JP2008070543A - Photosensitive composition and display element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition which exhibits good compression property when formed into spacers of a display element. <P>SOLUTION: The photosensitive composition contains a polyester-polyamic acid (A) obtained by bringing an acid anhydride (a1), a polyamine compound (a2) and a hydroxy compound (a3) into a reaction, a compound (B) having a polymerizable double bond and a photopolymerization initiator (C), wherein the acid anhydride (a1) contains a copolymer of a polymerizable monomer having an acid anhydride group and another radical polymerizable monomer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photosensitive composition, a transparent film or spacer produced from the composition, and a display element including the transparent film or the spacer, and is particularly suitable for production of liquid crystal display elements and EL display elements.

  Patterned transparent films are used as many parts constituting liquid crystal display elements such as spacers, insulating films, protective films, etc., and many photosensitive compositions have been proposed for this purpose ( For example, see Patent Document 1: Japanese Patent Application Laid-Open No. 2004-287232). Particularly in recent years, the demand for high-definition liquid crystal displays and mobile phone displays has increased, and as a result, small patterns with a diameter of 10 μm or less have been required for spacer applications.

  However, the proximity exposure machine generally used in the production line of liquid crystal displays has the disadvantage that the pattern size becomes larger than the mask size (pattern fatness) due to poor parallelism of light. Therefore, it is difficult to form a small pattern. Further, this tendency is more remarkable in a highly sensitive photosensitive composition, and it has been a very difficult problem to achieve both high sensitivity and a small pattern.

  In addition, it has become clear that the degree of pattern shrinkage when a load is applied and the restoration rate when the load is removed (hereinafter, this characteristic is referred to as compression characteristic) are largely related to defects in liquid crystal displays. . For this reason, a material that is well shrunk and has a high restoration rate, that is, a good compression property has been demanded.

  As spacer materials so far, compositions mainly composed of unsaturated carboxylic acid, acrylic, etc. have been proposed (for example, Patent Document 1: Japanese Patent Laid-Open No. 2004-287232, Patent Document 2: Japanese Patent Laid-Open No. 2006-126977). Patent Document 3: Japanese Patent Application Laid-Open No. 2004-264384). For example, a photosensitive resin composition mainly composed of an ethylenically unsaturated carboxylic acid has been proposed (see Patent Document 2: Japanese Patent Application Laid-Open No. 2006-12697). However, this composition has a high recovery rate but is hard, and therefore lacks the properties of shrinking well required as a spacer material.

  In addition, a photosensitive resin composition using a polyamic acid obtained from a tetracarboxylic dianhydride, a diol, and a diamine has been proposed in place of a conventional acrylic-based composition (for example, patent documents). 4: Refer to JP 2005-308874 A). However, since the photospacer obtained using this composition has low compression characteristics, it is not possible to obtain a spacer that sufficiently satisfies the requirements.

JP 2004-287232 A Japanese Patent Laid-Open No. 2006-126397 JP 2004-264384 A JP 2005-308874 A

  From the above situation, it has high sensitivity, satisfies the characteristics generally required for polymer compositions such as coating uniformity, developability, heat resistance, storage stability, etc., and is used in proximity exposure. There is a need for a photosensitive composition that can form a pattern that matches the size, and that has good compression characteristics when used as a spacer or transparent film for high-definition liquid crystal displays and mobile phone displays, for example. ing.

  The present inventors have successfully balanced the solubility of the polyester-polyamic acid in an alkaline developer and the curing reaction of the photopolymerization initiator and the compound having a polymerizable double bond that are generated by irradiation with ultraviolet rays. The present inventors have found that a pattern having a size corresponding to the mask size can be obtained by eliminating pattern weighting.

  Moreover, in order to express this balance, it discovered that it was important to use the polyester-polyamic acid manufactured using the specific material. That is, the present inventors obtained a polyester-polyamic acid (A), a compound (B) having a polymerizable double bond, a photopolymerization initiator (C), and optionally a compound (D) having a thermally crosslinkable functional group. By specifying the structure of the polyester-polyamic acid (A) in the photosensitive composition to be contained, it is possible to form a relatively small pattern with relatively high sensitivity and to obtain further excellent compression characteristics. The present invention was completed based on the finding and this finding.

  The present invention provides the following photosensitive composition, a transparent film produced using the same, a spacer, and a display device including these. The present invention comprises the following. In addition, in this specification, in order to show both acrylic acid and methacrylic acid, it may describe as "(meth) acrylic acid".

[1] Polyester-polyamic acid (A) obtained by reacting acid anhydride (a1), polyvalent amine compound (a2) and hydroxy compound (a3), compound (B) having a polymerizable double bond, And a photosensitive composition containing a photopolymerization initiator (C),
The photosensitive composition in which the said acid anhydride (a1) contains the copolymer of the polymerizable monomer which has an acid anhydride group, and another radically polymerizable monomer.

[2] The acid anhydride (a1) is a copolymer of maleic anhydride and another radical polymerizable monomer,
The polyvalent amine compound (a2) is a diamine;
The hydroxy compound (a3) is a monovalent or divalent alcohol compound;
The compound (B) having a polymerizable double bond contains a polyfunctional acrylate,
The photosensitive composition as described in said [1].

[3] The other radical polymerizable monomer in the acid anhydride (a1) is alkyl (meth) acrylate or styrene,
The polyvalent amine compound (a2) is a siloxane diamine,
The hydroxy compound (a3) is methanol, ethanol, 1-propanol, 2-propanol, 1,4-butanediol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, allyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, tetrahydrofurfuryl alcohol Caprolactone adduct, cyclohexanol, 3-cyclohexene-1-methanol, benzyl alcohol, 1- (2-hydroxyethyl) 2-pyrrolidone, ethylene glycol monoalkyl ether, and a diethylene glycol monoalkyl ether, propylene glycol monoalkyl ethers, and one or more selected from the group consisting of dipropylene glycol monoalkyl ethers,
The compound (B) having a polymerizable double bond is one selected from the group consisting of pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, urethane (meth) acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate. Containing 50% by weight or more based on the total weight of the compound (B) having a polymerizable double bond,
The photopolymerization initiator (C) is 3,3′-di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4′-di (methoxycarbonyl) -4,3. '-Di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2, -Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and 1,2- One or more selected from the group consisting of octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime) is used as a photopolymerization initiator (C ) 20% by weight or more based on the total weight of
The photosensitive composition as described in said [2].

[4] The above [1], wherein the hydroxy compound (a3) is one or more selected from the group consisting of 1,4-butanediol, benzyl alcohol, diethylene glycol monoalkyl ether, and dipropylene glycol monoalkyl ether. The photosensitive composition as described in any one of [3].

[5] The polyester-polyamic acid (A) is 30 to 90% by weight of the acid anhydride (a1) and 1 to 1 of the polyvalent amine compound (a2) based on the total weight of the polyester-polyamic acid (A). The photosensitive composition as described in any one of [1] to [4] above, obtained by reacting 50% by weight and 10 to 60% by weight of the hydroxy compound (a3).

[6] The photosensitive composition contains 20 to 300 parts by weight of a compound (B) having a polymerizable double bond and 100% by weight of a polyester-polyamic acid (A), and a photopolymerization initiator (C ) In an amount of 0.5 to 50 parts by weight, according to any one of the above [1] to [5].

[7] The photosensitive composition according to any one of [1] to [6], further including a compound (D) having a thermally crosslinkable functional group.

[8] The compound (D) having a thermally crosslinkable functional group is a radically polymerizable monomer having a thermally crosslinkable functional group, or a radically polymerizable monomer having a thermally crosslinkable functional group and another radically polymerizable monomer. The photosensitive composition as described in said [7] containing a copolymer.

[9] The photosensitive composition according to [7], wherein the thermally crosslinkable functional group is at least one selected from the group consisting of oxetanyl and oxiranyl.

[10] The radically polymerizable monomer having a thermally crosslinkable functional group is composed of glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3-ethyl-3- (meth) acryloxymethyloxetane. The photosensitive composition as described in said [8] which is 1 or more types chosen from a group.

[11] The other radical polymerizable monomer in the compound (D) having the thermally crosslinkable functional group is (meth) acrylic acid and γ-methacryloxypropylhepta (trifluoropropyl) -T8-silsesquioxane. The photosensitive composition as described in [8] above, which is at least one selected from the group consisting of:

（式（１）において、Ｒ¹が−（ＣＨ₂）_l−（ｌは２〜１０の整数）であり、Ｒ³が−（ＣＨ₂）_m−（ｍは２〜１０の整数）であり、Ｒ²がメチルであり、ｎが２〜５０の整数である）で表される化合物からなる群から選ばれる１種以上であり、
前記ヒドロキシ化合物（ａ３）が、ジ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エチルエーテル、ジプロピレングリコールモノメチルエーテル、およびジプロピレングリコールモノエチルエーテルからなる群から選ばれる１種以上であり、
前記重合性二重結合を有する化合物（Ｂ）が、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレート、およびウレタン（メタ）アクリレートからなる群から選ばれる１種以上を、重合性二重結合を有する化合物（Ｂ）の全重量に対して５０重量％以上含有し、
前記光重合開始剤（Ｃ）が、３，３’−ジ（メトキシカルボニル）−４，４’−ジ（ｔ−ブチルペルオキシカルボニル）ベンゾフェノン、３，４’−ジ（メトキシカルボニル）−４，３’−ジ（ｔ−ブチルペルオキシカルボニル）ベンゾフェノン、４，４’−ジ（メトキシカルボニル）−３，３’−ジ（ｔ−ブチルペルオキシカルボニル）ベンゾフェノン、および４，４’−ビス（ジエチルアミノ）ベンゾフェノンからなる群から選ばれる１種以上を、光重合開始剤（Ｃ）の全重量に対して２０重量％以上含有し、
前記熱架橋性官能基を有する化合物（Ｄ）が、グリシジル（メタ）アクリレートとγ−メタクリロキシプロピルヘプタ（トリフルオロプロピル）−Ｔ８−シルセスキオキサンとの共重合体である、感光性組成物。 [12] Polyester-polyamic acid (A) obtained by reacting acid anhydride (a1), polyvalent amine compound (a2) and hydroxy compound (a3), compound (B) having a polymerizable double bond, A photosensitive composition containing a photopolymerization initiator (C) and a compound (D) having a thermally crosslinkable functional group,
The acid anhydride (a1) is a styrene-maleic anhydride copolymer, or a mixture of a styrene-maleic anhydride copolymer and another acid anhydride,
The polyvalent amine compound (a2) is represented by the following general formula (1)

In (Equation (1), R ¹ is _{- (CH 2) l - (} l is an integer of 2 to 10), R ³ is _{- (CH 2) m - (} m is an integer) from 2 to 10 , R ² is methyl, and n is an integer of 2 to 50).
The hydroxy compound (a3) is at least one selected from the group consisting of diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether;
The compound having a polymerizable double bond, wherein the compound (B) having a polymerizable double bond is one or more selected from the group consisting of pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and urethane (meth) acrylate. Containing at least 50% by weight based on the total weight of (B),
The photopolymerization initiator (C) is 3,3′-di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4′-di (methoxycarbonyl) -4,3. From '-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, and 4,4'-bis (diethylamino) benzophenone One or more selected from the group consisting of 20% by weight or more based on the total weight of the photopolymerization initiator (C),
The photosensitive composition whose compound (D) which has the said heat crosslinkable functional group is a copolymer of glycidyl (meth) acrylate and (gamma) -methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane. .

[13] The photosensitive composition contains 20 to 300 parts by weight of the compound (B) having a polymerizable double bond and 100% by weight of the photopolymerization initiator (C) with respect to 100 parts by weight of the polyester-polyamic acid (A). The photosensitive composition as described in any one of [7] to [12] above, containing 0.5 to 50 parts by weight and 5 to 200 parts by weight of the compound (D) having a thermally crosslinkable functional group.

[14] A transparent film produced using the photosensitive composition according to any one of [1] to [13].

[15] A spacer produced using the photosensitive composition according to any one of [1] to [13].

[16] A color filter protective film produced using the photosensitive composition according to any one of [1] to [13].

[17] A display device comprising the transparent film according to [14].

[18] A display device comprising the spacer according to [15].

[19] A display element comprising the protective film according to [16].

  According to the photosensitive composition according to a preferred embodiment of the present invention, it has high sensitivity and satisfies characteristics generally required for a polymer composition such as coating uniformity, developability, heat resistance, and storage stability. In addition, it is possible to form a pattern having a size corresponding to the mask size in proximity exposure. Moreover, according to the photosensitive composition concerning the preferable aspect of this invention, it can also be equipped with a favorable compression characteristic. Therefore, it is possible to provide an optimum photosensitive composition for use as a spacer for a high-definition liquid crystal display or a mobile phone display. Further, by using the spacer, defects such as light leakage are reduced, and a high-definition liquid crystal panel can be manufactured with a high yield. Furthermore, the contact angle with respect to a glass substrate is large, and it is useful also as photosensitive ink for inkjets.

  Hereinafter, the photosensitive composition of the present invention, the transparent film produced using the photosensitive composition, the spacer, and the display element will be described in detail.

1 Photosensitive composition of the present invention The present invention contains polyester-polyamic acid (A), a compound (B) having a polymerizable double bond, and a photopolymerization initiator (C) as essential components, and optionally heat. It is a photosensitive composition containing the compound (D) which has a crosslinkable functional group.

  The present invention provides a good balance between the solubility of the polyester-polyamic acid in an alkali developer and the curing reaction of a photopolymerization initiator and a compound having a polymerizable double bond generated by irradiation with ultraviolet rays. A pattern having a size corresponding to the mask size can be obtained by eliminating the fatness. In order to develop this balance, it is important that the polyester-polyamic acid has a specific structure.

1.1 Polyester-polyamic acid (A)
The polyester-polyamic acid (A) is obtained by reacting an acid anhydride (a1), a polyvalent amine compound (a2) and a hydroxy compound (a3). The acid anhydride (a1) contains a copolymer of a polymerizable monomer having an acid anhydride group and another polymerizable monomer.

The constituent acid anhydride (a1) of the polyester-polyamic acid (A) contains a copolymer of a polymerizable monomer having an acid anhydride group and another radical polymerizable monomer.

  Examples of the polymerizable monomer having an acid anhydride group include maleic anhydride, itaconic anhydride, and citraconic anhydride.

  Other radical polymerizable monomers are not particularly limited as long as they are radical polymerizable monomers. For example, α-ethylene, propylene, styrene, α-methylstyrene, vinyl toluene, vinyl acetate, allyl acetate, acrylic acid, methacrylic acid 2-alkylpropenoic acid, methyl acrylate, ethyl acrylate, benzyl acrylate, hydroxyethyl acrylate, alkoxy polyethylene glycol acrylate, acryloyl morpholine, methyl methacrylate, ethyl methacrylate, benzyl methacrylate, hydroxy ethyl methacrylate, alkoxy polyethylene glycol methacrylate, methacryloyl morpholine, acrylamide N-alkyl acrylamide, dialkyl acrylamide, methacrylamide, N- Alkylmethacrylamide, dialkylmethacrylamide, 4-vinylpyridine, acrylonitrile, N-vinylpyrrolidone, N-vinylimidazole, butadiene, isoprene, divinylbenzene, pentaerythritol tetramethacrylate, diallyl phthalate, 2- (2-hydroxy-5- And methacryloxyethylphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole, aromatic tetracarboxylic acid, and aliphatic tetracarboxylic acid.

  Among these, a styrene-maleic anhydride copolymer, or a mixture of a styrene-maleic anhydride copolymer and another acid anhydride is preferable because of good compression characteristics.

  The polyvalent amine compound (a2) is not particularly limited as long as it is a polyvalent amine compound, and examples thereof include diamines, triamines, tetramines, pentamines, and hexamines.

Among these, diamines will be described. The diamines are not particularly limited as long as they have two amino groups. For example, NH ₂ —R ² —NH ₂ (wherein R ² represents A compound having 2 to 100 carbon atoms independently). Specific examples of this compound include compounds represented by the following general formulas (II) to (VIII).

［式（II）及び（IV）中、
Ａ₁は、−（ＣＨ₂）ｍ−であり、ここでｍは１〜６の整数であり、
式（VI）〜（VIII）中、
Ａ₁は、単結合、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ２−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｃ（ＣＨ₃）₂−、−Ｃ（ＣＦ₃）₂−、−（ＣＨ₂）ｍ−、−Ｏ−（ＣＨ₂）ｍ−Ｏ−、−Ｓ−（ＣＨ₂）ｍ−Ｓ−であり、ここでｍは１〜６の整数であり、
Ａ₂は、単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ₃）₂−、−Ｃ（ＣＦ₃）₂−または炭素数１〜３のアルキレンであり、
シクロヘキサン環またはベンゼン環に結合している水素は、−Ｆ、−ＣＨ₃と置き換えられていてもよい。］

[In the formulas (II) and (IV),
A ₁ is — (CH ₂ ) m —, where m is an integer of 1 to 6,
In formulas (VI) to (VIII),
A ₁ is a single bond, —O—, —S—, —S—S—, —SO 2 —, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF _{3) 2 -, - (CH} 2) m -, - O- (CH 2) m-O -, - S- (CH 2) m-S- where m is located at an integer from 1 to 6 ,
A ₂ is a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ — or alkylene having 1 to 3 carbon atoms,
Hydrogen bonded to a cyclohexane ring or a benzene ring may be replaced with -F or -CH ₃ . ]

  Examples of the diamine represented by the general formula (II) include diamines represented by the formulas (II-1) to (II-3).

Examples of the diamine represented by the general formula (III) include diamines represented by the formulas (III-1) and (III-2).

Examples of the diamine represented by the general formula (IV) include diamines represented by the formulas (IV-1) to (IV-3).

Examples of the diamine represented by the general formula (V) include diamines represented by the formulas (V-1) to (V-5).

Examples of the diamine represented by the general formula (VI) include diamines represented by the formulas (VI-1) to (VI-30).

Examples of the diamine represented by the general formula (VII) include diamines represented by the formulas (VII-1) to (VII-6).

Examples of the diamine represented by the general formula (VIII) include diamines represented by the formulas (VIII-1) to (VIII-11).

  Among the specific examples of the diamines represented by the general formulas (II) to (VIII), more preferably, the formulas (V-1) to (V-5) and the formulas (VI-1) to (VI-12). Formula (VI-26), Formula (VI-27), Formula (VII-1), Formula (VII-2), Formula (VII-6), and Formulas (VIII-1) to (VIII-5) Diamines represented by formulas (V-6), (V-7), and formulas (VI-1) to (VI-12) are more preferred.

［式（IX）中、
Ａ₃は、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−または−（ＣＨ₂）ｍ−（式中、ｍは１〜６の整数である）であり、
Ｒ⁶は、ステロイド骨格を有する基、下記式（Ｘ）で表される基、または、ベンゼン環に結合している２つのアミノの位置関係がパラ位のときは炭素数１〜２０のアルキル、もしくは該位置関係がメタのときは炭素数１〜１０のアルキルまたはフェニルであり、
該アルキルにおいては、任意の−ＣＨ₂−が−ＣＦ₂−、−ＣＨＦ−、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよく、−ＣＨ₃が−ＣＨ₂Ｆ、−ＣＨＦ₂または−ＣＦ₃で置き換えられていてもよく
該フェニルの環形成炭素に結合している水素は、−Ｆ、−ＣＨ₃、−ＯＣＨ₃、−ＯＣＨ₂Ｆ、−ＯＣＨＦ₂または−ＯＣＦ₃と置き換えられていてもよい。］ In the present invention, examples of the diamine further include a diamine represented by the general formula (IX).

[In the formula (IX),
A ₃ is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH— or — (CH ₂ ) m — (wherein m is an integer of 1 to 6). ,
R ⁶ is a group having a steroid skeleton, a group represented by the following formula (X), or an alkyl having 1 to 20 carbon atoms when the positional relationship between two amino groups bonded to the benzene ring is para, Alternatively, when the positional relationship is meta, it is alkyl or phenyl having 1 to 10 carbon atoms,
In the alkyl, any —CH ₂ — may be replaced by —CF ₂ —, —CHF—, —O—, —CH═CH— or —C≡C—, and —CH ₃ may be —CH _The hydrogen bonded to the ring-forming carbon of the phenyl which may be replaced by ₂ F, -CHF ₂ or -CF ₃ is -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ Alternatively, it may be replaced with —OCF ₃ . ]

［式（X）中、
Ａ₄およびＡ₅はそれぞれ独立して、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−または炭素数１〜１２のアルキレンであり、
Ｒ₇およびＲ₈はそれぞれ独立して、−Ｆまたは−ＣＨ₃であり、
環Ｓは１，４−フェニレン、１，４−シクロヘキシレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ナフタレン−１，５−ジイル、ナフタレン−２，７−ジイルまたはアントラセン−９，１０−ジイルであり、
Ｒ₉は−Ｈ、−Ｆ、炭素数１〜１２のアルキル、炭素数１〜１２のフッ素置換アルキル、炭素数１〜１２のアルコキシ、−ＣＮ、−ＯＣＨ₂Ｆ、−ＯＣＨＦ₂または−ＯＣＦ₃であり、
ａおよびｂはそれぞれ独立して０〜４の整数を表し、
ｃ、ｄおよびｅはそれぞれ独立して０〜３の整数を表し、ｅが２または３であるとき複数の環Ｓは同一の基であっても異なる基であってもよく、
ｆおよびｇはそれぞれ独立して０〜２の整数を表し、かつ
ｃ＋ｄ＋ｅ≧１である。］

[In the formula (X),
A ₄ and A ₅ are each independently a single bond, —O—, —COO—, —OCO—, —CONH—, —CH═CH—, or alkylene having 1 to 12 carbons,
R ₇ and R ₈ are each independently —F or —CH ₃ ;
Ring S is 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5- Diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl;
R ₉ is —H, —F, alkyl having 1 to 12 carbons, fluorine-substituted alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, —CN, —OCH ₂ F, —OCHF ₂ or —OCF _3. And
a and b each independently represents an integer of 0 to 4;
c, d and e each independently represent an integer of 0 to 3, and when e is 2 or 3, the plurality of rings S may be the same group or different groups,
f and g each independently represent an integer of 0 to 2 and c + d + e ≧ 1. ]

In the general formula (IX), two aminos are bonded to the phenyl ring carbon. Preferably, the bonding position of the two aminos is preferably the meta position or the para position. Further, the two amino groups are preferably bonded to the 3rd and 5th positions or the 2nd and 5th positions, respectively, when the bonding position of “R ⁶ —A ₃ —” is the 1st position.
Examples of the diamine represented by the general formula (IX) include diamines represented by the following formulas (IX-1) to (IX-11).

In the above formulas (IX-1), (IX-2), (IX-7) and (IX-8), R ₁₈ is an organic group having 2 to 30 carbon atoms, and among these, 3 to 12 carbon atoms. Or alkyl having 3 to 12 carbons is preferable, and alkyl having 5 to 12 carbons or alkoxy having 5 to 12 carbons is more preferable. In the formulas (IX-3) to (IX-6) and (IX-9) to (IX-11), R ₁₉ is an organic group having 2 to 30 carbon atoms. C-10 alkyl or C1-10 alkoxy is preferable, and C3-10 alkyl or C3-10 alkoxy is more preferable.

Examples of the diamine represented by the general formula (IX) further include diamines represented by the following formulas (IX-12) to (IX-17).

In the above formulas (IX-12) to (IX-15), R ₂₀ is an organic group having 2 to 30 carbon atoms, preferably an alkyl group having 4 to 16 carbon atoms, and more preferably an alkyl group having 6 to 16 carbon atoms. In the formula (IX-16) and the formula (IX-17), R ₂₁ is an organic group having 2 to 30 carbon atoms, preferably an alkyl group having 6 to 20 carbon atoms, and more preferably an alkyl group having 8 to 20 carbon atoms.

  Examples of the diamine represented by the general formula (IX) further include diamines represented by the following formulas (IX-18) to (IX-38).

The above formulas (IX-18), (IX-19), (IX-22), (IX-24), (IX-25), (IX-28), (IX-30), (IX-31), In (IX-36) and (IX-37), R ₂₂ is an organic group having 2 to 30 carbon atoms, preferably alkyl having 1 to 12 carbons and alkoxy having 1 to 12 carbons, and having 3 to 12 carbons. Alkyl or C3-C12 alkoxy is more preferable. In addition, the above formulas (IX-20), (IX-21), (IX-23), (IX-26), (IX-27), (IX-29), (IX-32) to (IX-35) ) And (IX-38), R ₂₃ is —H, —F, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, —CN, —OCH ₂ F, —OCHF ₂ or —OCF ₃ . Yes, C3-C12 alkyl or C3-C12 alkoxy is more preferable. In the above formulas (IX-33) and (IX-34), A ₉ is alkylene having 1 to 12 carbons.

Examples of the diamine represented by the general formula (IX) further include diamines represented by the following formulas (IX-39) to (IX-48).

  Of the diamines represented by the general formula (IX), diamines represented by the formulas (IX-1) to (IX-11) are preferable, and the formulas (IX-2), (IX-4), and ( IX-5) and diamines represented by formula (IX-6) are more preferable.

［式（XI）と（XII）中、
Ｒ₁₀は−Ｈまたは−ＣＨ₃であり、
Ｒ₁₁はそれぞれ独立して、−Ｈまたは炭素数１〜２０のアルキルもしくは炭素数２〜２０のアルケニルであり、
Ａ₆はそれぞれ独立して、単結合、−Ｃ（＝Ｏ）−または−ＣＨ₂−であり、
Ｒ₁₃およびＲ₁₄はそれぞれ独立して、−Ｈ、炭素数１〜２０のアルキルまたはフェニルである。］ In the present invention, examples of the diamine used further include compounds represented by the following general formulas (XI) and (XII).

[In the formulas (XI) and (XII)
R ₁₀ is —H or —CH ₃ ;
Each R ₁₁ is independently —H or alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons;
Each A ₆ is independently a single bond, —C (═O) — or —CH ₂ —;
R ₁₃ and R ₁₄ are each independently —H, C 1-20 alkyl or phenyl. ]

In the general formula (XI), it is preferable that one of the two “NH ₂ —Ph—A ₆ —O—” is bonded to the 3-position of the steroid nucleus and the other is bonded to the 6-position. The two amino groups are each bonded to a phenyl ring carbon, and preferably bonded to the meta position or the para position with respect to the bonding position of A ₆ .

Examples of the diamine represented by the general formula (XI) include diamines represented by the formulas (XI-1) to (XI-4).

In the general formula (XII), two “NH ₂ — (R ₁₄ —) Ph—A ₆ —O—” are each bonded to the phenyl ring carbon, but preferably to the carbon to which the steroid nucleus is bonded. On the other hand, it is bonded to carbon in the meta or para position. The two aminos are each bonded to the phenyl ring carbon, but are preferably bonded to the meta or para position with respect to A ₆ .

Examples of the diamine represented by the general formula (XII) include diamines represented by the formulas (XII-1) to (XII-8).

［式（XIII）中、Ｒ₁₅は−Ｈまたは炭素数１〜２０のアルキルであり、該アルキルのうち炭素数２〜２０のアルキルの任意の−ＣＨ₂−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、
Ａ₇はそれぞれ独立して−Ｏ−または炭素数１〜６のアルキレンであり、
Ａ₈は単結合または炭素数１〜３のアルキレンであり、
環Ｔは１，４−フェニレンまたは１，４−シクロヘキシレンであり、
ｈは０または１である。］ In the present invention, examples of the diamine used further include compounds represented by general formulas (XIII) and (XIV).

[In the formula (XIII), R ₁₅ is —H or alkyl having 1 to 20 carbons, and of the alkyls, any —CH ₂ — in the alkyl having 2 to 20 carbons is —O—, —CH═. CH— or —C≡C— may be substituted,
Each A ₇ is independently —O— or alkylene having 1 to 6 carbon atoms;
A ₈ is a single bond or alkylene having 1 to 3 carbon atoms,
Ring T is 1,4-phenylene or 1,4-cyclohexylene,
h is 0 or 1. ]

［式（XIV）中、
Ｒ₁₆は炭素数２〜３０のアルキルであり、
Ｒ₁₇は−Ｈまたは炭素数１〜３０のアルキルであり、
Ａ₇はそれぞれ独立して−Ｏ−または炭素数１〜６のアルキレンである。］

[In the formula (XIV),
R ₁₆ is alkyl having 2 to 30 carbons,
R ₁₇ is —H or alkyl having 1 to 30 carbons;
A ₇ is independently —O— or alkylene having 1 to 6 carbon atoms. ]

In the general formula (XIII), the two amino groups are each bonded to the phenyl ring carbon, but are preferably bonded to the meta position or para to A ₇ .
Examples of the diamine represented by the general formula (XIII) include diamines represented by the formulas (XIII-1) to (XIII-9).

上記式（XIII−１）〜（XIII−３）において、Ｒ₂₄は炭素数−Ｈ、１〜２０のアルキルが好ましく、（XIII−４）〜（XIII−９）においてＲ₂₅は−Ｈ、炭素数１〜１０のアルキルがさらに好ましい。

In the above formulas (XIII-1) to (XIII-3), R ₂₄ is preferably —H, alkyl having 1 to 20 carbon atoms, and in (XIII-4) to (XIII-9), R ₂₅ is —H, carbon. The alkyl having 1 to 10 is more preferable.

In the general formula (XIV), the two amino groups are each bonded to the phenyl ring carbon, but are preferably bonded to the meta position or the para position with respect to A ₇ .

Examples of the diamine represented by the general formula (XIV) include diamines represented by (XIV-1) to (XIV-3).

In the formulas (XIV-1) to (XIV-3), R ₂₆ is alkyl having 2 to 30 carbons, and among these, alkyl having 6 to 20 carbons is preferable, and R ₂₇ is —H or carbon number 1 to 1. 30 alkyl, and among these, -H or alkyl having 1 to 10 carbon atoms is more preferable.

  As above-mentioned, although the diamine represented by general formula (I)-(XIV) can be used for the diamine used in this invention, diamines other than these diamines can also be used, for example. For example, a naphthalene diamine having a naphthalene structure, a fluorene diamine having a fluorene structure, a siloxane diamine having a siloxane bond, or the like can be used alone or mixed with another diamine.

（式中、Ｒ₃₀およびＲ₃₁は独立して炭素数３〜２０のアルキルである。） Furthermore, Preferably, the diamine represented by following formula (11)-(18) may be used as a diamine used in this invention.

(In the formula, R ₃₀ and R ₃₁ are independently alkyl having 3 to 20 carbon atoms.)

Specific examples of the polyvalent amine compound (a2) used in the present invention include ethylenediamine, trimethylenediamine, tetramethylenediamine, tetraethylenediamine, pentamethylenediamine, hexamethylenediamine, hexaethylenediamine, and 1,4-diaminocyclohexane. 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 2,11-dodecanediamine, (o-, m-, p-) phenylenediamine, xylylene diene Amine, menthanediamine, isophoronediamine, 1,3-diaminocyclohexane, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 4,4'-diaminodiphenylmethane, 4,4'-diaminophenylethane, 4,4 ' -Diamino-3 3'-diethyl-5,5'-dimethyldiphenylmethane, 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylmethane, 4,4'-diaminophenyl ether, 3,4'-diaminodiphenyl ether 4,4′-diaminophenyl sulfide, 4,4′-diaminophenyl sulfone, 4,4′-di (methaminophenoxy) diphenyl sulfone, 4,4′-di (paraaminophenoxy) diphenyl sulfone, 1,5- Diaminonaphthalene, 1,8-diaminonaphthalene, 3,3-dimethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 6-amino -1- (4′-aminophenyl) -1,3,3-trimethylindane, 4,4′-diaminobenzanilide, 3,5-diamino 3'-trifluoromethylbenzanilide, 3,5-diamino-4'-trifluoromethylbenzanilide, 3,4'-diaminodiphenyl ether, 2,7-diaminofluorene, 2,2-bis (4-aminophenyl) Hexafluoropropane, 4,4′-methylene-bis (2-chloroaniline), 2,2 ′, 5,5-tetrachloro-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4 ′ -Diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2- Bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-diaminodiphenyl-2,2-propane, 2,2-bis [4- (4-aminophenoxy) phenyl Hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) -biphenyl, 1,3′- Bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-bis [4- (4-amino-2-trifluoromethyl) phenoxy]- Octafluorobiphenyl, diaminotetraphenylthiophene, 1,1-metaxylylenediamine, tetrahydrodicyclopentadi Nirenjiamin, hexahydro-4,7-meth Noin mite range diamine, tricyclo [6,2,1,0 ^2.7] - undecylenate range methyl diamine, 4,4'-methylenebis (cyclohexylamine), 3,3'-benzophenone, 4,4′-diaminobenzophenone, 1,4-diaminotoluene, 2,2′-dimethylbenzidine, diethylenetriamine, triethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, acetoguanamine, benzoguanamine, the above general formula Examples of the compound represented by (1) (siloxane-based diamine), bis (paraaminophenoxy) dimethylsilane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, and an amine adduct of an epoxy compound. Can do.

  Among these, Preferably, it is one chosen from the compound represented by ethylenediamine, trimethylenediamine, and General formula (1), and when these are chosen as a polyvalent amine compound (a2), compression characteristics will become favorable. .

Particularly preferred is a siloxane-based diamine compound represented by the general formula (1). In the general formula (1), l and m are 2 or more, preferably 2 to 10, more preferably 2 to 7, most preferably 3, and R ² is preferably an alkyl having 1 to 7 carbon atoms. More preferably alkyl having 1 to 4 carbon atoms, most preferably methyl, and n is preferably an integer of 2 to 50, more preferably an integer of 2 to 30, most preferably an integer of 2 to 20. . In the general formula (1), a compound in which R ¹ and R ³ are both —C ₃ H ₆ —, R ² is methyl, and n is 2 to 20 has a large displacement when a load is applied ( Soft).

In addition to the siloxane diamine compound represented by the general formula (1), a siloxane diamine compound represented by the following formula can also be used as the diamine. (However, n shown in the formula is 2 to 50).

  The hydroxy compound (a3) is not particularly limited as long as it is a hydroxy compound, and examples thereof include monovalent or divalent alcohol compounds. Examples of the hydroxy compound (a3) include methanol, ethanol, 1-propanol, 2-propanol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, penta Erythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, allyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, caprolactone adduct of tetrahydrofurfuryl alcohol, cyclohexanol, 3-cyclohexene-1-methanol, benzyl alcohol 1,4-butanediol, 1- (2-hydroxyethyl) -2-pyrrolidone, ethylene glycol, diethylene glycol, propylene glycol , Mention may be made of dipropylene glycol, ethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and dipropylene glycol monoalkyl ether.

  Among these, 1,4-butanediol, benzyl alcohol, diethylene glycol monoalkyl ether (particularly diethylene glycol monomethyl ether, diethylene glycol monoethyl ether), and dipropylene glycol monoalkyl ether (particularly dipropylene glycol monomethyl ether, dipropylene glycol) Monoethyl ether) is preferred. One selected from 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate Is preferable because compression characteristics are good. Further, diethylene glycol monoalkyl ether is preferable because of good developability.

Polyester-polyamic acid (A) composition ratio, etc. In the polyester-polyamic acid (A), the acid anhydride (a1) is 30 to 90% by weight with respect to the total amount of the polyester-polyamic acid (A), polyvalent amine compound The size of the pattern obtained from the photosensitive composition of the present invention is a polyester-polyamic acid obtained by reacting 1 to 50% by weight of (a2) and 10 to 60% by weight of the hydroxy compound (a3). This is preferable because it is close to the mask dimension and the chemical resistance of the coating film is increased. Furthermore, the polyester-polyamide obtained by reacting 40 to 80% by weight of the acid anhydride (a1), 3 to 40% by weight of the polyvalent amine compound (a2), and 15 to 50% by weight of the hydroxy compound (a3). An acid is more preferable because the developability is good. Particularly preferably, the polyester obtained by reacting 50 to 70% by weight of the acid anhydride (a1), 5 to 30% by weight of the polyvalent amine compound (a2), and 20 to 40% by weight of the hydroxy compound (a3). -If it is a polyamic acid, a compression characteristic will become further favorable.

The weight average molecular weight of the polyester-polyamic acid (A) is preferably in the range of 1000 to 100000, more preferably in the range of 1500 to 50000, and still more preferably in the range of 2000 to 30000. In addition, the weight average molecular weight of the polyester-polyamic acid (A) in this specification is a weight average molecular weight calculated according to the analysis conditions shown below.
<Analysis conditions>
Column: Shodex Asahipak GF-7MHQ (50 ° C. incubation)
Mobile phase: 0.59% H ₃ PO ₄ added DMF solution Flow rate: 0.6 mL / min
Detector: RI (heated at 30 ° C)
Standard: Monodisperse polystyrene

Synthesis Method of Polyester-Polyamide Acid (A) The method for synthesizing the polyester-polyamide acid (A) of the present invention is not particularly limited. The compound (a3) is reacted in an organic solvent at 50 to 200 ° C. for 2 to 20 hours. The reaction temperature and reaction time are appropriately set depending on the components and the type of solvent, but the reaction temperature is preferably 60 to 180 ° C., more preferably 70 to 160 ° C., and the reaction time is preferably 3 to 18 hours. More preferably, it is 4 to 16 hours. In order to accelerate the reaction, a small amount of a tertiary amine such as pyridine or triethylamine may be added.

  The solvent used in the above reaction is preferably a solvent that dissolves the produced polyester-polyamic acid (A). For example, methanol, ethanol, 1-propanol, 2-propanol, tetrahydrofurfuryl alcohol, caprolactone adduct of tetrahydrofurfuryl alcohol, cyclohexanol, 3-cyclohexene-1-methanol, benzyl alcohol, 1- (2-hydroxyethyl) -2-pyrrolidone, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether, acetone, 2-butanone, ethyl acetate, propyl acetate, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene , Cyclohexanone, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether Le, diethylene glycol methyl ethyl ether, methyl 3-methoxypropionate, an ethyl 3-ethoxypropionate, N, N- dimethylformamide, and N- methyl-2-pyrrolidone or the like, or a mixture thereof.

1.2 Compound (B) having a polymerizable double bond
Although it will not specifically limit as a compound (B) which has a polymerizable double bond used by this invention if it is a compound which has a polymerizable double bond, A polyfunctional acrylate is mentioned. Examples of the compound (B) having a polymerizable double bond include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and triethylene glycol diester. (Meth) acrylate, methoxytriethylene glycol (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, nonylphenoxyethylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, epichlorohydrin Modified ethylene glycol di (meth) acrylate, epichlorohydrin modified diethylene glycol di (meth) a Relate, epichlorohydrin modified triethylene glycol di (meth) acrylate, epichlorohydrin modified tetraethylene glycol di (meth) acrylate, epichlorohydrin modified polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate , Methoxydipropylene glycol (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, epichlorohydrin modified propylene glycol di (Meth) acrylate, epichlorohydrin modified dipropylene Glycol di (meth) acrylate, epichlorohydrin modified tripropylene glycol di (meth) acrylate, epichlorohydrin modified tetrapropylene glycol di (meth) acrylate, epichlorohydrin modified polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified Trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, epichlorohydrin modified trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri ( (Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate , Tetramethylolpropane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, glycerol acrylate methacrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin modified Glycerol tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, epichlorohydrin modified 1,6-hexanediol di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate, neopentyl glycol di (meth) acrylate , Hydroxypivalate neopentyl glycol di (meth) acrylate, caprolactone modified hydroxypivalate neopentylglycol Di (meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxylation Pentaerythritol tetra (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol tetra (meth) acrylate, Alkyl-modified dipentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Prolactone-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol poly (meth) acrylate, allylated cyclohexyl di (meth) acrylate, bis [(meth) acryloxyneopentyl glycol] adipate, bisphenol A di (meth) acrylate , Ethylene oxide modified bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, ethylene oxide modified bisphenol F di (meth) acrylate, bisphenol S di (meth) acrylate, ethylene oxide modified bisphenol S di (meth) acrylate, 1,4 -Butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1,9-nonanediol (meth) acrylate 2,4-diethyl-1,5-pentanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, 1,3-butylene glycol (meth) acrylate, Dicyclopentanyl diacrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, ethylene oxide modified phosphoric acid tri (meth) acrylate, caprolactone, ethylene oxide modified phosphoric acid di (meth) acrylate, caprolactone, ethylene oxide modified phosphoric acid tri (meth) acrylate , Epichlorohydrin modified phthalic acid di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate , Tris [(meth) acryloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, (meth) acrylated isocyanurate, and urethane (meth) acrylate, β-methacryloyloxyethyl Hydrogen phthalate, β-methacryloyloxyethyl hydrogen succinate, 3-chloro-2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene Glycol (meth) acrylate, β-acryloyloxyethyl hydrogen succinate, lauryl (meth) acrylate, 2-hydroxy 1,3 dimethacryloxy Propane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloxypolyethoxy) phenyl ] Propane, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, 2-hydroxy 1-acryloxy-3-methacryloxypropane, 1 -Acryloyloxypropyl-2-phthalate, isostearyl (meth) acrylate, polyoxyethylene alkyl ether (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 2,2-hydrogenated screw [ 4- (acryloxy / polyethoxy) phenyl] propane, 2,2-bis [4- (acryloxy / polypropoxy) phenyl] propane, triisocyanuric acid tri (ethane acrylate), triallyl isocyanuric acid, glycidyl allyl ether, 1,3,5 -Triacryloyl hexahydro-s-triazine, triallyl 1,3,5-benzenecarboxylate, triallylamine, triallyl citrate, triallyl phosphate, allobarbital, diallylamine, diallyldimethylsilane, diallyl disulfide, diallyl ether, zalyl sialate , Diallyl isophthalate, diallyl terephthalate, 1,3-dialyloxy-2-propanol, diallyl sulfide diallyl maleate, 4,4′-isopropylidene diphenol Di (meth) acrylate, 4,4′-isopropylidene diphenol di (meth) acrylate, and the like. These compounds (B) having a polymerizable double bond may be used alone or in combination of two or more.

  When the compound (B) having a polymerizable double bond is used in an amount of 20 to 300 parts by weight, more preferably 30 to 200 parts by weight, based on 100 parts by weight of the polyester-polyamic acid (A), the compression characteristics are good.

  Further, it is preferable that the compound (B) having a polymerizable double bond contains 50% by weight or more of a compound having 2 to 20 (meth) acryloyl, because adhesion at the time of development is high. In particular, when the compound (B) having a polymerizable double bond contains 50% by weight or more of a compound having 4 to 20 (meth) acryloyl, it is more preferable because of high sensitivity.

  Examples of the compound having 4 to 20 (meth) acryloyl include trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, diglycerin tetraacrylate, isocyania. Examples include nouric acid ethylene oxide-modified triacrylate and urethane (meth) acrylate.

  Furthermore, since the compound (B) having a polymerizable double bond contains 50% by weight or more of urethane (meth) acrylate having 4 to 20 (meth) acryloyl, the compression property is particularly good. preferable. Examples of urethane (meth) acrylates having 4 to 20 (meth) acryloyl include NK Oligo (trademark) U-4HA, U-6HA, U-15HA, U-15HA, U-4H manufactured by Shin-Nakamura Chemical Co., Ltd. , And U-6H.

1.3 Photopolymerization initiator (C)
Examples of the photopolymerization initiator (C) used in the present invention include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, Acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4′-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxy Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-o 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxy) Carbonyl) benzophenone, 3,4,4′-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4′-methoxystyryl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ′, 4′-dimethoxystyryl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl)- -Triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [p-N, N-di (ethoxycarbonylmethyl)]-2,6-di (Trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4′-methoxyphenyl) ) -S-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3′-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2-chlorophenyl) Enyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5 , 5′-Tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 3- (2-methyl-2-dimethylamino) Propionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (η ⁵ -2,4-cyclopentadien-1-yl) -Bis (2,6- Fluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, a compound represented by the following general formula (2), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O— Benzoyloxime) and the like. These photopolymerization initiators may be used alone or in combination of two or more.

（式中、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は、それぞれ独立して、炭素数１〜１３のアルキルであり；Ｘ¹およびＸ²は、それぞれ独立して、−Ｏ−、−Ｏ−Ｏ−、または−ＮＨ−である。） Among these, the photopolymerization initiator (C) is a compound represented by the following general formula (2), 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) ), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1. It is preferable to contain one or more of 20% by weight or more of (C) because of high sensitivity.

Wherein R ¹ , R ² , R ³ and R ⁴ are each independently alkyl having 1 to 13 carbons; X ¹ and X ² are each independently —O—, —O -O- or -NH-.)

  Examples of the compound represented by the general formula (2) include 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (t- (Hexylperoxycarbonyl) benzophenone, 3,3′-di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4′-di (methoxycarbonyl) -4,3′-di ( t-butylperoxycarbonyl) benzophenone, 4,4′-di (methoxycarbonyl) -3,3′-di (t-butylperoxycarbonyl) benzophenone, and the like.

  In particular, the photopolymerization initiator (C) is 3,3′-di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4′-di (methoxycarbonyl) -4, One or more selected from 3′-di (t-butylperoxycarbonyl) benzophenone and 4,4′-di (methoxycarbonyl) -3,3′-di (t-butylperoxycarbonyl) benzophenone are used as photopolymerization initiators ( When the content is 20% by weight or more of C), the adhesiveness is good and the development margin is widened, which is preferable. A mixture of these three kinds of compounds is referred to as “BT2”.

  A method for synthesizing the above compound is described in JP-A No. 2000-159827. According to this synthesis method, a mixture of the above three compounds is obtained. The mixture “BT2” of the three kinds of compounds thus obtained is used in the examples described later.

  The photopolymerization initiator (C) is preferably used in an amount of 0.5 to 50 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the polyester-polyamic acid (A). It is good.

1.4 Compound (D) having a thermally crosslinkable functional group
In the photosensitive composition of the present invention, the chemical resistance of the transparent film obtained from the photosensitive composition is improved by adding the compound (D) having a thermally crosslinkable functional group. The compound (D) having a thermally crosslinkable functional group is a radically polymerizable monomer having a thermally crosslinkable functional group, or a copolymer of a radically polymerizable monomer having a thermally crosslinkable functional group and another radically polymerizable monomer, Or it is preferable to contain an epoxy resin. The compound (D) having a thermally crosslinkable functional group is preferably 5 to 200 parts by weight, more preferably 10 to 100 parts by weight, with respect to 100 parts by weight of the polyester-polyamic acid (A). Is good.

  Epoxy is preferred as the thermally crosslinkable functional group. Among these, oxetanyl or oxiranyl has a high effect of increasing chemical resistance, and is more preferable.

  The radical polymerizable monomer having oxetanyl or oxiranyl is not particularly limited as long as it has such a functional group. Examples of the radical polymerizable monomer having oxetanyl or oxiranyl include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3-methyl-3- (meth) acryloxymethyl. Oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, p-vinylphenyl-3 Ethyl oxeta-3-ylmethyl ether, 2-phenyl-3- (meth) acryloxymethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxymethyl oxetane, and 4-trifluoromethyl-2- (meth) ) Acryloxymethyl Oxeta And the like. These radically polymerizable monomers having oxetanyl or oxiranyl can be used alone or in admixture of two or more.

  The epoxy resin is not particularly limited as long as it has oxirane, but a compound having two or more oxiranes is preferable. In the present invention, the concentration of the epoxy resin in the composition is not particularly limited, but is preferably 0.5 to 20% by weight, and more preferably 2 to 15% by weight. Within this concentration range, the coating film formed from the composition has good heat resistance and chemical resistance. Specific examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, glycidyl ester type epoxy resin, alicyclic epoxy resin, 2- [4- ( 2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane, 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxyphenyl) -1-methylethyl] phenyl] ethyl] phenoxy]- 2-propanol etc. are mentioned.

A commercial item can also be used as these epoxy resins. Specific examples include “Epicoat 807”, “Epicoat 815”, “Epicoat 825”, “Epicoat 827”, “Epicoat 828”, “Epicoat 190P”, “Epicoat 191P”, “Epicoat 1004”, “Epicoat 1004”. 1256 "," Epicoat 152 "," Epicoat 154 "," Epicoat 157S65 "," Epicoat 157S70 "(manufactured by Japan Epoxy Resin Co., Ltd.), trade names" EPPN-201 "," EPPN-202 "," EPPN " -501H "," EOCN-102 "," EOCN-103S "," EOCN-104S "," EOCN-1020 "," EOCN-1025 "," EOCN-1027 "(manufactured by Nippon Kayaku Co., Ltd.) , “Araldite CY177”, “Araldite CY” 84 ”(manufactured by Ciba Geigy Japan), trade name“ Celoxide 2021P ”,“ EHPE-3150 ”(manufactured by Daicel Chemical Industries), trade name“ Techmore VG3101L ”(manufactured by Mitsui Chemicals, Inc.), and the like. be able to. Among these, a polyfunctional epoxy resin such as “Techmore VG3101L” represented by the following formula (3) is preferable because of its excellent heat resistance.

  Among the above explanations, co-polymerization using one or more selected from the group consisting of glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3-ethyl-3- (meth) acryloxymethyloxetane A photosensitive composition to which a coalescence has been added is preferred because of its high transparency, heat resistance, chemical resistance, and high film hardness.

Examples of other radical polymerizable monomers that are copolymerized with a radical polymerizable monomer having a thermally crosslinkable functional group include styrene, methyl styrene, vinyl toluene, chloromethyl styrene, (meth) acrylamide, and tricyclo [5.2. 1.0 ^2,6 ] decanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, methyl (meth) acrylate, cyclohexyl (Meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, N-phenyl Reimide, polystyrene macromonomer, polymethyl methacrylate macromonomer, N-acryloylmorpholine, indene, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, (meth) acrylate of ethylene oxide adduct of lauryl alcohol, maleic anhydride, itaconic anhydride Acid, (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, ω-carboxypolycaprolactone mono (meth) acrylate, succinic acid mono [2- (meth) acryloyloxyethyl], mono [2- (meth) acryloyloxyethyl maleate], and mono [2- (meth) acryloyloxyethyl] cyclohexene-3,4-dicarboxylate, etc. is there

  In particular, a photosensitive composition to which a copolymer obtained by polymerizing a mixture of glycidyl (meth) acrylate and another radical polymerizable monomer as an essential component is added has transparency, heat resistance and chemical resistance. The film is preferable because it has a high film property and high film hardness and good developability.

  Examples of such a copolymer include (meth) acrylic acid / glycidyl (meth) acrylate copolymer, (meth) acrylic acid / glycidyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) Acrylic acid / glycidyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / glycidyl (meth) acrylate / benzyl (meth) acrylate / 3-ethyl-3- (meth) acryloxy Methyl oxetane copolymer, (meth) acrylic acid / glycidyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / 3-ethyl-3- (meth) acryloxymethyl oxetane copolymer, (meth) acrylic acid / Glycidyl (meth) acrylate / 2-hydroxyethyl (meta Acrylate / 3-ethyl-3- (meth) acryloxymethyloxetane / 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate copolymer, (meth) acrylic acid / glycidyl (meth) acrylate / 2-hydroxyethyl (meth) ) (Meth) acrylate copolymer of ethylene oxide adduct of acrylate / 3-ethyl-3- (meth) acryloxymethyloxetane / lauryl alcohol, (meth) acrylic acid / glycidyl (meth) acrylate / 5-tetrahydrofurfuryloxy Carbonylpentyl (meth) acrylate copolymer, (meth) acrylic acid / glycidyl (meth) acrylate / (meth) acrylate copolymer of ethylene oxide adduct of lauryl alcohol, and γ-methacryloxypropyl hepta (Trifluoropropyl) -T8-silsesquioxane / glycidyl (meth) acrylate copolymer and the like.

  Among these, γ-methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane / glycidyl (meth) acrylate copolymer or (meth) acrylic acid / glycidyl (meth) acrylate copolymer was added. A transparent film obtained from the photosensitive composition is preferable because of its good compression characteristics.

1.5 Solvent used in the present invention In the present invention, a solvent is used in the synthesis of each component compound. Moreover, the photosensitive composition of this invention can contain a solvent. The solvent used in the present invention is preferably a compound having a boiling point of 100 ° C. to 200 ° C. or a mixed solvent containing 20% by weight or more of this compound. Specific examples of the compound having a boiling point of 100 ° C. to 200 ° C. are water, butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate , Methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-D Ethyl xylpropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, pyrubin Methyl acetate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tri Propylene glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol Monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, toluene, xylene, γ-butyrolactone, and N, N-dimethylacetami And the like.

  Among these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, Use of at least one selected from diethylene glycol methyl ethyl ether and ethyl lactate is more preferable because the coating uniformity is increased. In particular, when a solvent selected from propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, and ethyl lactate is used, coating uniformity is high and safety to the human body is improved. Since it becomes high, it is much more preferable.

1.6 Additives Used in the Present Invention Various additives can be added to the photosensitive composition of the present invention in order to improve resolution, coating uniformity, developability, and adhesion. Examples of additives include acrylic, styrene, polyethyleneimine or urethane polymer dispersants, anionic, cationic, nonionic or fluorine surfactants, coating improvers such as silicone resins, silane Adhesion improvers such as coupling agents, UV absorbers such as alkoxybenzophenones, anti-aggregation agents such as sodium polyacrylate, thermal cross-linking agents such as epoxy compounds, melamine compounds or bisazide compounds, and alkali dissolution such as organic carboxylic acids Sex promoters and the like.

  Specific examples of additives include EFKA-745, EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all of which are trademarks, manufactured by Morishita Sangyo), Solspurs (Trademark) 3000, 5000, 9000, 12000, 13240, 13940, 17000, 20000, 24000, 24000GR, 26000, 28000, 32000 (above, manufactured by Zeneca), Disperseade (trademark) 6, 8, 15, 9100 (above) , Manufactured by San Nopco), Polyflow (trademark) No. 45, no. 75, no. 90, no. 95, KL-245 (above, manufactured by Kyoeisha Chemical Industry), Disperbyk (trademark) 161, 162, 163, 164, 166, 170, 180, 181, 182; BYK300, 310, 320, 330, 346 ( (Made by Big Chemie), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene) Ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethyleneoctylphenyl ether Tellurium, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate , Polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene Sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthylate , Alkyl benzene sulfonates, and alkyl diphenyl ether disulfonic acid salts and the like. These additives can be used alone or in admixture of two or more.

  Among these, fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether) It is preferable to use an additive selected from fluoroalkyltrimethylammonium salts and fluoroalkylaminosulfonates since the coating uniformity is increased.

1.7 Development of Photosensitive Composition of the Present Invention The developer used when developing the photosensitive composition of the present invention after exposure is preferably an alkaline aqueous solution. Specific examples of the alkali include tetramethylammonium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like, and these aqueous solutions are preferably used.

  A surfactant may be added to the developer for the purpose of reducing development residue and optimizing the pattern shape. The surfactant can be selected from anionic, cationic and nonionic surfactants. In particular, the addition of nonionic polyoxyethylene alkyl ether is preferable because the pattern shape is improved.

  The development method is not particularly limited. Any of dip development, paddle development, and shower development can be used.

  When the photosensitive composition of the present invention is stored in the dark at a temperature in the range of -5 ° C to 25 ° C, the composition has good stability over time. When the storage temperature is 0 ° C. to 10 ° C., the temporal stability is even better.

2 Transparent Film, Spacer, Protective Film, and Display Element of the Present Invention The present invention is a transparent film produced using the above photosensitive composition. The transparent film of the present invention has a high resolution during patterning and is optimal for forming a spacer having a small diameter. Moreover, the transparent film of the present invention is also suitably used as a protective film and a planarizing film. The protective film is formed for the purpose of protecting the TFT, for example, in the manufacturing process of the liquid crystal display element. The planarization film is formed for the purpose of planarizing the unevenness of the color filter surface on the substrate, for example, in the manufacturing process of the liquid crystal display element. The transparent film is formed as follows. First, the photosensitive composition is applied onto a substrate such as glass by spin coating, roll coating, slit coating, or the like. Next, it is dried at 60 to 120 ° C. for 1 to 5 minutes in a hot plate or oven. The dried substrate is irradiated with ultraviolet rays through a mask having a desired pattern shape. An irradiation amount of 5 to 1000 mJ is appropriate for i-line. The portion exposed to ultraviolet light becomes a three-dimensional cross-linked product by polymerization of the acrylic monomer, and becomes insoluble in the alkali developer. Next, the substrate is immersed in an alkaline developer by shower development, spray development, paddle development, dip development or the like, and unnecessary portions are dissolved and removed. Finally, by baking at 180 to 250 ° C. for 10 to 120 minutes, a transparent film having a desired pattern can be obtained.

  Moreover, this invention is a display element containing the said transparent film | membrane, a spacer, or a protective film. Since the spacer diameter of the present invention is small, even if it is formed on a thin black matrix, it does not protrude from the black matrix. Accordingly, liquid crystal alignment unevenness due to the spacer does not occur, and a high-quality display element without light leakage can be obtained. That is, according to the display element of the present invention, it is possible to increase the yield at the time of manufacturing and to avoid the deterioration of the quality in the process of being incorporated into the final product after manufacturing.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these.

[Synthesis Example 1] Synthesis of polyester-polyamic acid (A1) First, the following reagents were charged in a four-necked flask equipped with a stirrer, and stirred and dissolved at room temperature.
・ Styrene-maleic anhydride copolymer
(Molar ratio 1: 1, molecular weight 1,500) 50 g
・ Diethylene glycol monoethyl ether 31.29 g
・ Propylene glycol monomethyl ether acetate 86.79g
(PGMEA)

Next, the following mixed solution was added dropwise with stirring.
Compound represented by formula (1) (FM3311: manufactured by Chisso Corporation) 7.07 g
・ PGMEA 21.21g

Furthermore, after raising the temperature to 130 ° C. and refluxing for 2 hours, the mixture was cooled to obtain a 45 wt% PGMEA solution of polyester-polyamic acid (A1).

[Synthesis Example 2] Synthesis of polyester-polyamic acid (A2) First, the following reagents were charged in a four-necked flask equipped with a stirrer, and stirred and dissolved at room temperature.
・ Styrene-maleic anhydride copolymer
(Molar ratio 1: 1, molecular weight 1,500) 50 g
・ Diethylene glycol monoethyl ether 29.40g
・ PGMEA 91.93g

Next, the following mixed solution was added dropwise with stirring.
-Compound represented by Formula (1) (FM3311: manufactured by Chisso Corporation) 14.2 g
・ PGMEA 22.47g

Furthermore, the temperature was raised to 135 ° C., refluxed for 2 hours, and then cooled to obtain a 45 wt% PGMEA solution of polyester-polyamic acid (A2).

[Synthesis Example 3]
Synthesis of copolymer (A3) described in Example 1 of JP-A-2005-308874 (comparative example)

First, the following reagents were charged into a 500 ml separable flask equipped with a stirrer, and reacted at 120 ° C. for 2 hours under a nitrogen stream.
・ BPADA 52.05g
・ 2,2-dimethyl-1,3-propanediol 5.21 g
・ N, N'-dimethylformamide (DMF) 100.0 g
* BPADA = 4,4 '-(4,4'-isopropylidenephenoxy) bisphthalic anhydride

Next, the reaction solution was allowed to cool, the following reagents were added, and the mixture was reacted at 20 ° C. for 1 hour under a nitrogen stream to obtain a polyamic acid solution.
・ Siliconediamine KF-8010 (manufactured by Shin-Etsu Silicone) 41.5g

Further, this polyamic acid solution was heated in a vacuum oven at 200 ° C. for 2 hours (10 hPa) to obtain 94 g of a polyimide composition.

[Synthesis Example 4]
Synthesis of a copolymer (D1) obtained by polymerizing a mixture of radically polymerizable monomers containing a radically polymerizable monomer having a thermally crosslinkable functional group as an essential component

First, the following reagents were charged in a four-necked flask equipped with a stirrer and heated at reflux temperature for 4 hours.
・ PGMEA 125.0g
・ Glycidyl methacrylate 40.0g
・ Γ-Methacryloxypropyl hepta (trifluoropropyl)
-T8-silsesquioxane 10.0 g
・ 2,2′-azobis (2,4-dimethylvaleronitryl) 2.0 g

Next, the reaction solution was cooled to room temperature to obtain a 28.6 wt% PGMEA solution of copolymer (D1).

[Synthesis Example 5]
Synthesis of a copolymer (D2) obtained by polymerizing a mixture of radically polymerizable monomers containing a radically polymerizable monomer having a thermally crosslinkable functional group as an essential component

First, the following reagents were charged in a four-necked flask equipped with a stirrer and heated at reflux temperature for 4 hours.
・ PGMEA 125.0g
・ Glycidyl methacrylate 47.5g
・ Γ-Methacryloxypropyl hepta (trifluoropropyl)
-T8-silsesquioxane 2.5g
・ 2,2′-azobis (2,4-dimethylvaleronitryl) 2.0 g

Next, the reaction solution was cooled to room temperature to obtain a 28.6 wt% PGMEA solution of copolymer (D2).

[Synthesis Example 6]
Synthesis of a copolymer (D3) obtained by polymerizing a mixture of radically polymerizable monomers containing a radically polymerizable monomer having a thermally crosslinkable functional group as an essential component

First, the following reagents were put in a four-necked flask with a stirrer.
・ Diethylene glycol methyl ethyl ether 350.0g

Next, the following reagents were mixed to prepare a dropping solution, and heated at reflux temperature for 6 hours while dropping into the flask.

・ Glycidyl methacrylate 225.0g
・ Methacrylic acid 25.0g
・ Diethylene glycol methyl ethyl ether (EDM) 100.0g
・ 2,2′-azobis (2,4-dimethylvaleronitryl) 2.0 g

Further, the following reagents were added as line washing, and after cooling, 0.75 g of 4 methoxyphenol was added.
・ Diethylene glycol methyl ethyl ether 100.0g

As described above, a 33.3% by weight EDM solution of the copolymer (D3) was obtained.

[Example 1]
Polyester-polyamic acid (A1), pentaerythritol tetraacrylate which is a compound (B) having a polymerizable double bond (Aronix (trademark) M450 manufactured by Toa Gosei Co., Ltd., hereinafter abbreviated as “M450”) and urethane (meta) Acrylate (NK Naka ™ U-15HA manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter abbreviated as “U-15HA”), “BT2” (26% by weight anisole solution: Chisso) which is a photopolymerization initiator (C) Co., Ltd.), a copolymer (D1) obtained by polymerizing a mixture of radically polymerizable monomers containing a radically polymerizable monomer having a thermally crosslinkable functional group as an essential component, Neos which is a fluorosurfactant ( FOANTENT (trademark) DFX-18 (hereinafter abbreviated as “DFX-18”) manufactured by Hodogaya Chemical Co., Ltd., which is a sensitizer AB-F (hereinafter referred to as "EAB-F"), and MQ (the hydroquinone monomethyl ether (Tokyo Chemical Industry Co., Ltd.) and EDM were mixed and dissolved in the following composition as a solvent to obtain a photosensitive composition.
-50% by weight solution of polyester-polyamic acid (A1) 5.00 g
・ M450 (B) 1.58 g
・ U-15HA (B) 0.29 g
・ BT2 (C) 0.27 g
-30% by weight solution of copolymer (D1) 2.36 g
・ DFX-18 0.003g
-EAB-F 0.02 g
・ MQ 0.01 g
・ EDM 1.70 g

This photosensitive composition was spin-coated on a glass substrate at 1000 rpm for 10 seconds, and dried on a hot plate at 100 ° C. for 2 minutes. This substrate was exposed in air using a proximity exposure machine TME-400PRC manufactured by Topcon Corporation through a dot pattern mask with an exposure gap of 100 μm. At this time, light of 350 nm or less was cut through a wavelength cut filter, and g, h, and i rays were taken out and exposed. The exposure amount was 50 mJ / cm ^{2 as} measured by an integrated light meter UIT-150 manufactured by Ushio Corporation and a photoreceiver UVD-S365. The exposed glass substrate was dip-developed with a 0.04 wt% aqueous potassium hydroxide solution for 90 seconds to remove unexposed portions. The developed substrate was washed with pure water for 20 seconds and then dried. The residual film ratio after development (film thickness after development × 100 / film thickness before development) was 91.0%, and it was confirmed that the film had sufficient sensitivity. Furthermore, it was post-baked in an oven at 220 ° C. for 30 minutes. The film thickness was 3.4 μm. When observed with a 1000 × optical microscope, the size of the dot pattern when using a 10 μm square mask was 12 μm.

The dot pattern was subjected to a load-unload test using a flat indenter with a dynamic micro hardness tester DUH-W201S manufactured by Shimadzu Corporation. The load is increased at a load speed of 2.2 mN / sec, the maximum load is 50 mN, the holding time at the maximum load is 5 seconds, the load is decreased at an unload speed of 0.4 mN / sec, and the final load is 1 mN. did. When the displacement when the load first becomes 1 mN is L ₀ , the displacement when the maximum load is held at 10 mN for 5 seconds is L ₁ , and the displacement at the final load ₁ mN is L ₂ , the maximum displacement L _MAX (μm ) And the restoration rate R (%) are expressed by the following equations.
L _MAX = L ₁ −L ₀
R = (L ₁ −L ₂ ) × 100 / (L ₁ −L ₀ )
The maximum displacement L _MAX of the dot pattern obtained in Example 1 was 0.75 μm, and the restoration rate R was 66%.

[Examples 2 to 4]
In the same manner as in Example 1, photosensitive compositions of Examples 2 to 4 were prepared with the compositions shown in Table 1 below. The amount of the solvent added was adjusted so that the solid concentration was 40%. Next, the photosensitive compositions of Examples 2 to 4 were spin-coated at a rotational speed such that the film thickness after post-baking was 3.0 to 3.5 μm, and the same evaluation as in Example 1 was performed. It was. The results of the remaining film rate and the pattern size are shown in Table 1 below, and the results of the maximum displacement L _MAX and the restoration rate R are shown in Table 2 below.

[Example 5]
In the same manner as in Example 1, polyester-polyamic acid (A1), M450 which is a compound (B) having a polymerizable double bond, IRGACURE907 (Ciba Specialty Chemicals Co., Ltd.), which is a photopolymerization initiator, hereinafter Irg907 And “Techmore VG3101L” (manufactured by Mitsui Chemicals, Inc.), which is a polyfunctional epoxy resin, was mixed and dissolved in the following composition to obtain a photosensitive composition.
-Polyester-polyamic acid (A1) 50% by weight solution 10.0 g
・ M450 (B) 6.0g
・ Irg907 (C) 1.0g
・ VG3101L (D) 1.0g
・ PGMEA 34.0g

The amount of the solvent added was adjusted so that the solid concentration was 25%. This photosensitive composition was spin-coated at a rotation speed such that the film thickness after post-baking was 3.0 to 3.5 μm, and the same evaluation as in Example 1 was performed. However, in the exposure, full line exposure was performed without using a wavelength cut filter. The results of the remaining film rate and the pattern size are shown in Table 1 below, and the results of the maximum displacement L _MAX and the restoration rate R are shown in Table 2 below.

[Comparative Example 1]
Polyimide composition (A3), modified acrylate EB3708 (manufactured by Daicel UC Corporation) and BR-42M (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), which are compounds (B) having a carbon-carbon double bond, light Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, which is a reaction initiator (C), was mixed and dissolved in the following composition so as to have a solid content concentration of 30% to obtain a photosensitive composition.
・ Polyimide composition (A3) 54g
・ EB3708 (B4) 25g
・ BR-42M (B5) 20g
・ Bis (2,4,6-trimethylbenzoyl)
Phenylphosphine oxide (C2) 1g

The photosensitive composition of Comparative Example 1 was spin-coated at a rotation speed such that the film thickness after post-baking was 3.0 to 3.5 μm, and the same evaluation as in Example 1 was performed. The results of the remaining film rate and the pattern size are shown in Table 1 below, and the results of the maximum displacement L _MAX and the restoration rate R are shown in Table 2 below.

表１におけるカッコ内の数字は固形分の重量比である。
表１における略号は以下を表す。
Ｂ１：新中村化学工業（株）製、ＮＫオリゴ（商標）Ｕ−１５ＨＡ
Ｂ２：ペンタエリスリトールテトラアクリレート
東亜合成（株）製、アロニックス（商標）Ｍ４５０
Ｂ３：ジペンタエリスリトールヘキサアクリレート
東亜合成（株）製、アロニックス（商標）Ｍ４０２
Ｃ１：３，３’−ジ（メトキシカルボニル）−４，４’−ジ（ｔ−ブチルペルオキシカルボニル）ベンゾフェノン、３，４’−ジ（メトキシカルボニル）−４，３’−ジ（ｔ−ブチルペルオキシカルボニル）ベンゾフェノン、および４，４’−ジ（メトキシカルボニル）−３，３’−ジ（ｔ−ブチルペルオキシカルボニル）ベンゾフェノンの３０：５０：２０の混合物
Ｃ３：２−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（チバ・スペシャリティ・ケミカルズ製、イルガキュア９０７（商標））
Ｄ３：ＶＧ３１０１Ｌ（三井化学（株）製）

The numbers in parentheses in Table 1 are the weight ratio of the solid content.
Abbreviations in Table 1 represent the following.
B1: Shin-Nakamura Chemical Co., Ltd., NK Oligo (trademark) U-15HA
B2: Pentaerythritol tetraacrylate
Aronix (trademark) M450, manufactured by Toa Gosei Co., Ltd.
B3: Dipentaerythritol hexaacrylate
Aronix (trademark) M402, manufactured by Toa Gosei Co., Ltd.
C1: 3,3′-di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4′-di (methoxycarbonyl) -4,3′-di (t-butylperoxy) 30:50:20 mixture of carbonyl) benzophenone and 4,4′-di (methoxycarbonyl) -3,3′-di (t-butylperoxycarbonyl) benzophenone C3: 2-methyl-1- [4- ( Methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals, Irgacure 907 ™)
D3: VG3101L (Mitsui Chemicals, Inc.)

  As is clear from the above, the photosensitive compositions of Examples 1 to 5 each had a high pattern remaining film ratio, and a pattern having a pattern size close to the mask size could be obtained. Moreover, the pattern obtained from the photosensitive composition of Examples 1-5 had high maximum displacement. On the other hand, although the pattern of the magnitude | size equivalent to an Example is obtained for the photosensitive composition of the comparative example 1, the remaining film rate is low. Also, in the compression characteristics, the restoration rate is the same as that of the example, but the maximum displacement is small. This indicates that the comparative example is harder. From these, it can be seen that the photosensitive compositions of Examples 1 to 5 are superior to the comparative example in terms of sensitivity to ultraviolet rays and further excellent in compression characteristics required as a spacer material.

Claims (19)

Polyester-polyamic acid (A) obtained by reacting acid anhydride (a1), polyvalent amine compound (a2) and hydroxy compound (a3), compound (B) having a polymerizable double bond, and photopolymerization A photosensitive composition containing an initiator (C),
The photosensitive composition in which the said acid anhydride (a1) contains the copolymer of the polymerizable monomer which has an acid anhydride group, and another radically polymerizable monomer. The acid anhydride (a1) is a copolymer of maleic anhydride and another radical polymerizable monomer,
The polyvalent amine compound (a2) is a diamine;
The hydroxy compound (a3) is a monovalent or divalent alcohol compound;
The compound (B) having a polymerizable double bond contains a polyfunctional acrylate,
The photosensitive composition of Claim 1. The other radical polymerizable monomer in the acid anhydride (a1) is alkyl (meth) acrylate or styrene,
The polyvalent amine compound (a2) is a siloxane diamine,
The hydroxy compound (a3) is methanol, ethanol, 1-propanol, 2-propanol, 1,4-butanediol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, allyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, tetrahydrofurfuryl alcohol Caprolactone adduct, cyclohexanol, 3-cyclohexene-1-methanol, benzyl alcohol, 1- (2-hydroxyethyl) 2-pyrrolidone, ethylene glycol monoalkyl ether, and a diethylene glycol monoalkyl ether, propylene glycol monoalkyl ethers, and one or more selected from the group consisting of dipropylene glycol monoalkyl ethers,
The compound (B) having a polymerizable double bond is one selected from the group consisting of pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, urethane (meth) acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate. Containing 50% by weight or more based on the total weight of the compound (B) having a polymerizable double bond,
The photopolymerization initiator (C) is 3,3′-di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4′-di (methoxycarbonyl) -4,3. '-Di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2, -Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and 1,2- One or more selected from the group consisting of octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime) is used as a photopolymerization initiator (C ) 20% by weight or more based on the total weight of
The photosensitive composition of Claim 2.   The hydroxy compound (a3) is one or more selected from the group consisting of 1,4-butanediol, benzyl alcohol, diethylene glycol monoalkyl ether, and dipropylene glycol monoalkyl ether. A photosensitive composition described in 1.   The polyester-polyamic acid (A) is 30 to 90% by weight of the acid anhydride (a1) and 1 to 50% by weight of the polyvalent amine compound (a2) based on the total weight of the polyester-polyamic acid (A). The photosensitive composition according to any one of claims 1 to 4, which is obtained by reacting 10 to 60% by weight of a hydroxy compound (a3).   The photosensitive composition contains 20 to 300 parts by weight of the compound (B) having a polymerizable double bond and 0% of the photopolymerization initiator (C) with respect to 100 parts by weight of the polyester-polyamic acid (A). The photosensitive composition in any one of Claims 1-5 containing 0.5-50 weight part.   Furthermore, the photosensitive composition in any one of Claims 1-6 containing the compound (D) which has a heat crosslinkable functional group.   The compound (D) having a thermally crosslinkable functional group is a radically polymerizable monomer having a thermally crosslinkable functional group, or a copolymer of a radically polymerizable monomer having a thermally crosslinkable functional group and another radically polymerizable monomer. The photosensitive composition of Claim 7 containing this.   The photosensitive composition according to claim 7, wherein the thermally crosslinkable functional group is at least one selected from the group consisting of oxetanyl and oxiranyl.   The radically polymerizable monomer having a thermally crosslinkable functional group is selected from the group consisting of glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3-ethyl-3- (meth) acryloxymethyloxetane. The photosensitive composition of Claim 8 which is 1 or more types selected.   The other radical polymerizable monomer in the compound (D) having a thermally crosslinkable functional group is selected from the group consisting of (meth) acrylic acid and γ-methacryloxypropylhepta (trifluoropropyl) -T8-silsesquioxane. The photosensitive composition according to claim 8, which is one or more selected. Polyester-polyamic acid (A) obtained by reacting acid anhydride (a1), polyvalent amine compound (a2) and hydroxy compound (a3), compound (B) having a polymerizable double bond, photopolymerization initiation A photosensitive composition comprising an agent (C) and a compound (D) having a thermally crosslinkable functional group,
The acid anhydride (a1) is a styrene-maleic anhydride copolymer, or a mixture of a styrene-maleic anhydride copolymer and another acid anhydride,
The polyvalent amine compound (a2) is represented by the following general formula (1)

In (Equation (1), R ¹ is _{- (CH 2) l - (} l is an integer of 2 to 10), R ³ is _{- (CH 2) m - (} m is an integer) from 2 to 10 , R ² is methyl, and n is an integer of 2 to 50).
The hydroxy compound (a3) is at least one selected from the group consisting of diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether;
The compound having a polymerizable double bond, wherein the compound (B) having a polymerizable double bond is one or more selected from the group consisting of pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and urethane (meth) acrylate. Containing at least 50% by weight based on the total weight of (B),
The photopolymerization initiator (C) is 3,3′-di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4′-di (methoxycarbonyl) -4,3. From '-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, and 4,4'-bis (diethylamino) benzophenone One or more selected from the group consisting of 20% by weight or more based on the total weight of the photopolymerization initiator (C),
The photosensitive composition whose compound (D) which has the said heat crosslinkable functional group is a copolymer of glycidyl (meth) acrylate and (gamma) -methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane. .   The photosensitive composition contains 20 to 300 parts by weight of the compound (B) having a polymerizable double bond and 0.5% of the photopolymerization initiator (C) with respect to 100 parts by weight of the polyester-polyamic acid (A). The photosensitive composition in any one of Claims 7-12 which contains 5-200 weight part of compounds (D) which have ~ 50 weight part and a heat-crosslinkable functional group.   The transparent film manufactured using the photosensitive composition in any one of Claims 1-13.   The spacer manufactured using the photosensitive composition in any one of Claims 1-13.   The protective film for color filters manufactured using the photosensitive composition in any one of Claims 1-13.   A display element comprising the transparent film according to claim 14.   A display element comprising the spacer according to claim 15.   A display device comprising the protective film according to claim 16.