example 2 were in close contact as test substrates. A 5.0% KOH aqueous solution (KOH), a 30% organic amine solution (organic amine), and a mixed solution of phosphoric acid and nitric acid (acid solution) are used as a drug solution, and the test substrate is 45 for KOH. C. for 3 minutes, organic amines for 3 minutes at 75.degree. C., and acid solutions for 100 seconds at 40.degree. C., and then the treated substrate was observed with a microscope to observe film peeling and the like. The evaluation of adhesion after drug resistance test was judged as follows.
◎: no peeling (adhesion ratio 100%).
:: Partially peeled off (adhesion ratio 90 to 99%)
Δ: Partially peeled off (adhesion ratio 30 to 89%).
X: Peeling in most part (adhesion ratio 0 to 29%).
The results are shown in Table 3.

  From Table 3, compared with Comparative Example 2, the photosensitive compositions of the present invention of Examples 10 to 18 were all good in adhesion after the drug resistance test for various substrates. Further, in Example 13 in which the silane compound was used in combination, the substrate adhesion was further improved with respect to the ITO after the organic amine treatment and the ITO after the acid solution treatment than in Example 12 in which a single silane compound was used.

  From these results, it can be seen that the photosensitive composition of the present invention is also very excellent in adhesion after drug resistance test. Further, in comparison with Example 12, in Example 13, a silicon compound having an isocyanate represented by the general formula (1) as a silane coupling agent of the component (B) and a table of the following general formula (2) By using the silane compound represented by General formula (3) together with the silane compound which is a reaction product with the silicon compound to be produced, it is understood that the substrate adhesion to ITO is further improved.

Claims (6)

A photosensitive composition comprising (A) an acrylic resin, (B) a silane coupling agent, and (C) a polymerizable compound, wherein the (B) silane coupling agent is represented by the following general formula (1): A photosensitive composition which is a silane compound which is a reaction product of a silicon compound having an isocyanate and a silicon compound represented by the following general formula (2).

(Wherein, R ^{1 to} R ³ may be the same or different, all or at least one is an alkoxy group having 1 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms). Is a substituted or unsubstituted linear or branched alkylene group having 2 to 18 carbon atoms, and may contain a divalent or trivalent linking group, and q is an integer of 1 to 3. r is an integer of 1 to 3.)

(Wherein, R ^{4 to} R ⁶ may be the same or different, and are an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms. B is a substituted or unsubstituted carbon number 2 A linear or branched alkylene group, which may contain a divalent linking group, p is an integer of 0 or 1. X is O, NH, NH-CO-NH, It is S. s is an integer of 1 to 3. t is an integer of 1 to 3. However, in the case of p = 0, s = 1 and t = 1.) The photosensitive composition according to claim 1, wherein the (A) acrylic resin has an alicyclic unit, an epoxy unit and a carboxylic acid unit. The photosensitive composition according to any one of claims 1 or 2, wherein the (B) silane coupling agent further contains a silane compound represented by the following general formula (3).

[Wherein, R ^{12 to} R ¹⁴ may be the same or different and are hydroxy or an alkoxy group having 1 to 5 carbon atoms, and R ¹⁵ is a carboxylic acid anhydride group, —CHR ¹⁶ (CH ₂ ) _u COOH or -CH (COOH) (CH ₂ ) _u R ¹⁶ (wherein, R ¹⁶ is a carboxylic acid group or a carboxylic acid ester group, u is an integer of 0 to 3), and D is a substituted or unsubstituted Is a linear or branched alkylene group having 2 to 10 carbon atoms, or a substituted or unsubstituted alkylene group having at least one double bond of a linear or branched chain having 2 to 10 carbon atoms. ] The silane compound which is a reaction product of the compound represented by the general formula (1) and the compound represented by the general formula (2) is a compound represented by the following formula (4) or (5) The photosensitive composition of any one of Claims 1-3.

(Wherein, R ^{1 to} R ³ may be the same or different, all or at least one is an alkoxy group having 1 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms. ^{4 to} R ^{6, which} may be the same or different, are an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms.A is a substituted or unsubstituted straight chain having 2 to 18 carbon atoms. Or a branched alkylene group which may contain a divalent or trivalent linking group B is a substituted or unsubstituted linear or branched alkylene group having 2 to 15 carbon atoms, 2 X may be O, NH, NH-CO-NH or S. p is an integer of 0 or 1. q is an integer of 1 to 3. r is an integer of 1 to 3. s is an integer of 1 to 3. t is an integer of 1 to 3. ) In the linear or branched alkylene group having 2 to 18 carbon atoms having a linking group represented by A, the divalent or trivalent linking group is at least selected from the group consisting of the following formula [A1] It is one,
In the linear or branched alkylene group having 2 to 15 carbon atoms having a linking group, represented by B, the divalent linking group is at least one selected from the group consisting of the following formula [B1] The photosensitive composition of any one of Claims 1-4.

[R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an aryl group of 6 to 12 carbon atoms, -CH =,

(R ⁹ and R ^{10 each} represent an alkyl group of 1 to 5 carbon atoms, m 3 is an integer of 1 to 5),

(M4 is an integer of 1 to 5),

(R ¹¹ is an alkyl group of 1 to 5 carbon atoms) or a monovalent or divalent group represented by a cycloalkane of 3 to 6 carbon atoms which may have a substituent. When one of R ^{7 and} R ⁸ is a divalent group, the other is a hydrogen atom or a monovalent group. ],

A substituted or unsubstituted cycloalkane having 3 to 6 carbon atoms, having at least two bonds

The cured film which hardens the photosensitive composition of any one of Claims 1-5.

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