JP5406605B2 - Heat resistant resin and resin composition containing the same - Google Patents

Description

  The present invention relates to a resin having excellent heat resistance, and for example, to a highly heat resistant resin that can be used in the production of color filters and the like and can obtain a resin composition having excellent shape retention performance under thermosetting conditions. .

  A color liquid crystal display device includes a liquid crystal unit that controls the amount of light transmitted or reflected and a color filter as constituent elements. In this method of manufacturing a color filter, the surface of a transparent substrate such as glass or plastic sheet is usually used. A method is adopted in which a black matrix is formed, and subsequently different hues such as 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. Color filters are an important member that affects the visibility of these color liquid crystal display devices. One.

  As a general method for forming a black matrix, a photosensitive resin composition containing a carbon pigment, a resin pigment, or the like is patterned by a photolithographic method, and the photosensitive resin composition is used as a black matrix. Here, in post-baking, which is a thermosetting step after development and rinsing, it is necessary to maintain the formed tapered shape when exposed to heat at around 230 ° C. for several minutes to several tens of minutes.

  In particular, when a color pattern (pixel) is formed by an ink jet method, a black matrix is used as an ink holding frame, and therefore, at least 1 μm or more is required to obtain a thickness of a colored portion that satisfies the color characteristics of the color filter. Therefore, it is more difficult to maintain a tapered shape during post-baking.

  In the production of a color filter, it is exposed to heat at around 250 ° C. in the process of adhering ITO as an electrode. However, in order to prevent the color filter from cracking, a heat and heat resistant material is required. come.

  Therefore, for example, in Patent Document 1, an unsaturated group-containing compound obtained by further reacting a reaction product of a specific aromatic epoxy compound and (meth) acrylic acid with a polybasic carboxylic acid or an anhydride thereof is used as a resin main component. Black resist containing as a component has a high light-shielding rate, easy to form fine patterns by photolithography, and also has a light-shielding thin film with excellent insulation, heat resistance, adhesion, and room temperature storage stability Reported to be a forming composition. However, this Patent Document 1 describes a black resist for a thin film having a standard thickness of 1 μm, which is a standard thickness of a black matrix, and guarantees the shape retention performance when the film thickness exceeds 1.5 μm. There is no direct mention of the heat resistance to do this.

  On the other hand, Patent Documents 2 and 3 are examples of color filter-related materials that are thick films. Among these, Patent Document 2 is a method for forming a film by repeating thin film printing, and relates to the formation of a color filter by a printing method that does not have exposure and thermal baking processes, and considers the heat resistance of the formed color filter. There is no description to do. Further, Patent Document 3 relates to a method for increasing the development time each time the number of development processes for forming a black matrix is repeated, and obtains a black matrix having excellent shape reproducibility with little variation in shape. There is no description considering the heat resistance of the black matrix.

  Patent Documents 4 and 5 describe resin compositions for color filters that are excellent in various performances such as resolution and heat resistance by using an alkali-soluble novolak resin such as a cresol novolak resin and a styrene / hydroxystyrene polymer as a binder resin. Suppose you get things. However, in these patent documents, the heat resistance evaluation of the obtained colored pattern is performed at 200 ° C., and the shape retention performance under higher temperature conditions is not mentioned.

JP-A-8-278629 JP-A-5-045513 JP 2003-270431 A JP-A-6-194427 JP-A-6-194835

  Therefore, the present inventors can maintain the shape in a high-temperature thermosetting process even when a thick film such as a color pattern or a black matrix is obtained in the production of a color filter. As a result of diligent research on a resin having heat resistance that can withstand an ITO bonding process exceeding 1%, a new resin in which a predetermined fluorene skeleton is connected with a novolac structure can satisfy all of the above performances. The present invention has been completed by finding out what can be done.

  Accordingly, an object of the present invention is to provide a resin that is excellent in heat resistance and can retain its shape even under high temperature thermosetting conditions in the production of color filters, for example.

  Another object of the present invention is to provide a resin composition excellent in shape retention performance under heating conditions.

（ｎ₁〜ｎ₂はそれぞれ独立して０〜２０の整数を示し、ｎ₃は０〜１０の整数を示し、ｎ₁〜ｎ₃の合計は１以上の整数である。また、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、及びＲ⁷は水素原子、ハロゲン原子、アルキル基又はアリール基から選ばれる同一あるいは相異なる一価の置換基であり、Ｒ¹とＲ²及び／又はＲ⁵とＲ⁶とＲ⁷は環を形成していてもよい。Ｚは、水素原子又は以下の一般式（II）で示される構造を持つ１価の末端基である。）

（Ｒ⁸〜Ｒ¹²のうち主鎖（-CHR⁴-）に対してオルソ位又はパラ位の３つの置換基のうち少なくとも一つは水酸基を示す。その他のＲ⁸〜Ｒ¹²は、水素原子、ハロゲン原子、水酸基、アルキル基又はアリール基から選ばれる同一あるいは相異なる一価の置換基を示し、Ｒ⁸〜Ｒ¹²の隣り合う二つの置換基は環を形成していてもよい。） That is, the present invention is a resin represented by the following general formula (I) and having a molecular weight of 500 to 10,000.

(N ₁ ~n ₂ each independently an integer of 0 to 20, n ₃ represents an integer of 0, the sum of n ₁ ~n ₃ is an integer of 1 or more. Further, R ^1, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different monovalent substituents selected from a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and R ¹ and R ² And / or R ⁵ , R ⁶ and R ⁷ may form a ring, and Z is a hydrogen atom or a monovalent end group having a structure represented by the following general formula (II).

(Backbone (-CHR ⁴ of R ⁸ ~R ¹² -. At least one of) three substituents ortho or para to show the hydroxyl group other R ⁸ to R ¹² is a hydrogen atom And the same or different monovalent substituent selected from a halogen atom, a hydroxyl group, an alkyl group or an aryl group, and two adjacent substituents of R ^{8 to} R ¹² may form a ring.)

（ｎ₁〜ｎ₂はそれぞれ独立して０〜２０の整数を示し、ｎ₃は０〜１０の整数を示し、ｎ₁〜ｎ₃の合計は１以上の整数を示す。Ｒ ¹ 、Ｒ ² 、Ｒ ³ 、Ｒ ⁴ 、Ｒ ⁵ 、Ｒ ⁶ 、及びＲ ⁷ は水素原子、ハロゲン原子、アルキル基又はアリール基から選ばれる同一あるいは相異なる一価の置換基であり、Ｒ ¹ とＲ ² 及び／又はＲ ⁵ とＲ ⁶ とＲ ⁷ は環を形成していてもよい。Ｘは水素原子あるいは(メタ)アクリル基を示し、Ｒ⁸〜Ｒ¹²のうち主鎖（-CHR⁴-）に対してオルソ位又はパラ位の３つの置換基のうち少なくとも一つはＯＸ基を示し、かつ、全てのＸの総数に対して(メタ)アクリル基の割合は１０〜１００％である。その他のＲ ⁸ 〜Ｒ ¹² は、水素原子、ハロゲン原子、水酸基、アルキル基又はアリール基から選ばれる同一あるいは相異なる一価の置換基を示し、Ｒ ⁸ 〜Ｒ ¹² の隣り合う二つの置換基は環を形成していてもよい。） The present invention is also a photosensitive resin represented by the following general formula (III) and having a molecular weight of 600 to 12000.

(N ₁ ~n ₂ each independently an integer of 0 to 20, n ₃ represents an integer of 0, the sum of n ₁ ~n ₃ represents an integer of 1 or more. R ^1, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different monovalent substituents selected from a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and R ¹ and R ² and / or Or R ⁵ , R ^6, and R ⁷ may form a ring, X represents a hydrogen atom or a (meth) acryl group, and R ^{8 to} R ^{12 represent} the main chain (—CHR ⁴ —). At least one of the three substituents in the ortho-position or para-position represents an OX group, and the ratio of the (meth) acryl group is 10 to 100% with respect to the total number of all X. Other R ⁸ to R ¹² is a hydrogen atom, a halogen atom, a hydroxyl group, the same or different monovalent substituents selected from alkyl or aryl group Shown, two substituents adjacent to R ⁸ to R ¹² may form a ring.)

  Furthermore, the present invention provides a photosensitive resin composition comprising (A) any one of the above resins, (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, and (C) a photopolymerization initiator. It is a thing.

The resin represented by the general formula (I) has a bisphenolfluorene skeleton bonded with a novolac structure. N ₁ in formula ~n ₂ each independently an integer of 0 to 20, n ₃ represents an integer of 0, the sum of n ₁ ~n ₃ is an integer of 1 or more. Among these, regarding the repeating structure of n ₂ and n ₃ , the resin of the general formula (I) is not limited to block copolymerization, and may be an alternating copolymer or a random copolymer. Good. The photosensitive resin represented by the general formula (III) can be obtained by reacting the resin of the above general formula (I) with (halogen) (meth) acrylate or (meth) acrylic anhydride. Hereinafter, the present invention including these resins will be described in detail.

The resin represented by the general formula (I) has a novolak structure in which bisphenolfluorenes and phenols are crosslinked using aldehydes. When the terminal group Z is a hydrogen atom, that is, when only the bisphenolfluorenes and the phenols represented by the repeating structure of n ₂ and n ₃ are crosslinked, the solubility in organic solvents is poor, and the molecular weight control during synthesis is difficult. It is desirable to add a phenol which is the terminal group Z represented by the general formula (II), that is, a phenol having only one hydrogen atom at the ortho-position or para-position of the phenolic hydroxyl group at the time of resin synthesis. In addition, a structure in which phenols are inserted as spacers between bisphenol fluorenes by adding phenols having two hydrogen atoms in the ortho-position and para-position at the time of resin synthesis, or by using dimethylolphenols for crosslinking By using a resin having the above, it is possible to make the resin further excellent in organic solvent solubility.

The resin represented by the general formula (I) has a structure containing one or more bisphenolfluorenes, and n ₃ is 0 to 10, preferably 1 to 10, more preferably 1 to 4. When n ₃ is 0, the heat resistance is poor, and when it is 5 or more, the workability is poor. Further, the numbers n ₁ and n ₂ of phenols serving as spacers are each an integer of 0 to 20, and the total of n ₁ and n ₂ is preferably 0 to 11 and more preferably 0 to 5. It is good. If the total of n ₁ and n ₂ is 12 or more, the heat resistance is poor.

  Preferred bisphenol fluorenes that give the resin of the general formula (I) include the following. 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9 -Bis (4-hydroxy-3-allylphenyl) 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-hydroxynaphthyl) 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) fur Luolene and the like can be mentioned.

  Preferred aldehydes or dimethylolphenols that give the resin of the general formula (I) include the following. That is, formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeric aldehyde, isovaleric aldehyde, 2-methylbutyraldehyde, 1-hexanal, 2-ethylbutyraldehyde, benzaldehyde, o-tolualdehyde M-tolualdehyde, p-tolualdehyde, 2,6-bis (hydroxymethyl) -p-cresol, 2,4-bis (hydroxymethyl) -o-cresol, and the like.

  Examples of the phenols that can serve as the spacer of the resin of the general formula (I) include the following. That is, o-cresol, p-cresol, 2-ethylphenol, 4-ethylphenol, 2-propylphenol, 4-propylphenol, 2-isopropylphenol, 4-isopropylphenol, 2-tert-butylphenol, 4-tert- Examples include butylphenol, 2-sec-butylphenol, 4-sec-butylphenol, 2-methoxyphenol, 4-methoxyphenol, 2-naphthol and the like.

  Examples of the phenols that can be a terminal group of the resin of the general formula (I) include the following. 2,4-dimethylphenol, 2,6-dimethylphenol, 2-chloro-o-cresol, 2-chloro-p-cresol, 4-chloro-o-cresol, 2-bromo-o-cresol, 2- Bromo-p-cresol, 4-bromo-o-cresol, 2-tert-butyl-o-cresol, 4-tert-butyl-p-cresol, 4-tert-butyl-o-cresol, 2,4-di- tert-butylcresol, 2-methoxy-o-cresol, 2-methoxy-p-cresol, 4-methoxy-o-cresol, 2,6-di-tert-butylcresol, 2-allyl-o-cresol, 2- Examples include allyl-p-cresol and 1-naphthol.

In the present invention, among the substituents of the general formulas (I) and (II), a preferred embodiment is that R ¹ is a halogen atom or a hydrocarbon having 7 or less carbon atoms, and among R ⁵ , R ⁶ , and R ⁷ All the substituents corresponding to the ortho-position and para-position of the phenolic hydroxyl group are halogen atoms or hydrocarbons having 7 or less carbon atoms, and all the substituents corresponding to the ortho-position and para-position of the phenolic hydroxyl group among R ^{8 to} R ¹² are It may be a halogen atom or a hydrocarbon having 7 or less carbon atoms. If it is such an aspect, it can be set as resin linearly synthesize | combined. In addition, the molecular weight (Mw) of resin represented by general formula (I) is 500-10000, Preferably it is 500-5000, More preferably, it is 800-2000.

  Moreover, in this invention, the photosensitive resin represented by general formula (III) can be obtained by using the resin of general formula (I) as a precursor and introduce | transducing a (meth) acryl group into this. The photosensitive resin of general formula (III) is a resin in which 10% or more of (meth) acrylic groups are introduced with respect to the number of all phenolic hydroxyl groups of general formula (I), and 50% or more is introduced. It is more preferable. When the amount of (meth) acrylic group introduced is less than 10%, the number of crosslinking points at the time of curing decreases, and the effect of further improving the heat resistance when the resin is cured cannot be expected. In addition, the ratio of the (meth) acryl group said here is based on the number of the (meth) acryl groups introduce | transduced with respect to the number of the phenolic hydroxyl groups of general formula (I).

  Although the synthesis method of the photosensitive resin of general formula (III) is shown below, the photosensitive resin of this invention is not restricted to what was obtained by this synthesis method. This photosensitive resin of general formula (III) is a (meth) such as acrylic acid chloride, acrylic acid bromide, acrylic acid chloride, methacrylic acid bromide in the presence of an acid catalyst or a base with respect to the resin of general formula (I). It can be synthesized by reacting an acrylic acid halide or (meth) acrylic anhydride. Among these, examples of the acid catalyst include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as methylsulfonic acid and p-toluenesulfonic acid. Bases include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and cesium hydroxide, trimethylamine, triethylamine, tripropylamine, tributylamine, triisopropylamine, triisobutylamine, diazabicycloundecene, pyridine Etc. In addition, the molecular weight (Mw) of resin represented by general formula (III) is 600-12000, Preferably it is 600-6000, More preferably, it is 1000-3000.

  Further, in the present invention, using the resin represented by the general formula (I) or (III), the “photopolymerizable monomer having at least one ethylenically unsaturated bond” as the component (B), and By blending with the “photopolymerization initiator” of component (C), a photosensitive resin composition can be obtained. From the viewpoint of further improving the crosslinking density, the resin represented by the general formula (III) is used together with the component (B) and the component (C) to obtain a photosensitive resin composition. preferable. In the photosensitive resin composition of the preferable aspect containing resin of general formula (III), it is desirable to contain the photosensitive resin of general formula (III) 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. Moreover, containing as a main component means that the photosensitive resin of general formula (III) is contained 30 wt% or more, preferably 50 wt% or more in the resin component. In a preferred embodiment, the photosensitive resin of the general formula (III) may be included as an essential component, and components other than the photosensitive resin may include various fillers in addition to a colorant such as a pigment and a solvent.

  Examples of the component (B) “photopolymerizable monomer having at least one ethylenically unsaturated bond” include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-ethylhexyl. Monomers having a hydroxyl group such as (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, dimethylol tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, List of (meth) acrylic acid esters such as intererythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, etc. be able to. These compounds can be used alone or in combination of two or more thereof.

  About the mixture ratio of these (B) component and the photosensitive resin represented by general formula (III) of (A) component, the weight ratio [(A) in a total of 100 weight part of (A) component and (B) component [(A ) / (B)] should be 20 parts by weight / 80 parts by weight to 90 parts by weight / 10 parts by weight, and preferably 40 parts by weight / 60 parts by weight to 80 parts by weight / 20 parts by weight. Good.

  Examples of the photopolymerization initiator of component (C) 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-methoxyphene B) -4,5-diphenylbiimidazole, biimidazole compounds such as 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2- Halomethylthiazole such as trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole Compounds, 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 (trichloromethyl) -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- (4 -Methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine and other halomethyl-s-triazine compounds, 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, O-acyloxime compounds such as 2-dione-2-oxime-o-acetate and 1- (4-methylsulfanylphenyl) butan-1-oneoxime-o-acetate, benzyldimethyl ketal, thioxanthone, 2-chlorothio Xanthone, 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 used as the component (C) is based on a total of 100 parts by weight of the photosensitive resin represented by the general formula (III) of the component (A) and the photopolymerizable monomer of the component (B). It should be 1 to 50 parts by weight, preferably 2 to 40 parts by weight. Incidentally, the photopolymerization initiator of the component (C) includes those having a photosensitizing action, but there is no problem even if a photosensitizer is added separately.

  The photosensitive resin composition containing the photosensitive resin represented by the general formula (III) of the component (A), the photopolymerizable monomer of the component (B), and the photopolymerization initiator of the component (C) as essential components, The present invention can be applied to color filter materials such as color filter inks and protective films, semiconductor resist materials, and structure forming photoresist materials. If necessary, this photosensitive resin composition can be dissolved in a solvent shown below, or various additives can be blended.

  When using the photosensitive resin composition of this invention for a color filter use, it is preferable to mix | blend a solvent other than each component of said (A)-(C). 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 has a photosensitivity represented by the general formula (III) of the component (A) in the solid content excluding the solvent (the solid content includes a monomer that becomes a solid content after curing). The total amount of the resin, the photopolymerizable monomer (B) and the photopolymerization initiator (C) is preferably 70 wt% or more, preferably 80 wt% or more, 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 of the resin composition.

  The cured film (cured product) of the present invention is obtained by, for example, applying the above-mentioned photosensitive resin composition solution to a substrate or the like, drying it, and irradiating it with light (including ultraviolet rays and radiation) to cure it. Can be obtained. In general, first, a photosensitive resin composition is applied on the surface of a substrate, and then pre-baked to evaporate the solvent to form a coating film. Subsequently, after exposing this coating film, a hardened | cured material is obtained by post-baking after that. 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 solvent is removed (prebaked) to form a cured film. In particular, the photosensitive resin composition of the present invention contains a highly heat-resistant resin represented by the general formula (I) or (III), and retains the shape under the thermosetting conditions such as the following post-bake. Therefore, the present invention can be suitably used when a thick cured film having a thickness of 2 μm or more is obtained. 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 to be used, and are performed, for example, at a temperature of 80 to 120 ° C. for 1 to 10 minutes.

  As the radiation used for producing the cured film, 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. After curing by exposure, heat treatment (post-bake) is performed at a temperature of 150 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 coating film and the substrate.

  The resin of the present invention exhibits high heat resistance because the fluorene skeleton exhibiting high heat resistance is connected with a novolac structure exhibiting high heat resistance. Therefore, for example, when a photosensitive resin composition is used in the production of a color filter, it exhibits excellent shape retention under conditions such as post-baking and other heat curing and ITO bonding processes exceeding 200 ° C. In particular, it can be suitably used when a thick cured film is required.

Hereinafter, the present invention will be described in more detail based on reference examples, examples, and comparative examples. The scope of the present invention is not limited by these reference examples, examples and comparative examples. In addition, the molecular weight of the resin in the following Examples and the like 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 and the like are as follows.
BCFL: 9,9-bis (4-hydroxy-3-methylphenyl) fluorene PGMEA: propylene glycol monomethyl ether acetate ANON: cyclohexanone

[Reference Example 1]
To a 200 mL separable flask equipped with a stirrer and a condenser were added BCFL 5.68 g, 2,6-dimethylphenol 1.22 g, paraformaldehyde 0.60 g, and p-toluenesulfonic acid monohydrate 95 mg, and toluene 50 g The mixture was stirred at 100 ° C. for 5 hours. Neutralization was performed by adding 0.27 g of a 10% aqueous sodium carbonate solution, and the solvent was distilled off under reduced pressure to obtain 6.77 g of Resin-1. About obtained resin-1, Mw by GPC was 908 and Mw / Mn was 1.52. Moreover, the result of ¹ HNMR is as follows. ¹ HNMR (CDCl ₃ , δ) 7.75-7.60 (6H, m, Ar—H), 7.35-6.46 (34H, m, Ar—H), 3.84-3.57 ( 8H, m, Ar-CH2-Ar), and 2.30-1.93 (30H, m, Ar-CH3).

[Reference Example 2]
A 200 mL separable flask equipped with a stirrer and a condenser was added with 5.68 g of BCFL, 1.43 g of 4-chloro-o-cresol, 0.60 g of paraformaldehyde, and 95 mg of p-toluenesulfonic acid monohydrate. The mixture was stirred at 100 ° C. in 50 g for 5 hours. The mixture was neutralized with 0.27 g of 10% aqueous sodium carbonate solution, and the solvent was distilled off under reduced pressure to obtain 6.67 g of Resin-2. About obtained resin-2, Mw by GPC was 1534 and Mw / Mn was 1.81. Moreover, the result of ¹ HNMR is as follows. ¹ HNMR (CDCl ₃ , δ) 7.78-7.61 (6H, m, Ar—H), 7.39-6.30 (34H, m, Ar—H), 3.80-3.52 ( 8H, m, Ar-CH2-Ar), 2.30-1.88 (24H, m, Ar-CH3).

[Reference Example 3]
226 g of BCFL, 82.3 g of 2,4-di-t-butylphenol, 24.0 g of paraformaldehyde, and 1.9 g of p-toluenesulfonic acid monohydrate were added to a 1 L separable flask equipped with a stirrer and a condenser. The mixture was stirred in 500 g of toluene at 100 ° C. for 5 hours. The mixture was neutralized with 5.3 g of a 10% aqueous sodium carbonate solution, and the solvent was distilled off under reduced pressure to obtain 264 g of Resin-3. About obtained resin-3, Mw by GPC was 1290, and Mw / Mn was 1.51. Moreover, the result of ¹ HNMR is as follows. ¹ HNMR (CDCl ₃ , δ) 7.79-7.56 (6H, m, Ar—H), 7.37-6.31 (34H, m, Ar—H), 3.92-3.50 ( 8H, m, Ar-CH2-Ar), 2.5-1.83 (18H, m, Ar-CH3), 1.52-1.13 (36H, m, Ar-tBu).

[Reference Example 4]
In a 200 mL separable flask equipped with a stirrer and a condenser, BCFL 5.68 g, 2,6-dimethylphenol 1.23 g, 2,6-bis (hydroxymethyl) phenol 3.37 g, and p-toluenesulfonic acid monohydrate 95 mg of the Japanese product was added, and the mixture was stirred at 100 ° C. for 5 hours in 50 g of toluene. The mixture was neutralized with 0.27 g of 10% aqueous sodium carbonate solution, and the solvent was distilled off under reduced pressure to obtain 9.06 g of Resin-4. About obtained resin-4, Mw by GPC was 1570, and Mw / Mn was 1.77. Moreover, the result of ¹ HNMR is as follows. ¹ HNMR (CDCl ₃ , δ) 7.78-7.65 (6H, m, Ar—H), 7.40-6.48 (42H, m, Ar—H), 3.85-3.59 ( 16H, m, Ar-CH2-Ar), 2.35-1.88 (42H, m, Ar-CH3).

[Reference Example 5]
In a 200 mL separable flask equipped with a stirrer and a condenser, 5.68 g of BCFL, 1.46 g of 4-chloro-o-cresol, 3.36 g of 2,6-bis (hydroxymethyl) phenol, and one p-toluenesulfonic acid Hydrate (95 mg) was added, and the mixture was stirred in toluene (50 g) at 100 ° C. for 5 hours. The mixture was neutralized with 0.27 g of 10% aqueous sodium carbonate solution, and the solvent was distilled off under reduced pressure to obtain 8.69 g of Resin-5. About obtained resin-5, Mw by GPC was 2260, and Mw / Mn was 2.30. Moreover, the result of ¹ HNMR is as follows. ¹ HNMR (CDCl ₃ , δ) 7.78-7.60 (6H, Ar—H), 7.40-6.35 (42H, m, Ar—H), 3.85-3.51 (16H, m, Ar-CH2-Ar), 2.32-1.82 (36H, m, Ar-CH3).

[Reference Example 6]
In a 200 mL separable flask equipped with a stirrer and a condenser, 22.7 g of BCFL, 8.25 g of 2,4-di-t-butylphenol, 13.4 g of 2,6-bis (hydroxymethyl) phenol, and p-toluenesulfone The acid monohydrate 0.19g was added and it stirred at 100 degreeC in 80g of toluene for 5 hours. The mixture was neutralized with 0.53 g of 10% aqueous sodium carbonate solution, and the solvent was distilled off under reduced pressure to obtain 32.2 g of Resin-6. About obtained resin-6, Mw by GPC was 1773, and Mw / Mn was 1.68. Moreover, the result of ¹ HNMR is as follows. ¹ H NMR (CDCl ₃ , δ) 7.82-7.60 (6H, m, Ar—H), 7.39-6.42 (42H, m, Ar—H), 4.02-3.59 ( 16H, m, Ar-CH2-Ar), 2.35-1.89 (30H, m, Ar-CH3), 1.55-1.20 (36H, m, Ar-tBu).

[Example 7]
A 200 mL separable flask equipped with a stirrer and a condenser was added with 19.9 g of resin-3, 1.51 g of acrylic anhydride, and 96 mg of methylsulfonic acid, and the mixture was stirred in 100 g of toluene at 50 ° C. for 15 hours. The resulting reaction mixture was neutralized and washed with saturated aqueous sodium hydrogen carbonate, and the solvent was distilled off under reduced pressure. Resin-7 in which acrylic groups were introduced into 83% of the total number of phenolic hydroxyl groups in Resin-3 Of 17.7 g. About obtained resin-7, Mw by GPC was 1493 and Mw / Mn was 1.43. Moreover, the result of ¹ HNMR is as follows. ¹ HNMR (CDCl ₃ , δ) 7.80-7.69 (6H, Ar—H), 7.43-5.68 (34H, m, Ar—H, 20H, m, H ₂ C═CH—) 3.75-3.39 (8H, m, Ar-CH2-Ar), 2.18-1.88 (30H, m, Ar-CH3), 1.50-1.20 (36H, m, Ar) -TBu).

[Example 8]
To a 200 mL separable flask equipped with a stirrer and a condenser, 23.2 g of resin-6, 22.2 g of acrylic anhydride and 96 mg of methylsulfonic acid were added, and the mixture was stirred at 100 ° C. for 15 hours in 50 g of toluene. The mixture obtained was neutralized and washed with saturated aqueous sodium hydrogen carbonate, and the solvent was distilled off under reduced pressure, whereby resin-8 having an acrylic group introduced into 75% of the total number of phenolic hydroxyl groups of resin-6. 21.6 g was obtained. About obtained resin-8, Mw by GPC was 2136, and Mw / Mn was 1.74. Moreover, the result of ¹ HNMR is as follows. ¹ HNMR (CDCl ₃ , δ) 7.80-7.63 (6H, Ar—H), 7.39-5.63 (42H, m, Ar—H, 27H, m, H ₂ C═CH—) 3.79-3.35 (16H, m, Ar-CH2-Ar), 2.30-1.92 (18H, m, Ar-CH3), 1.56-1.13 (36H, m, Ar) -TBu).

[Example 9]
Using the photosensitive resin-7 and the resin-8 obtained above, a photosensitive resin composition was prepared as follows, and heat resistance was evaluated using Tg as an index.

3.60 g of resin-7, 3.60 g of DCP-A (manufactured by Kyoeisha Chemical Co., Ltd., dimethylol tricyclodecane diacrylate), 0.22 g of Irgacure OXE-2 (manufactured by Ciba Japan, photoinitiator), interface Prepare 0.03 g of activator SH3775 (manufactured by Kao), 0.06 g of coupling agent S-510 (manufactured by Shin-Etsu Chemical), 4.50 g of PGMEA, and 3.00 g of ANON, and mix them. A photosensitive resin composition was prepared. The obtained resin composition was applied to a glass substrate using a spin coater, pre-baked at 90 ° C. for 3 minutes, and then irradiated with ultraviolet rays of 100 mJ / cm ² with an ultrahigh pressure mercury lamp with an I-line illuminance of 30 mW / cm ^2. Irradiated to carry out photocuring reaction of the photosensitive part. Subsequently, post-baking was performed at 150 ° C. for 30 minutes and subsequently at 230 ° C. for 30 minutes to obtain a cured film having a thickness of 80 μm. The cured film was measured for viscoelasticity and Tg was measured from tan δ. The results are shown in Table 1.

[Example 10]
Resin-7 was replaced with resin-8, and other than that, a photosensitive resin composition was prepared at the same blending ratio as in Example 9, and evaluated in the same manner as in Example 9. The results are shown in Table 1.

[Comparative Example 1]
Resin-7 was replaced with V-259ME (manufactured by Nippon Steel Chemical Co., Ltd., fluorene type epoxy acrylate / acid anhydride polymerization adduct), and other than that, a photosensitive resin composition was prepared at the same mixing ratio as Example 9. Then, evaluation was performed in the same manner as in Example 9. The results are shown in Table 1.

Claims (3)

A photosensitive resin represented by the following general formula (III) and having a molecular weight of 600 to 12,000.

(N ₁ ~n ₂ each independently an integer of 0 to 20, n ₃ represents an integer of 0, the sum of n ₁ ~n ₃ represents an integer of 1 or more. R ^1, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different monovalent substituents selected from a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and R ¹ and R ² and / or Or R ⁵ , R ^6, and R ⁷ may form a ring, X represents a hydrogen atom or a (meth) acryl group, and R ^{8 to} R ^{12 represent} the main chain (—CHR ⁴ —). At least one of the three substituents in the ortho-position or para-position represents an OX group, and the ratio of the (meth) acryl group is 10 to 100% with respect to the total number of all X. Other R ⁸ to R ¹² is a hydrogen atom, a halogen atom, a hydroxyl group, the same or different monovalent substituents selected from alkyl or aryl group Shown, two substituents adjacent to R ⁸ to R ¹² may form a ring.) The photosensitive resin composition containing following (A)-(C).
(A) the resin according to claim 1 ,
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, and (C) a photopolymerization initiator. A cured product formed by curing the photosensitive resin composition according to claim 2 .