JP5449666B2 - Alkali-soluble resin and method for producing the same, and photosensitive resin composition, cured product, and color filter using alkali-soluble resin - Google Patents

Description

  The present invention relates to an alkali-soluble resin that can be cured by irradiation with ultraviolet rays or an electron beam and can be patterned by alkali development, a method for producing the same, and a photosensitive resin composition using the alkali-soluble resin. Is a photosensitive resin composition suitable for obtaining a resist for a color filter, and also relates to an alkali-soluble resin suitable for forming the photosensitive resin composition.

  A color liquid crystal display device has a liquid crystal part for controlling the amount of light transmitted or reflected and a color filter as components, and the manufacturing method of the color filter is usually applied to the surface of a transparent substrate such as glass or plastic sheet. A method is used in which a black matrix is formed, and subsequently, different hues of red, green, and blue are sequentially formed in a color pattern such as a stripe shape or a mosaic shape. In recent years, color liquid crystal display devices have been used in various fields such as liquid crystal televisions, liquid crystal monitors, and color liquid crystal mobile phones, and color filters are one of the important components that influence the visibility of these color liquid crystal display devices. is there. The pattern size varies depending on the use of the color filter and the respective colors, but red, green and blue pixels are thinned from 100 μm to 50 μm or less, and the black matrix is thinned from 20 μm to 10 μm or less. Therefore, the photosensitive resin composition is required to form a pattern with high dimensional accuracy.

  In general, a photosensitive resin composition for such an application uses a polyfunctional photocurable monomer having a polymerizable unsaturated bond, an alkali-soluble binder resin, and a composition obtained by combining them with a photopolymerization initiator. It has been. For example, Japanese Patent Application Laid-Open No. 61-213213 (Patent Document 1) and Japanese Patent Application Laid-Open No. 1-152449 (Patent Document 2) exemplify application as a material for a color filter, and has a carboxyl group as a binder resin ( A copolymer of (meth) acrylic acid or (meth) acrylic acid ester, maleic anhydride and other polymerizable monomer is disclosed. However, since the copolymer disclosed here is a random copolymer, an alkali dissolution rate distribution occurs in the light irradiated part as well as in the light non-irradiated part, and the margin during the developing operation is narrow. In addition, it is difficult to obtain an acute pattern shape or a fine pattern. In particular, when a high concentration of pigment is included, the exposure sensitivity is remarkably lowered, and a fine negative pattern cannot be obtained. JP-A-4-340965 (Patent Document 3) discloses that an alkali-soluble unsaturated compound having a polymerizable unsaturated double bond and a carboxyl group in one molecule can form a negative pattern such as a color filter. It is disclosed that it is effective. Since molecules having alkali solubility are insolubilized by light irradiation, it is predicted that the sensitivity will be higher than the combination of the binder resin and the polyfunctional polymerizable monomer described above, but the compounds exemplified here are Acrylic acid and acid anhydride, which are polymerizable unsaturated bonds, are arbitrarily added to the hydroxyl group of the phenol oligomer, and even in such a proposal, the distribution of the alkali dissolution rate is due to the heterogeneity of the molecular composition. It is difficult to form a wide and fine negative pattern.

  On the other hand, JP-A-4-345673 (Patent Document 4), JP-A-4-345608 (Patent Document 5), JP-A-4-355450 (Patent Document 6), and JP-A-4-363311 (Patent). Document 7) discloses a liquid resin using a reaction product of an epoxy (meth) acrylate having a bisphenolfluorene structure and an acid anhydride. However, the resins exemplified by them have a low molecular weight because they are reaction products of epoxy (meth) acrylate and acid monoanhydride. Therefore, the sensitivity of the compound is low and a fine pattern cannot be formed.

  Further, JP-A-5-339356 (Patent Document 8), JP-A-5-146132 (Patent Document 9), and WO94 / 00801 pamphlet (Patent Document 10) disclose dihydroxypropyl acrylate compounds and acid dianhydrides. An alkali-developable unsaturated resin composition by copolymerization with a product, or an alkali-developable unsaturated resin composition by copolymerization of an acid monoanhydride and acid dianhydride and a dihydroxypropyl acrylate compound is disclosed. In this case, the copolymerization of the acid dianhydride and the dihydroxypropyl acrylate compound proceeds to obtain an oligomer. However, since the number of polymerizable unsaturated bonds in the repeating unit is constant, the crosslinking density cannot be improved, and it may be difficult to form a fine line pattern under a high concentration pigment, and there is room for improvement. .

Japanese Patent Laid-Open No. 9-325494 (Patent Document 11) increases the molecular weight of a carboxyl group-containing copolymer to polyfunctionalize an alkali-soluble resin composition. However, in this case as well, the crosslinking density cannot be improved because the number of polymerizable unsaturated bonds in the repeating unit is constant as in the above-mentioned patent document.
JP 61-213213 Japanese Unexamined Patent Publication No. 1-152449 Japanese Unexamined Patent Publication No. 4-340965 JP-A-4-345673 JP-A-4-345608 JP-A-4-355450 Japanese Unexamined Patent Publication No. 4-363311 JP-A-5-339356 JP-A-5-146132 WO94 / 00801 pamphlet JP-A-9-325494

  Therefore, as a result of intensive studies to solve the problems in the conventional photosensitive resin composition as described above, the present inventors have found that a diol compound containing a polymerizable unsaturated group and a tetracarboxylic acid or an acid diacid thereof. By reacting a carboxyl group-containing copolymer obtained by reacting with an anhydride with an epoxy compound containing a polymerizable unsaturated bond group, and further reacting with a dicarboxylic acid or its acid monoanhydride, a photosensitive resin is obtained. It has been found that an alkali-soluble resin suitable for forming a composition can be obtained. By using this alkali-soluble resin, the crosslink density is improved while controlling the solubility in alkali developer, the difference in solubility between the hardened part and the uncured part in the alkaline developer is increased, and fine line patterns are formed beautifully. In addition, it has succeeded in obtaining a photosensitive resin composition having high sensitivity and a wide development adhesion margin.

  Accordingly, an object of the present invention is to provide a photosensitive resin composition that is excellent in forming a fine pattern and is suitable as a material for high light-shielding or high-definition color filters, and an alkali-soluble resin that forms this photosensitive resin composition. There is to do.

  Another object of the present invention is to provide a coating film (cured product) and a color filter formed using the above-described high-sensitivity photosensitive resin composition.

（但し、Ｒ₁、Ｒ₂、Ｒ₃、及びＲ₄は、独立に水素原子、炭素数１〜５のアルキル基、ハロゲン原子又はフェニル基を示し、Ｒ₅は水素原子又はメチル基を示す。また、Xは-CO-、-SO₂-、-C(CF₃)₂-、-Si(CH₃)₂-、-CH₂-、-C(CH₃)₂-、-O-、9,9-フルオレニレン基又は直結合を示し、Yは、飽和環状炭化水素で置換されていてもよい飽和直鎖炭化水素テトラカルボン酸二無水物、飽和炭化水素で置換されていてもよい脂環式テトラカルボン酸二無水物、及び芳香族テトラカルボン酸二無水物から選ばれた１種以上のテトラカルボン酸二無水物のカルボン酸残基を示す。Gは下記一般式（２）で表される重合性二重結合とカルボキシル基を有する置換基を示す。Zは下記一般式（３）で表される置換基を示し、ｎは１〜２０の数を表す。）

（但し、Ｒ₈は炭素数３〜６の脂肪族炭化水素基、Ｒ₆は２価のアルキレン基、Ｒ₇は水素原子またはメチル基を示し、Ｚは下記一般式（３）と同じであり、ｑは０または１の数を表す。）

（但し、Lは、炭化水素基で置換されていてもよい飽和直鎖炭化水素ジカルボン酸、飽和炭化水素基で置換されていてもよい飽和環状炭化水素ジカルボン酸、不飽和ジカルボン酸、芳香族ジカルボン酸、クエン酸、トリメリット酸及びヘキサヒドロトリメリット酸から選ばれた１種以上のカルボン酸残基を示し、pは１または２である） That is, the present invention is an alkali-soluble resin represented by the following general formula (1) and having a carboxylic acid residue and a polymerizable unsaturated group in the molecule.

_{(Wherein, R 1, R 2, R} 3, and R ₄ are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ represents a hydrogen atom or a methyl group. X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9 , 9-fluorenylene group or a direct bond, Y is a saturated linear hydrocarbon tetracarboxylic dianhydride which may be substituted with a saturated cyclic hydrocarbon, an alicyclic which may be substituted with a saturated hydrocarbon 1 represents a carboxylic acid residue of one or more tetracarboxylic dianhydrides selected from tetracarboxylic dianhydrides and aromatic tetracarboxylic dianhydrides, where G is represented by the following general formula (2). A substituent having a polymerizable double bond and a carboxyl group is shown, Z is a substituent represented by the following general formula (3), and n is a number of 1 to 20.

(However, R ₈ is an aliphatic hydrocarbon group having 3 to 6 carbon atoms, R ₆ is a divalent alkylene group, R ₇ is a hydrogen atom or a methyl group, and Z is the same as in the following general formula (3). Q represents a number of 0 or 1.)

(However, L is a saturated linear hydrocarbon dicarboxylic acid optionally substituted with a hydrocarbon group, a saturated cyclic hydrocarbon dicarboxylic acid optionally substituted with a saturated hydrocarbon group, an unsaturated dicarboxylic acid, or an aromatic dicarboxylic acid. 1 or more carboxylic acid residues selected from acid, citric acid, trimellitic acid and hexahydrotrimellitic acid, and p is 1 or 2)

（但し、Ｒ ₁ 、Ｒ ₂ 、Ｒ ₃ 、及びＲ ₄ は、独立に水素原子、炭素数１〜５のアルキル基、ハロゲン原子又はフェニル基を示し、Ｒ ₅ は水素原子又はメチル基を示す。また、Xは-CO-、-SO ₂ -、-C(CF ₃ ) ₂ -、-Si(CH ₃ ) ₂ -、-CH ₂ -、-C(CH ₃ ) ₂ -、-O-、9,9-フルオレニレン基又は直結合を示す。）と、下記の一般式で表されるテトラカルボン酸二無水物（B）

（但し、Yは、飽和環状炭化水素で置換されていてもよい飽和直鎖炭化水素テトラカルボン酸二無水物、飽和炭化水素で置換されていてもよい脂環式テトラカルボン酸二無水物、及び芳香族テトラカルボン酸二無水物から選ばれた１種以上のテトラカルボン酸二無水物のカルボン酸残基を示す。）とを反応させて得られたカルボキシル基を有する反応物に、下記の一般式で表され、重合性二重結合を少なくとも１つ以上含有し、かつ、オキシラン環を１つ含有するオキシラン化合物（C）

（但し、Ｒ ₆ は２価のアルキレン基、Ｒ ₇ は水素原子またはメチル基を示し、ｑは０または１の数を表す。）を反応させることで水酸基を有する反応物を得て、次いで、この水酸基を有する反応物に、下記の一般式で表され、ジカルボン酸、クエン酸、トリメリット酸及びヘキサヒドロトリメリット酸から選ばれた１種以上の酸一無水物（D）

（但し、Lは、炭化水素基で置換されていてもよい飽和直鎖炭化水素ジカルボン酸、飽和炭化水素基で置換されていてもよい飽和環状炭化水素ジカルボン酸、不飽和ジカルボン酸、芳香族ジカルボン酸、クエン酸、トリメリット酸及びヘキサヒドロトリメリット酸から選ばれた１種以上のカルボン酸残基を示し、pは１または２である）を反応させて得られるアルカリ可溶性樹脂であって、
上記（A）成分と（B）成分とを反応させる際の（A）成分と（B）成分のモル比〔(B)/(A)〕が５０モル％以上１００モル％未満であり、
（A）成分と（B）成分との反応物に（C）成分を反応させる際の（B）成分と（C）成分のモル比〔(C)/(B)〕が１６０〜２２０モル％であり、
（A）成分と（B）成分との反応物にさらに（C）成分を反応させて得られた反応物と（D）成分とを反応させる際、（D）成分のモル比が、（A）〜（C）成分のモル数から求められる［2×〔(A)−(B)〕+(C)］に対して２０〜１１０モル％であることを特徴とするアルカリ可溶性樹脂である。
また、本発明は、（ｉ）上記のアルカリ可溶性樹脂、（ii）少なくとも1個以上のエチレン性不飽和結合を有する光重合性モノマー、及び（iii）光重合開始剤を必須の成分として含有する感光性樹脂組成物である。 The present invention also provides a diol compound (A) containing a polymerizable unsaturated group represented by the following general formula:

_{(Wherein, R 1, R 2, R} 3, and R ₄ are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ represents a hydrogen atom or a methyl group. X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9 , 9-fluorenylene group or a direct bond.) And tetracarboxylic dianhydride (B) represented by the following general formula

(However, Y is a saturated linear hydrocarbon tetracarboxylic dianhydride which may be substituted with a saturated cyclic hydrocarbon, an alicyclic tetracarboxylic dianhydride which may be substituted with a saturated hydrocarbon, and A carboxylic acid residue of one or more tetracarboxylic dianhydrides selected from aromatic tetracarboxylic dianhydrides.) And a reaction product having a carboxyl group obtained by reacting with An oxirane compound (C) represented by the formula and containing at least one polymerizable double bond and one oxirane ring

(Wherein R ₆ represents a divalent alkylene group, R ₇ represents a hydrogen atom or a methyl group, and q represents a number of 0 or 1) to obtain a reaction product having a hydroxyl group, One or more acid monoanhydrides (D) represented by the following general formula and selected from dicarboxylic acid, citric acid, trimellitic acid and hexahydrotrimellitic acid

(However, L is a saturated linear hydrocarbon dicarboxylic acid optionally substituted with a hydrocarbon group, a saturated cyclic hydrocarbon dicarboxylic acid optionally substituted with a saturated hydrocarbon group, an unsaturated dicarboxylic acid, or an aromatic dicarboxylic acid. An alkali-soluble resin obtained by reacting at least one carboxylic acid residue selected from acid, citric acid, trimellitic acid and hexahydrotrimellitic acid, and p is 1 or 2.
The molar ratio [(B) / (A)] of the component (A) and the component (B) when the component (A) and the component (B) are reacted is 50 mol% or more and less than 100 mol%,
The molar ratio [(C) / (B)] of (B) component and (C) component when reacting (C) component with the reaction product of (A) component and (B) component is 160-220 mol% And
When the reaction product obtained by further reacting the component (C) with the reaction product of the component (A) and the component (B) and the component (D) are reacted, the molar ratio of the component (D) is (A ) To (C) It is an alkali-soluble resin characterized by being 20 to 110 mol% with respect to [2 × [(A)-(B)] + (C)] determined from the number of moles of the component.
The present invention also includes (i) the above alkali-soluble resin, (ii) a photopolymerizable monomer having at least one ethylenically unsaturated bond, and (iii) a photopolymerization initiator as essential components. It is a photosensitive resin composition.

  Moreover, this invention is the hardened | cured material obtained by hardening the said photosensitive resin composition. Furthermore, this invention is a color filter formed with the hardened | cured material obtained by apply | coating the said photosensitive resin composition and making it harden | cure.

（但し、Ｒ ₁ 、Ｒ ₂ 、Ｒ ₃ 、及びＲ ₄ は、独立に水素原子、炭素数１〜５のアルキル基、ハロゲン原子又はフェニル基を示し、Ｒ ₅ は水素原子又はメチル基を示す。また、Xは-CO-、-SO ₂ -、-C(CF ₃ ) ₂ -、-Si(CH ₃ ) ₂ -、-CH ₂ -、-C(CH ₃ ) ₂ -、-O-、9,9-フルオレニレン基又は直結合を示す。）と、下記の一般式で表されるテトラカルボン酸二無水物（B）

（但し、Yは、飽和環状炭化水素で置換されていてもよい飽和直鎖炭化水素テトラカルボン酸二無水物、飽和炭化水素で置換されていてもよい脂環式テトラカルボン酸二無水物、及び芳香族テトラカルボン酸二無水物から選ばれた１種以上のテトラカルボン酸二無水物のカルボン酸残基を示す。）とを反応させて得られたカルボキシル基を有する反応物に、下記の一般式で表され、重合性二重結合を少なくとも１つ以上含有し、かつ、オキシラン環を１つ含有するオキシラン化合物（C）

（但し、Ｒ ₆ は２価のアルキレン基、Ｒ ₇ は水素原子またはメチル基を示し、ｑは０または１の数を表す。）を反応させることで水酸基を有する反応物を得て、次いで、この水酸基を有する反応物に、下記の一般式で表され、ジカルボン酸、クエン酸、トリメリット酸及びヘキサヒドロトリメリット酸から選ばれた１種以上の酸一無水物（D）

（但し、Lは、炭化水素基で置換されていてもよい飽和直鎖炭化水素ジカルボン酸、飽和炭化水素基で置換されていてもよい飽和環状炭化水素ジカルボン酸、不飽和ジカルボン酸、芳香族ジカルボン酸、クエン酸、トリメリット酸及びヘキサヒドロトリメリット酸から選ばれた１種以上のカルボン酸残基を示し、pは１または２である）を反応させることを特徴とするアルカリ可溶性樹脂の製造方法であって、
上記（A）成分と（B）成分とを反応させる際の（A）成分と（B）成分のモル比〔(B)/(A)〕が５０モル％以上１００モル％未満であり、
（A）成分と（B）成分との反応物に（C）成分を反応させる際の（B）成分と（C）成分のモル比〔(C)/(B)〕が１６０〜２２０モル％であり、
（A）成分と（B）成分との反応物にさらに（C）成分を反応させて得られた反応物と（D）成分とを反応させる際、（D）成分のモル比が、（A）〜（C）成分のモル数から求められる［2×〔(A)−(B)〕+(C)］に対して２０〜１１０モル％であることを特徴とするアルカリ可溶性樹脂の製造方法である。 Furthermore, the present invention provides a diol compound (A) containing a polymerizable unsaturated group represented by the following general formula:

_{(Wherein, R 1, R 2, R} 3, and R ₄ are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ represents a hydrogen atom or a methyl group. X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9 , 9-fluorenylene a group or a straight bond.), tetracarboxylic acid dianhydride represented by the following formula (B)

(However, Y is a saturated linear hydrocarbon tetracarboxylic dianhydride which may be substituted with a saturated cyclic hydrocarbon, an alicyclic tetracarboxylic dianhydride which may be substituted with a saturated hydrocarbon, and the reactants with aromatic tetracarboxylic acid dianhydride shown a carboxylic acid residue of one or more tetracarboxylic acid dianhydrides selected from thereof.) and reacting the obtained carboxyl group, generally below An oxirane compound (C) represented by the formula and containing at least one polymerizable double bond and one oxirane ring

(Wherein R ₆ represents a divalent alkylene group, R ₇ represents a hydrogen atom or a methyl group, and q represents a number of 0 or 1) to obtain a reaction product having a hydroxyl group, One or more acid monoanhydrides (D) represented by the following general formula and selected from dicarboxylic acid , citric acid, trimellitic acid and hexahydrotrimellitic acid

(However, L is a saturated linear hydrocarbon dicarboxylic acid optionally substituted with a hydrocarbon group, a saturated cyclic hydrocarbon dicarboxylic acid optionally substituted with a saturated hydrocarbon group, an unsaturated dicarboxylic acid, or an aromatic dicarboxylic acid. Production of an alkali-soluble resin characterized by reacting at least one carboxylic acid residue selected from acids, citric acid, trimellitic acid and hexahydrotrimellitic acid, wherein p is 1 or 2) A method ,
The molar ratio [(B) / (A)] of the component (A) and the component (B) when the component (A) and the component (B) are reacted is 50 mol% or more and less than 100 mol%,
The molar ratio [(C) / (B)] of (B) component and (C) component when reacting (C) component with the reaction product of (A) component and (B) component is 160-220 mol% And
When the reaction product obtained by further reacting the component (C) with the reaction product of the component (A) and the component (B) and the component (D) are reacted, the molar ratio of the component (D) is (A ) To (C) 20 to 110 mol% with respect to [2 × [(A)-(B)] + (C)] determined from the number of moles of the component, It is.

Hereinafter, the present invention will be described in detail.
The photosensitive resin composition of the present invention is a resin composition having properties as an alkali developing photosensitive resin composition containing an alkali-soluble resin represented by the general formula (1) as a main component. The alkali-soluble resin represented by the general formula (1) has a photopolymerizable unsaturated group derived from a diol compound having (meth) acrylic acid, and thus has radical polymerizability, dicarboxylic acid or its acid monoanhydride. And has an acid solubility derived from tetracarboxylic acid or acid dianhydride, and thus has alkali solubility.

  The alkali-soluble resin of the general formula (1) is obtained by reacting (meth) acrylic acid with an epoxy compound having two glycidyl ether groups derived from bisphenols, and obtaining a diol compound having a polymerizable unsaturated group ( A) is reacted with a tetracarboxylic acid or its acid dianhydride (B), and the resulting reaction product is further reacted with an oxirane compound (C) containing a polymerizable double bond, and further with a dicarboxylic acid or its acid. It is a carboxyl group-containing alternating copolymer obtained by reacting an anhydride (D). Since the alkali-soluble resin of the general formula (1) has both a polymerizable unsaturated double bond and a carboxyl group, it gives excellent photocurability, good developability, and patterning characteristics to the alkali-developable photosensitive resin composition. The physical properties of the protective film, light shielding film, red, green, and blue pixels are improved.

The method for producing the alkali-soluble resin represented by the general formula (1) will be described in detail. First, the alkali-soluble resin of the general formula (1) is an epoxy compound having two glycidyl ether groups derived from bisphenols, particularly preferably an epoxy compound represented by the general formula (4) and (meth) acrylic acid. It is derived from a diol compound (A) containing a polymerizable unsaturated group obtained by reacting with.

In the general formula (4), R ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, preferably a hydrogen atom, It is a C1-C5 alkyl group or a phenyl group, More preferably, it is a hydrogen atom. X represents —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —Si (CH ₃ ) ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, 9 , 9-fluorenylene group or a direct bond, preferably 9,9-fluorenylene group. Here, the 9,9-fluorenylene group refers to a group represented by the following general formula (5).

Such a reaction between the epoxy compound and (meth) acrylic acid can be carried out using a known method, for example, using about 2 moles of (meth) acrylic acid per mole of the epoxy compound. The reactant obtained by this reaction is described in, for example, Patent Document 6 mentioned above. The reaction product obtained by this reaction is a diol compound (A) containing a polymerizable unsaturated group, and is an epoxy (meth) acrylate compound represented by the following general formula (6).

  Preferred bisphenols that give the alkali-soluble resin of the general formula (1) include the following. Bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4 -Hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) Hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4- Hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) Methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2 , 2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, Bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether and the like. In addition, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4- Hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4- Hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, etc. are also preferred Can be mentioned. Furthermore, 4,4′-biphenol, 3,3′-biphenol and the like are also preferred.

The alkali-soluble resin of the general formula (1) can be obtained from an epoxy compound derived from bisphenols as described above. In addition to such an epoxy compound, a phenol novolac type epoxy compound, a cresol novolak type epoxy compound, and the like are also available. Any compound that significantly contains a compound having two glycidyl ether groups can be used. In addition, when the bisphenol is glycidyl etherified, an oligomer unit represented by the following general formula (7) is mixed. The average value of m in the general formula (7) is 0 to 10, preferably 0. If it is in the range of ˜2, there is no problem in the performance of the resin composition.

（ただし、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｘ、Ｙ及びＧは上記一般式（１）の場合と同じである。また、Ｒ₆は２価のアルキレン基、Ｒ₇は水素原子またはメチル基を示し、Ｚは上記一般式（３）で表される置換基を示す。更に、ｎは１〜２０の数であり、ｐは一般式（３）の場合と同じであり、ｑは０または１の数を示す。） Next, a diol compound (A) containing a polymerizable unsaturated group, a tetracarboxylic acid or its acid dianhydride (B), an oxirane compound (C) containing a polymerizable unsaturated group, and a dicarboxylic acid or its acid The method for producing the alkali-soluble resin of the present invention represented by the general formula (1) by the reaction of the monoanhydride (D) will be described. An example of the method for producing the alkali-soluble resin of the present invention is shown in the following reaction formula (I).

(However, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , X, Y and G are the same as those in the general formula (1). R ₆ is a divalent alkylene group, R ₇ Represents a hydrogen atom or a methyl group, Z represents a substituent represented by the general formula (3), n is a number of 1 to 20, and p is the same as in the general formula (3). And q represents a number of 0 or 1.)

  Regarding the reaction formula (I), first, the epoxy (meth) acrylate compound of the general formula (6) obtained by the reaction of the above-described epoxy compound with (meth) acrylic acid [diol containing a polymerizable unsaturated group] Compound (A)] and an acid component are reacted to obtain a compound represented by the general formula (8) (reactant having a carboxyl group). The reaction conditions such as the solvent and catalyst used in this case are not particularly limited. For example, a solvent having no hydroxyl group and having a boiling point higher than the reaction temperature is preferably used as the reaction solvent. Cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high boiling point ether or ester solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, cyclohexanone, diisobutyl ketone, etc. It is preferable to use a ketone solvent. The catalyst used may be a known catalyst such as ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine. it can. These are described in detail in the aforementioned Patent Document 11. Moreover, it is good to use the tetracarboxylic dianhydride (B) which can react with the hydroxyl group in an epoxy (meth) acrylate compound molecule as an acid component. This acid component is effective either saturated or unsaturated. Among these, as tetracarboxylic dianhydride (B), acid dianhydride of saturated linear hydrocarbon tetracarboxylic acid, acid dianhydride of alicyclic tetracarboxylic acid, acid dianhydride of aromatic tetracarboxylic acid Things can be used.

Here, examples of the acid dianhydride of the saturated linear hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid dianhydride, and the like. or cyclic hydrocarbon substituted saturated linear acid dianhydride hydrocarbon tetracarboxylic acid.

In addition, as the acid dianhydride of alicyclic tetracarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid dianhydride, etc. It can be exemplified, and further may be a dianhydride of alicyclic tetracarboxylic acids substituted with a saturated hydrocarbon. Examples of the acid dianhydride of aromatic tetracarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and diphenylsulfone tetracarboxylic acid dianhydride. it can. The acid dianhydride in the present invention is preferably an acid dianhydride of biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, or biphenyl ether tetracarboxylic acid, and more preferably an acid dianhydride of biphenyl tetracarboxylic acid or biphenyl ether tetracarboxylic acid. It is a thing. Two or more of these acid dianhydrides can be used in combination. In addition, about these, you may use simple tetracarboxylic acid instead of an acid dianhydride.

  The method for producing the compound represented by the general formula (8) by reacting the epoxy (meth) acrylate compound and the acid component is not particularly limited, and for example, as described in Patent Document 11 described above. A known method such as reacting an epoxy (meth) acrylate compound with tetracarboxylic dianhydride at a reaction temperature of 90 to 140 ° C. can be employed. Preferably, the diol compound (A) having a polymerizable unsaturated group represented by the general formula (6) and the acid dianhydride (B) so that the terminal of the compound represented by the general formula (8) is a hydroxyl group. It is desirable to make the reaction quantitatively so that the molar ratio [(B) / (A)] to 50) is less than 100 mol%. When the molar ratio is less than 50 mol%, the content of the unreacted epoxy (meth) acrylate compound is increased, and there is a concern that the stability over time of the alkali-soluble resin composition is lowered. On the other hand, when the molar ratio is 100 mol% or more, the terminal of the compound represented by the general formula (8) becomes an acid anhydride, and after the content of unreacted acid dianhydride increases, There are concerns about side reactions during the reaction. The reaction temperature is preferably 90 to 130 ° C. and the raw materials are uniformly dissolved and reacted, followed by reaction and aging at 40 to 80 ° C.

  Subsequently, the compound represented by the general formula (8) is reacted with the oxirane compound (C) to obtain a compound represented by the general formula (9) (reactant having a hydroxyl group). The oxirane compound is a compound containing one or more polymerizable double bonds and one oxirane ring, and includes glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3,4- Examples include epoxy cyclohexyl methacrylate.

  About the manufacturing method of the compound represented by General formula (9), it does not specifically limit, The general reaction conditions of addition reaction of carboxylic acid and an epoxy compound can be used. In addition, as described in the above-mentioned Patent Document 11, an epoxy compound and (meth) acrylic acid that react bisphenolfluorene type epoxy resin and acrylic acid at 100 ° C. using tetraethylammonium bromide or the like as a catalyst. The manufacturing method of the epoxy (meth) acrylate compound by reaction with can also be referred. The reaction temperature for synthesizing the compound represented by the general formula (9) is preferably in the range of 40 to 120 ° C, more preferably 40 to 90 ° C. The molar ratio of the oxirane compound (C) when synthesizing the compound represented by the general formula (9) is the acid dianhydride (B) used in the reaction of the compound represented by the general formula (8). In other words, the molar ratio [(C) / (B)] is preferably 160 to 220 mol%. When the molar ratio is less than 160 mol%, part of the ester bond derived from the acid dianhydride in the compound represented by the general formula (9) becomes a half ester due to the presence of the unreacted carboxylic acid. There is a concern that the molecular weight may decrease due to the regeneration reaction of the acid anhydride. On the other hand, when the molar ratio exceeds 220 mol%, there is a concern about the change over time of the alkali-soluble resin represented by the general formula (1) due to a side reaction or the like derived from the unreacted oxirane compound.

Subsequently, the hydroxyl group of the compound represented by the general formula (9) is reacted with dicarboxylic acid or its acid monoanhydride (D) to obtain an alkali-soluble resin represented by the general formula (10). Here, as the dicarboxylic acid, a saturated linear hydrocarbon dicarboxylic acid, a saturated cyclic hydrocarbon dicarboxylic acid, an aromatic dicarboxylic acid, or the like can be used. Of these, examples of the saturated linear hydrocarbon dicarboxylic acid include succinic acid, acetyl succinic acid, adipic acid, azelaic acid, citralmalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, and sebacic acid. , suberic acid, and the like can be mentioned diglycolic acid, further can be a straight-chain hydrocarbon dicarboxylic acid substituted with a hydrocarbon group. As the saturated cyclic hydrocarbon dicarboxylic acids, for example, hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane carboxylic acid, can be cited hexa hydro trimellitic acid or the like, it is substituted with a saturated hydrocarbon An alicyclic dicarboxylic acid may be used. Further, examples of the unsaturated dicarboxylic acid include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, and trimellitic acid. Among these, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid and trimellitic acid are preferable, and succinic acid, itaconic acid and tetrahydrophthal are more preferable. The anhydride (D) is preferably an anhydride of succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, trimellitic acid, more preferably succinic acid, itaconic acid, tetrahydrophthalic acid anhydride. It is a thing. In addition, it cannot be overemphasized that the alkali-soluble resin represented by General formula (10) is an example of the alkali-soluble resin represented by General formula (1).

  The reaction temperature for synthesizing the compound represented by the general formula (10) by reacting the hydroxyl group of the compound represented by the general formula (9) with the acid monoanhydride (D) is 20 to 120 ° C. The range is preferably 40 to 90 ° C. The molar ratio of the dicarboxylic acid or its acid monoanhydride (D) when synthesizing the compound represented by the general formula (10) is the diol compound (A) having a polymerizable unsaturated group, tetracarboxylic acid or its With respect to the formula (2 × ((A)-(B)) + (C)) converted from the number of moles (mol) of the acid dianhydride (B) and the oxirane compound (C), that is, the molar ratio [( D) / [2 [(A)-(B) + (C)]]] is preferably 20 to 110 mol%. The molar ratio of the component (D) can be arbitrarily changed within the above range for the purpose of adjusting the acid value of the alkali-soluble resin represented by the general formula (1).

An example of the method for producing the general formula (1) will be specifically described in the case where 9,9-bis (4-hydroxyphenyl) fluorene is used as a starting material.
First, 9,9-bis (4-hydroxyphenyl) fluorene and epichlorohydrin are reacted to synthesize a bisphenolfluorene type epoxy compound represented by the following general formula (11). A bisphenolfluorene type epoxy (meth) acrylate resin represented by the following general formula (12) is synthesized by reacting with (meth) acrylic acid represented by CH ₂ = CHR ₅ -COOH (R ₅ is the same as above). To do. Then, this bisphenolfluorene type epoxy (meth) acrylate resin is heated in a solvent such as propylene glycol monomethyl ether acetate, and then tetracarboxylic acid or its acid dianhydride (B), oxirane compound (C), dicarboxylic acid or its acid. By reacting with the monoanhydride (D) sequentially, the alkali-soluble resin of the general formula (1) is obtained.

  Moreover, the photosensitive resin composition of this invention contains the alkali-soluble resin of the said General formula (1) as a main component of a resin component. Here, the resin component refers to a component that becomes a resin by polymerization or curing, and includes an oligomer and a monomer in addition to the resin. Further, “containing as a main component” means that the alkali-soluble resin represented by the general formula (1) is contained in the resin component at 30 wt% or more, preferably 50 wt% or more, more preferably 60 wt% or more. The photosensitive resin composition of the present invention may contain an alkali-soluble resin represented by the general formula (1) as an essential component, and components other than the resin of the general formula (1) may be resin components, And non-resin components such as fillers and colorants.

  In order to take advantage of the characteristics of the photosensitive resin composition, it is preferable to contain the following components (i) to (iii) as essential components. That is, (i) an alkali-soluble resin represented by the general formula (1), (ii) a photopolymerizable monomer having at least one ethylenically unsaturated bond, and (iii) a photopolymerization initiator are essential. Contains as an ingredient.

  Among these, as the photopolymerizable monomer having at least one ethylenically unsaturated bond as the component (ii), for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Monomers having a hydroxyl group such as ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pen Pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate of a (meth) acrylic acid esters. These compounds can be used alone or in combination of two or more thereof.

  The blending ratio [(i) / (ii)] of these (ii) component and (i) the alkali-soluble resin represented by the general formula (1) is preferably 20/80 to 90/10, Preferably it is 40 / 60-80 / 20. When the blending ratio of the alkali-soluble resin is small, the cured product after photocuring becomes brittle, and the acid value of the coating film is low in the unexposed area, so that the solubility in an alkali developer is lowered and the pattern edge is distorted. The problem of not getting sharp will occur. On the contrary, when the blending ratio of the alkali-soluble resin is larger than the above range, the ratio of the photoreactive functional group in the resin is small and the formation of the crosslinked structure is not sufficient, and the acid value in the resin component is too high, Since the solubility with respect to the alkaline developer in the exposed portion is increased, there is a possibility that the formed pattern becomes thinner than the target line width or the pattern is easily lost.

  Examples of the photopolymerization initiator of component (iii) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyl. Acetophenones such as acetophenone, benzophenone, 2-chlorobenzophenone, benzophenones such as p, p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2- (o-chlorophenyl) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4,5-diphenyl Biimidazole, 2- (o-methoxyphenyl) ) -4,5-diphenylbiimidazole, biimidazole compounds such as 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloro Halomethylthiazole compounds such as methyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloroRmethyl) -1,3,5-triazine, 2- ( 4-methoxystyryl) -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- ( Halomethyl-s-triazine compounds such as 4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 1,2-octanedione, 1- [4- (phenylthio) phenyl ]-, 2- (o-benzoyloxime), 1- (4-phenylsulfanylphenyl) butane-1,2-dione-2-oxime-o-benzoate, 1- (4-methylsulfanylphenyl) butane-1 , 2-dione-2-oxime-o-acetate, 1- (4-methylsulfanylphenyl) butan-1-oneoxime-o-acetate, etc., o-acyloxime compounds, benzyldimethyl ketal, thioxanthone, 2-chloro Thioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxone Organic compounds such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, anthraquinones such as 2,3-diphenylanthraquinone, organic peroxidation such as azobisisobutylnitrile, benzoyl peroxide, cumene peroxide Products, thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine. One or more of these photopolymerization initiators can be used.

  The amount of the photopolymerization initiator (iii) used is 2 to 50 parts by weight based on 100 parts by weight of the total of (i) the alkali-soluble resin represented by the general formula (1) and (ii) the photopolymerizable monomer. Preferably, the amount is 15 to 40 parts by weight. When the blending ratio of the photopolymerization initiator as the component (ii) is small, the speed of photopolymerization becomes slow and the sensitivity is lowered. On the other hand, if the number is too large, the sensitivity is too strong and the pattern line width becomes thicker than the pattern mask, and the line width that is faithful to the mask cannot be reproduced, or the pattern edge does not rattle and become sharp. Problems may arise. Incidentally, the photopolymerization initiator (iii) includes those having a photosensitizing action, but it is possible to add a photosensitizer separately.

  A photosensitive resin composition comprising, as essential components, an alkali-soluble resin represented by general formula (1) of component (i), a photopolymerizable monomer of component (ii), and a photopolymerization initiator of component (iii), It is useful for color filter materials such as color filter inks and protective films, and can be dissolved in the solvents shown below or mixed with various additives as necessary.

  When the photosensitive resin composition of the present invention is used for a color filter or the like, it is preferable to use a solvent in addition to the above components. Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2- Ketones such as pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene Glycol ethers such as glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Examples include acetates such as ether acetate, and the like, and these can be dissolved and mixed to form a uniform solution-like composition.

  Moreover, the photosensitive resin composition of the present invention may contain additives such as a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a solvent, a leveling agent, and an antifoaming agent as necessary. . Among these, examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl. Examples of the filler include glass fiber, silica, mica, and alumina. Examples of the antifoaming agent and leveling agent include silicon-based, fluorine-based, and acrylic compounds.

  The photosensitive resin composition of the present invention comprises an alkali-soluble resin represented by the general formula (1) in a solid content excluding a solvent (the solid content includes a monomer that becomes a solid content after curing), (ii) It is desirable that the total amount of the photopolymerizable monomer and (iii) the photopolymerization initiator is 70 wt% or more, preferably 80 wt%, more preferably 90 wt% or more. The amount of the solvent varies depending on the target viscosity, but is preferably in the range of 20 to 80 wt% with respect to the total amount. When using the photosensitive resin composition of this invention for color filters, it is suitable for a protective film use.

  The coating film (cured product) of the present invention is obtained, for example, by applying a solution of the photosensitive resin composition to a substrate or the like, drying, irradiating light (including ultraviolet rays, radiation, etc.) and curing it. can get. A coating film having a desired pattern can be obtained by providing a portion that is exposed to light and a portion not exposed to light, curing only the portion that is exposed to light, and dissolving the other portion with an alkaline solution.

  Next, the manufacturing method of the color filter using the photosensitive resin composition is demonstrated. First, after applying the photosensitive resin composition on the surface of the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Next, this coating film is exposed through a photomask, and then developed using an alkaline developer to dissolve and remove the unexposed portions of the coating film, and then post-baked to define the portions where pixels are to be formed. A black matrix formed as described above is obtained. For example, after applying a liquid composition of a photosensitive resin composition in which a red pigment is dispersed on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Next, after exposing the coating film through a photomask, development using an alkaline developer is performed to dissolve and remove the unexposed portion of the coating film, and then post-baking to form a predetermined red pixel pattern. A pixel array arranged in an array is formed. Thereafter, using the liquid composition of the photosensitive resin composition in which the green or blue pigment is dispersed, the liquid composition is coated, pre-baked, exposed, developed and post-baked in the same manner as described above. By sequentially forming a pixel array and a blue pixel array on the same substrate, a pixel array of three primary colors of red, green and blue is arranged on the substrate, and further, a protective film is formed on the photosensitive resin composition as a protective film thereon. In the same manner as described above, the liquid composition is applied, pre-baked, exposed, developed and post-baked to obtain a color filter on which a protective film is formed.

  When applying the photosensitive resin composition to the substrate, any method such as a method using a roller coater machine, a land coater machine, or a spinner machine can be adopted in addition to a known solution dipping method and spray method. . After applying to a desired thickness by these methods, the film is formed by removing the solvent (pre-baking). Pre-baking is performed by heating with an oven, a hot plate, etc., vacuum drying, or a combination thereof. The heating temperature and heating time in the pre-baking are appropriately selected according to the solvent used, and for example, the heating is performed at a temperature of 80 to 120 ° C. for 1 to 10 minutes.

  As the radiation used when producing the color filter, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like can be used, and radiation having a wavelength in the range of 250 to 450 nm is preferable. . Examples of the developer suitable for the alkali development include, for example, an aqueous solution of an alkali metal or alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like. It is better to develop at a temperature of 20-30 ° C. using a weakly alkaline aqueous solution containing 0.05-10% by weight of carbonate such as lithium carbonate, and a fine image using a commercially available developing machine or ultrasonic cleaner. Can be formed precisely. In addition, it is usually washed with water after alkali development. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 10 to 120 seconds at room temperature.

  After the development as described above, a heat treatment (post-bake) is performed at a temperature of 180 to 250 ° C. and a condition of 20 to 100 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned coating film and the substrate. This is performed by heating with an oven, a hot plate or the like, as in the pre-bake. The patterned coating film of this invention is formed through each process by the above photolithography method.

  Examples of the substrate used when forming a color filter having pixels and / or a black matrix include glass and transparent films (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.). In addition, these substrates are optionally subjected to appropriate pretreatments such as application of a transparent electrode layer, chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc. It can also be applied.

  Since the photosensitive resin composition of the present invention contains an alkali-soluble resin represented by the general formula (1), it has higher solubility in an alkali developer than conventional ones, and is ethylenically unsaturated in one molecule. Due to the large number of bonding groups, the crosslinking density after curing is high. That is, since the difference in solubility in the alkaline developer between the cured portion and the uncured portion after irradiation with ultraviolet rays or electron beams is increased, a fine pattern can be formed even in a thin film or at a high colorant concentration. Therefore, the photosensitive resin composition of the present invention is suitable for forming a color filter, and is particularly suitable as a color filter protective film material. The color filter thus obtained is extremely useful for, for example, a transmissive, reflective, or transflective color liquid crystal display device, a color imaging tube element, a color sensor, and the like.

  Hereinafter, the present invention will be described in more detail based on examples and comparative examples. The scope of the present invention is not limited by these examples and comparative examples. Moreover, evaluation of resin in the following examples etc. was performed as follows unless otherwise noted.

[Solid content]
1 g of a resin solution (including the case of a reaction product or an alkali-soluble resin) obtained in the examples (including comparative examples) is impregnated in a glass filter [weight: W ₀ (g)] and weighed [ W ₁ (g)], and the weight after heating at 160 ° C. for 2 hours [W ₂ (g)] was obtained from the following formula.
Solid content concentration (% by weight) = 100 × (W ₂ −W ₀ ) / (W ₁ −W ₀ )

[Acid value]
The resin solution was dissolved in dioxane and titrated with a 1/10 N-KOH aqueous solution using phenolphthalein as an indicator.

[Molecular weight]
This is a value obtained by calculating the weight average molecular weight (Mw) as a standard polystyrene conversion value by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent.

The abbreviations used in the examples are as follows.
FHPA: Equivalent reaction product of bisphenolfluorene type epoxy resin and acrylic acid (manufactured by Nippon Steel Chemical Co., Ltd., ASF-400 solution: solid content concentration 50wt%, solid content converted acid value 1.28mgKOH / g)
FHPPA: Equivalent reaction product of bis (phenylphenol) fluorene type epoxy resin and acrylic acid (50wt% PGMEA solution, solid content equivalent acid value 7.51mgKOH / g)
BisA-GEA: Equivalent reaction product of bisphenol A diglycidyl ether and acrylic acid (50wt% PGMEA solution, acid value 1.72mgKOH / g in solid content)
BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride
BTDA: 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride
ODPA: 3,3 ', 4,4'-oxydiphenyltetracarboxylic dianhydride
CHDA: 3,3 ', 4,4'-oxydiphenyltetracarboxylic dianhydride
THPA: 1,2,3,6-tetrahydrophthalic anhydride
HHPA: Hexahydrophthalic anhydride
GMA: Glycidyl methacrylate
HBAGE: 4-hydroxybutyl acrylate glycidyl ether
TEAB: Tetraethylammonium bromide
TPP: Triphenylphosphine
PGMEA: Propylene glycol monomethyl ether acetate

[Example 1]
In a 1000 ml four-necked flask with a reflux condenser, 600.00 g (0.49 mol) of a 50% PGMEA solution of FHPA [component (A)], 72.75 g (0.247 mol) of BPDA [component (B)], and 39.56 PGMEA 1.30 g of g and TPP were charged, stirred at 120 to 125 ° C. with heating for 2 hours, and further heated and stirred at 70 to 75 ° C. for 6 hours to obtain a reaction product (a). The solid content concentration of the obtained reaction product (a) was 52.4 wt%, the acid value (converted to solid content) of the resin was 78.0 mgKOH / g, and the weight average molecular weight (Mw) by GPC analysis was 3400.

  Next, 73.92 g (0.52 mol) of GMA [component (C)] was charged into the reaction product (a), and the mixture was stirred at 80 ° C. for 8 hours to be reacted. Further, 156.71 g (1.03 mol) of THPA [component (D)] was charged into the flask and stirred at 80 ° C. for 7 hours to synthesize an alkali-soluble resin (1) -1. The obtained alkali-soluble resin had a solid content of 62.0 wt%, an acid value (in terms of solid content) of 111.8 mg KOH / g, and Mw of 3700 by GPC analysis. In addition, (A)-(D) component name used for the synthesis | combination of alkali-soluble resin (1) -1 which concerns on Example 1, and a mixture ratio, the weight average molecular weight of obtained alkali-soluble resin (1) -1, and The acid values are collectively shown in Table 1 (the same applies to the following Examples and Reference Examples).

[Example 2]
In a 1000 ml four-necked flask equipped with a reflux condenser, 600.00 g (0.49 mol) of a 50% PGMEA solution of FHPA (A), 96.02 g (0.33 mol) of BPMDA (component (B)), 4.36 g of PGMEA, and TEAB was added in an amount of 1.02 g, and the mixture was stirred at 120 to 125 ° C. for 2 hours with heating, and further heated and stirred at 60 to 65 ° C. for 8 hours to obtain a reaction product (b). The obtained reaction product (b) had a solid content concentration of 57.8 wt%, an acid value (converted to a solid content) of 91.6 mg KOH / g, and Mw by GPC analysis of 8800.

  Next, 93.82 g (0.66 mol) of GMA [component (C)] was charged into the reaction product (b), and the mixture was stirred at 80 ° C. for 24 hours to be reacted. Furthermore, 153.67 g (1.01 mol) of THPA [(D) component] and 153.67 g of PGMEA were charged into the flask and stirred at 80 ° C. for 24 hours to synthesize an alkali-soluble resin (1) -2. The obtained alkali-soluble resin had a solid content concentration of 59.2 wt%, an acid value (in terms of solid content) of 126.8 mgKOH / g, and Mw of 6800 by GPC analysis.

[Example 3]
In a 500 ml four-necked flask equipped with a reflux condenser, 200.0 g of the reaction product (b) obtained in Example 2 above and 13.36 g (0.094 mol) of GMA [component (C)] were charged at 80 ° C. for 24 hours. The mixture was further stirred for 28 hours, and 28.91 g (0.19 mol) of THPA [component (D)] and 28.91 g of PGMEA were charged in the flask and stirred at 80 ° C. for 24 hours to synthesize an alkali-soluble resin (1) -3. The obtained alkali-soluble resin had a solid content concentration of 59.2 wt%, an acid value (in terms of solid content) of 100.3 mg KOH / g, and Mw by GPC analysis of 6700.

[Example 4]
Into a 500 ml four-necked flask equipped with a reflux condenser, 200.0 g of the reaction product (b) obtained in Example 2 and 27.01 g (0.19 mol) of GMA (component (C)) were charged, and the mixture was heated at 80 ° C for 24 hours The mixture was further stirred, and 12.78 g (0.084 mol) of THPA [component (D)] and 12.78 g of PGMEA were charged into the flask and stirred at 80 ° C. for 24 hours to synthesize an alkali-soluble resin (1) -4. The obtained alkali-soluble resin had a solid content concentration of 60.5 wt%, an acid value (in terms of solid content) of 32.5 mgKOH / g, and Mw of 6400 by GPC analysis.

[Examples 5 to 14]
In place of at least a part of the components (A) to (D) used in Example 2 above, the raw materials described in Table 1 below, that is, instead of FHPA, BPDA, THPA or GMA in Example 2, Table 1 The reaction was carried out in the same manner as in Example 2 except that the raw materials described were used to obtain alkali-soluble resins (1) -5 to (1) -14.

[Example 15]
A reaction was carried out in the same manner as in Example 1 except that the amount of THPA [component (D)] in Example 1 was changed to 118.68 g (0.78 mol) to obtain an alkali-soluble resin (1) -15. .

[Reference Example 1]
In a 500 ml four-necked flask with a reflux condenser, 206.26 g (0.17 mol) of a 50% PHPEA solution of FHPA, 0.085 mol of BPDA, 0.085 mol of THPA, 26.0 g of PGMEA and 0.45 g of TPP are charged, 120 to 125 The mixture was stirred for 6 hours while heating at 0 ° C. to obtain Resin (Reference) -1. The obtained resin solution had a solid content concentration of 55.6 wt%, an acid value (in terms of solid content) of 103.0 mg KOH / g, and Mw by GPC analysis of 2600.

[Reference Example 2]
In a 1000 ml four-necked flask equipped with a reflux condenser, 600.00 g (0.49 mol) of 50% PHPEA solution of FHPA, 96.02 g (0.33 mol) of BPDA, 4.36 g of PGMEA, and 1.02 g of TEAB are charged, 120 to 125 The mixture was stirred for 2 hours while being heated at ° C, and further heated and stirred at 60 to 65 ° C for 8 hours to obtain Resin (Reference) -2. The obtained resin solution had a solid content concentration of 58.5 wt%, an acid value (converted to solid content) of 91.0 mgKOH / g, and Mw by GPC analysis of 8600.

Next, the present invention will be specifically described based on examples and comparative examples relating to the manufacture of color filters. The present invention is not limited to these. Here, the raw materials and abbreviations used in the production of the color filters according to the examples and comparative examples are as follows.
(1) Component: (1) -1 to (1) -4, (Reference) -1, and (Reference) -2 [Alkali-soluble resin obtained in Examples 1 to 4 and Reference Examples 1 and 2 above]
(ii) -1 Component: Dipentaerythritol hexaacrylate
(iii) -1 component: oxime ester photopolymerization initiator (Irgacure OXE01, manufactured by Ciba Specialty Chemicals)
(iii) -2 component: Michler's ketone (photosensitizer)
(v) Component: Tetramethylbiphenyl type epoxy resin Solvent: Cellosolve acetate

  By blending the above blending components [(1), (ii), (iii) and (v)] in the proportions shown in Table 2, the alkali-solubility obtained in Examples 1-4 and Reference Examples 1-2 above. A photosensitive resin composition using a resin was prepared.

[Examples 16 to 19, Comparative Examples 1 and 2]
The film thickness after post-baking the photosensitive resin composition using the alkali-soluble resin obtained in Examples 1 to 4 and Reference Examples 1 and 2 onto a 125 mm × 125 mm glass substrate using a spin coater Was applied to a thickness of 2 μm and prebaked at 90 ° C. for 2 minutes to prepare a coated plate. Thereafter, UV irradiation of 10 mW / cm ² with a wavelength of 365 nm was irradiated for 10 seconds with a 500 W / cm ² high-pressure mercury lamp through a pattern mask to carry out a photocuring reaction of the photosensitive part. Next, the exposed coated plate was developed and washed with water for 20 seconds after a desired pattern was visually recognized at 25 ° C. in a 1 wt% sodium carbonate aqueous solution, and the unexposed portion of the coating film was removed. Thereafter, a heat drying treatment was performed at 230 ° C. for 30 minutes using a hot air dryer to obtain a test color filter. The developability, development adhesion, etc. of the test color filters of Examples 16 to 19 and Comparative Examples 1 and 2 were evaluated. Specifically, the obtained sample was evaluated for the drying property of the coating film, the developability with respect to the aqueous alkali solution, the exposure sensitivity, the coating film hardness, the adhesion to the substrate, the heat resistance, and the chemical resistance. The results are shown in Table 3. Various physical property data were measured under the following conditions.

(1) Drying property of coating film The drying property of the coating film was evaluated according to JIS-K5400. The rank of evaluation is as follows.
○: Tack is not recognized at all Δ: Slightly tack is recognized ×: Tack is remarkably recognized

(2) Developability for aqueous alkali solution
After the pattern was developed in a 1% by weight sodium carbonate aqueous solution at 25 ° C., the pattern was further immersed for 20 seconds for development. After development, the resin remaining after 40 times magnification was visually evaluated. The rank of evaluation is as follows.
○: Good developability (no resist remains on the glass)
Δ: Slightly poor developability (slightly resist remains on glass)
X: Those with poor developability (those with a little resist remaining on the glass)

(3) Exposure sensitivity
An exposure mask having a 10 μm fine line pattern was adhered to the coating film, and a light amount of 100 mJ / cm ² was irradiated using a 500 W high-pressure mercury lamp. Next, the pattern was developed at 25 ° C. in a 1 wt% sodium carbonate aqueous solution with respect to an aqueous alkali solution, and then developed by dipping for another 20 seconds. After development, the line width of the formed fine line pattern was evaluated (in this evaluation method, the higher the sensitivity, the thicker the line width).

(4) Coating film hardness After the exposure and development, the coating film heated at 230 ° C for 30 minutes was coated with a load of 1 kg using a pencil hardness tester according to the test method of JIS-K5400. Displayed with the highest hardness without scratches. The pencil used is "Mitsubishi High Uni".

(5) Adhesion to substrate After exposure and development, cross-cuts are made in the coating film heated at 230 ° C for 30 minutes to make at least 100 grids, and then peeled off using cello tape (registered trademark). A test was conducted, and the state of peeling of the grid was visually evaluated. The rank of evaluation is as follows.
○: No peeling at all ×: Even a little peeling is recognized

(6) Heat resistance After exposure and development, the coating film heated at 230 ° C. for 30 minutes was placed in an oven at 250 ° C. for 3 hours to evaluate the state of the coating film. The rank of evaluation is as follows.
○: No abnormality in the appearance of the coating film ×: The appearance of the coating film is peeled off and colored.

(7) Chemical resistance After exposure and development, the coating film heated at 230 ° C. for 30 minutes was immersed in the following chemicals under the following conditions, and the appearance and adhesion after immersion were evaluated.
Acid resistance test: Alkaline resistance test for 24 hours in 5% HCl 1: Alkaline resistance test for 24 hours in 5% NaOH 2: Alkali resistance test for 10 minutes in 4% KOH at 50 ° C 3: Alkaline resistance test in 5% 1% NaOH at 80 ° C for 5 hours 1 minute immersion solvent resistance test 1: 10 minutes immersion in NMP (N-methyl-pyrrolidone) at 40 ° C. 2: 2 minute immersion in NMP at 80 ° C.

  As is clear from the results in Table 3 above, Examples 16 to 19, especially Examples 16 and 17, are excellent in developability and adhesion as compared with Comparative Examples. That is, the cured portion has a large difference in solubility in the alkaline developer between the cured portion and the uncured portion after irradiation with ultraviolet light or electron beam, and has good developability and high adhesion by increasing the number of ethylenically unsaturated bond groups in one molecule. It has been found that a membrane can be provided.

  The photosensitive resin composition of the present invention has higher solubility in an alkali developer than conventional ones, and has a high crosslinking density after curing because of the large number of ethylenically unsaturated bond groups in one molecule. That is, since the difference in solubility in the alkaline developer between the cured portion and the uncured portion after irradiation with ultraviolet rays or electron beams is increased, a fine pattern can be formed even in a thin film or at a high colorant concentration. Therefore, the photosensitive resin composition of the present invention includes various multicolor displays such as color liquid crystal display devices, color facsimiles, and image sensors, and color inks for color filters used in optical devices, and the like. It can be suitably used for a color filter having a formed black matrix, a television, a video monitor, or a computer display. In particular, it is suitable as a color filter protective film material. The color filter thus obtained is extremely useful for, for example, a transmissive, reflective, or transflective color liquid crystal display device, a color imaging tube element, a color sensor, and the like.

Claims (6)

An alkali-soluble resin represented by the following general formula (1) and having a carboxylic acid residue and a polymerizable unsaturated group in the molecule.

_{(Wherein, R 1, R 2, R} 3, and R ₄ are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ represents a hydrogen atom or a methyl group. X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9 , 9-fluorenylene group or a straight bond, Y is a saturated cyclic hydrocarbon optionally substituted with saturated straight-chain hydrocarbon tetracarboxylic acid dianhydride, saturated hydrocarbons which may be substituted by cycloaliphatic 1 represents a carboxylic acid residue of one or more tetracarboxylic dianhydrides selected from tetracarboxylic dianhydrides and aromatic tetracarboxylic dianhydrides, where G is represented by the following general formula (2). A substituent having a polymerizable double bond and a carboxyl group is shown, Z is a substituent represented by the following general formula (3), and n is a number of 1 to 20.

(However, R ₈ is an aliphatic hydrocarbon group having 3 to 6 carbon atoms, R ₆ is a divalent alkylene group, R ₇ is a hydrogen atom or a methyl group, and Z is the same as in the following general formula (3). Q represents a number of 0 or 1.)

(Where, L is a hydrocarbon group which may be substituted saturated linear hydrocarbon dicarboxylic acids, saturated optionally substituted with a saturated hydrocarbon group a cyclic hydrocarbon dicarboxylic acids, unsaturated dicarboxylic acids, aromatic dicarboxylic 1 or more carboxylic acid residues selected from acid, citric acid, trimellitic acid and hexahydrotrimellitic acid, and p is 1 or 2) Diol compound (A) containing a polymerizable unsaturated group represented by the following general formula

_{(Wherein, R 1, R 2, R} 3, and R ₄ are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ represents a hydrogen atom or a methyl group. X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9 , 9-fluorenylene group or a direct bond.) And tetracarboxylic dianhydride (B) represented by the following general formula

(However, Y is a saturated linear hydrocarbon tetracarboxylic dianhydride which may be substituted with a saturated cyclic hydrocarbon, an alicyclic tetracarboxylic dianhydride which may be substituted with a saturated hydrocarbon, and the reactants with aromatic tetracarboxylic acid dianhydride shown a carboxylic acid residue of one or more tetracarboxylic acid dianhydrides selected from thereof.) and reacting the obtained carboxyl group, generally below An oxirane compound (C) represented by the formula and containing at least one polymerizable double bond and one oxirane ring

(Wherein R ₆ represents a divalent alkylene group, R ₇ represents a hydrogen atom or a methyl group, and q represents a number of 0 or 1) to obtain a reaction product having a hydroxyl group, One or more acid monoanhydrides (D) represented by the following general formula and selected from dicarboxylic acid, citric acid, trimellitic acid and hexahydrotrimellitic acid

(However, L is a saturated linear hydrocarbon dicarboxylic acid optionally substituted with a hydrocarbon group, a saturated cyclic hydrocarbon dicarboxylic acid optionally substituted with a saturated hydrocarbon group, an unsaturated dicarboxylic acid, or an aromatic dicarboxylic acid. An alkali-soluble resin obtained by reacting at least one carboxylic acid residue selected from acid, citric acid, trimellitic acid and hexahydrotrimellitic acid, and p is 1 or 2 .
The molar ratio [(B) / (A)] of the component (A) and the component (B) when the component (A) and the component (B) are reacted is 50 mol% or more and less than 100 mol%,
The molar ratio [(C) / (B)] of (B) component and (C) component when reacting (C) component with the reaction product of (A) component and (B) component is 160-220 mol% And
When the reaction product obtained by further reacting the component (C) with the reaction product of the component (A) and the component (B) and the component (D) are reacted, the molar ratio of the component (D) is (A ) To (C) Alkali-soluble resin, characterized in that it is 20 to 110 mol% based on [2 × [(A)-(B)] + (C)] determined from the number of moles of the component.   (I) The alkali-soluble resin according to claim 1, (ii) a photopolymerizable monomer having at least one ethylenically unsaturated bond, and (iii) a photopolymerization initiator as essential components. The photosensitive resin composition characterized by the above-mentioned.   A cured product obtained by curing the photosensitive resin composition according to claim 3.   A color filter formed by a cured product obtained by applying and curing the photosensitive resin composition according to claim 3. Diol compound (A) containing a polymerizable unsaturated group represented by the following general formula

_{(Wherein, R 1, R 2, R} 3, and R ₄ are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ represents a hydrogen atom or a methyl group. X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9 , 9-fluorenylene group or a direct bond.) And tetracarboxylic dianhydride (B) represented by the following general formula

(However, Y is a saturated linear hydrocarbon tetracarboxylic dianhydride which may be substituted with a saturated cyclic hydrocarbon, an alicyclic tetracarboxylic dianhydride which may be substituted with a saturated hydrocarbon, and the reactants with aromatic tetracarboxylic acid dianhydride shown a carboxylic acid residue of one or more tetracarboxylic acid dianhydrides selected from thereof.) and reacting the obtained carboxyl group, generally below An oxirane compound (C) represented by the formula and containing at least one polymerizable double bond and one oxirane ring

(Wherein R ₆ represents a divalent alkylene group, R ₇ represents a hydrogen atom or a methyl group, and q represents a number of 0 or 1) to obtain a reaction product having a hydroxyl group, One or more acid monoanhydrides (D) represented by the following general formula and selected from dicarboxylic acid, citric acid, trimellitic acid and hexahydrotrimellitic acid

(However, L is a saturated linear hydrocarbon dicarboxylic acid optionally substituted with a hydrocarbon group, a saturated cyclic hydrocarbon dicarboxylic acid optionally substituted with a saturated hydrocarbon group, an unsaturated dicarboxylic acid, or an aromatic dicarboxylic acid. Production of an alkali-soluble resin characterized by reacting at least one carboxylic acid residue selected from acids, citric acid, trimellitic acid and hexahydrotrimellitic acid, wherein p is 1 or 2) A method,
The molar ratio [(B) / (A)] of the component (A) and the component (B) when the component (A) and the component (B) are reacted is 50 mol% or more and less than 100 mol%,
The molar ratio [(C) / (B)] of (B) component and (C) component when reacting (C) component with the reaction product of (A) component and (B) component is 160-220 mol% And
When the reaction product obtained by further reacting the component (C) with the reaction product of the component (A) and the component (B) and the component (D) are reacted, the molar ratio of the component (D) is (A ) To (C) 20 to 110 mol% with respect to [2 × [(A)-(B)] + (C)] determined from the number of moles of the component, .