TWI655503B - Photosensitive resin composition, spacer, protection film and liquid crystal display element - Google Patents

Abstract

A photosensitive resin composition comprising an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), and a solvent (D). The ethylenically unsaturated group-containing compound (B) includes the first compound (B-1) having an ethylenically unsaturated group having the structure of the formula (II). The photoinitiator (C) includes a photoinitiator (C-1) represented by the formula (1). Formula (II) Formula 1)

Description

Photosensitive resin composition, interstitial body, protective film, and liquid crystal display element

The present invention relates to a photosensitive resin composition and a spacer or protective film formed using the composition, and a liquid crystal display element thereof. In particular, there is a photosensitive resin composition having high-speed coating properties, good adhesion during development, and excellent refractive index, hardness, and resolution, and a spacer or protective film formed using the composition and liquid crystal thereof. Display component.

In general, the color-printed pixels on the surface of the color filter layer and the black matrix may cause irregularities, and a protective film is generally formed on the surface of the color filter layer, thereby hiding the unevenness and thereby achieving flattening. Claim.

However, in the manufacture of optical elements such as liquid crystal display elements or solid-state imaging devices, handling procedures under severe conditions, such as treatment with an acidic solvent or an alkaline solution on the surface of the substrate or formation of wiring by sputtering, are encountered. When the electrode layer is used, local corrosion or high temperature is generated. Therefore, it is necessary to lay a protective film on the surface of these components to prevent damage to the components during manufacture. In order for the protective film to have characteristics against the above treatment, the protective film needs to have excellent adhesion to the substrate, and also has high transparency, high surface hardness, and a smooth surface. The protective film with high heat resistance and light resistance can also be deteriorated due to discoloration, yellowing or whitening under long-term use. In addition, the protective film also needs to have good water resistance, chemical resistance, solvent resistance, acid resistance, alkali resistance and the like.

On the other hand, in the prior art, in the color liquid crystal display element, in order to maintain a fixed layer spacing (cell gap) between the two substrates, a polystyrene bead or a bead is randomly sprayed on the entire substrate, wherein the bead is The diameter is the distance between the two substrates. However, this conventional method causes the light of the backlight to be scattered by the beading due to the uneven distribution of the position and density of the bead, further reducing the contrast of the display element. Therefore, the photosensitive composition for the interstitial body developed by the photolithography method has become the mainstream in the industry. The gap body is formed by applying the photosensitive composition for the spacer body to the substrate, and then placing a mask of a predetermined shape between the substrate and the exposure source, and developing the spacer after exposure. . According to this method, a gap body can be formed at a specified position outside the R, G, and B pixels to solve the problem of the prior art; the cell gap can also be controlled by the thickness of the coating film formed by the photosensitive component to make the cell gap The distance becomes easy to control and has the advantage of high precision.

Since the protective film or gap system is formed on a color filter or a substrate, the transparency is extremely high. If the transparency of the protective film or the spacer is not good, when applied to the liquid crystal display element, the brightness of the liquid crystal display element is insufficient, which affects the display quality of the liquid crystal display element. In order to increase the transparency of the protective film or the spacer, Japanese Patent Laid-Open No. 2010-054561 discloses a photosensitive composition for a protective film comprising (A) an alkali-soluble binder resin; (B) a compound having an ethylenically unsaturated group; C) a photoinitiator; and (D) a solvent; wherein the (B) ethylenically unsaturated group compound has an unsaturated equivalent of from 90 to 450 g/eq, and (B) ethylenic unsaturation In the compound of the group, the unsaturated double bond of the single compound is between 2 and 4, and the weight average molecular weight of the (A) alkali-soluble binder resin is between 10,000 and 20,000. On the other hand, Japanese Patent Laid-Open No. 2004-240241 discloses a photosensitive composition comprising (A) a copolymer which is an ethylenically unsaturated carboxylic acid (anhydride) having an epoxy group. a compound of an unsaturated group and a compound of another ethylenic unsaturated group; (B) a copolymer of a polymer of an ethylenically unsaturated group; and (C) a photoinitiator which is 2-butyl Keto-[4-methylthiobenzene]-2-(O-indole acetate), 1,2-butanedione-1-(4-morpholinylphenyl)-2-(O-benzamide) , 1,2-octanedione-1-[4-phenylthiobenzene]-2-[O-(4-methylbenzhydrazinium) oxime] or an analogue thereof. However, the photosensitive resin composition has a problem of poor adhesion, hardness, and coatability during development, and cannot satisfy the increasing demand for refractive index and resolution in the industry today.

Therefore, how to simultaneously achieve the requirements of good adhesion, hardness, coatability, refractive index, and resolution in development in the prior art is an object of diligent research in the technical field to which the present invention pertains.

The present invention provides a photosensitive resin composition comprising an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), and a solvent (D). Wherein the ethylenically unsaturated group-containing compound (B) comprises the first compound (B-1) having an ethylenically unsaturated group having the structure of the formula (II), Wherein A ⁵ represents a hydrogen atom or a methyl group; A ⁶ represents a hydrogen atom, an acryloyl group or a methacryl group; and r represents 3 to 4; and the photoinitiator (C) includes a formula (1) Representation of photoinitiator (C-1) Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen, C ₁ -C ₂₀ alkyl, COR ₁₆ , OR ₁₇ , halogen, NO ₂ , a group represented by the formula (2) or a group represented by the formula (3), Formula (2) ; Formula (3); or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are independently of each other via formula (4) Substituted C ₂ -C ₁₀ alkenyl group Formula (4); or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are each independently taken as —(CH ₂ ) _p —Y—(CH ₂ ) _q —; or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are independent of each other The group together is a group represented by the formula (5); Formula (5); but the condition is that at least one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are The group represented by the formula (5), R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently hydrogen, C ₁ -C ₂₀ alkyl, and the C ₁ -C ₂₀ alkyl group is unsubstituted or passed through a Or substituted with more than one of the following groups: halogen, phenyl, CN, OH, SH, C ₁ -C ₄ -alkoxy, -(CO)OH or -(CO)O-(C ₁ -C ₄ alkyl) Or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are, independently of each other, an unsubstituted phenyl group or a phenyl group substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, CN, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently halogen, CN, OR ₁₇ , SR ₁₈ , SOR ₁₈ , SO ₂ R ₁₈ or NR ₁₉ R ₂₀ , wherein The substituents OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ optionally form a 5- or 6-membered ring via a carbon atom in the naphthyl ring via the groups R ₁₇ , R ₁₈ , R ₁₉ and/or R ₂₀ ; Or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a group represented by COR ₁₆ , NO ₂ or formula (2), Formula (2); Y represents O, S, NR ₂₆ or a direct bond; p represents an integer of 0, 1, 2 or 3; q represents an integer 1, 2 or 3; X represents CO or a direct bond; R ₁₃ represents C ₁ - a C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ , NR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ or a group represented by the formula (6); Formula (6); or R ₁₃ represents a C ₂ -C ₂₀ alkyl group in which one or more of O, S, SO, SO ₂ , NR ₂₆ or CO, or a C ₂ -C ₁₂ alkenyl group, which is not Interstitial or heterozygous with one or more O, CO or NR ₂₆ , wherein the interstitial C ₂ -C ₂₀ alkyl group and the uninterstitial or interstitial C ₂ -C ₁₂ alkenyl group are unsubstituted or Or a plurality of halogen substitutions; or R ₁₃ represents a C ₄ -C ₈ cycloalkenyl group, a C ₂ -C ₁₂ alkynyl group or a C ₃ -C ₁₀ having no or hetero or hetero or one or more O, S, CO or NR ₂₆ Cycloalkyl; or R ₁₃ represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , COR ₁₆ , CN, NO ₂ , a halogen, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₄ haloalkyl group, a hetero group having one or more C ₂ -C ₂₀ alkyl groups of O, S, CO or NR ₂₆ or a group represented by the formula (7), Formula (7); each warp or a C ₃ -C ₁₀ cycloalkyl, or interrupted by one or more O, S, CO or NR ₂₆ of the C ₃ -C ₁₀ cycloalkyl; K represents integer of 1 to 10; R ₁₄ represents hydrogen, C ₃ -C ₈ cycloalkyl, C ₂ -C ₅ alkenyl, C ₁ -C ₂₀ alkoxy or C ₁ -C ₂₀ alkyl, which is unsubstituted or one or more of the following Substituents: halogen, phenyl, C ₁ -C ₂₀ alkylphenyl or CN; or R ₁₄ represents phenyl or naphthyl, each unsubstituted or substituted by one or more of the following groups: C ₁ - C ₆ alkyl, C ₁ -C ₄ haloalkyl, halogen, CN, OR ₁₇ , SR ₁₈ and/or NR ₁₉ R ₂₀ ; or R ₁₄ represents C ₃ -C ₂₀ heteroaryl, C ₁ -C ₈ alkoxy a benzyloxy group or a phenoxy group which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl and/ Or halogen; R ₁₅ represents C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ Haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ , SO-C ₁ -C ₁₀ alkyl, SO ₂ -C ₁ -C ₁₀ alkyl One or one A O, S or NR C ₂₆ of ₂ -C ₂₀ alkyl group; or each warp substituted C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl which is unsubstituted or substituted with one or more of the following groups Substitution: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryl Oxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ represents hydrogen, C ₂ -C ₁₂ alkenyl, unmixed or hetero-has one or more O, CO or NR ₂₆ C ₃ -C ₈ a cycloalkyl group; or R ₁₅ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, C _3- C ₂₀ Heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ , PO(OC _k H _{2k+1 2} ) a phenyl group, a group represented by the formula (6) or a group represented by the formula (8), Formula (6) Formula (8); or the C ₁ -C ₂₀ alkyl group is substituted by a phenyl group which is halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R _{20 is} substituted; or R ₁₅ represents a C ₂ -C ₂₀ alkyl group in which one or more O, SO or SO ₂ are heterogeneous, and the interstitial C ₂ -C ₂₀ alkyl group is unsubstituted or subjected to one or Substituted by a plurality of groups: halogen, OR ₁₇ , COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl or phenyl substituted with OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ represents C ₂ -C ₂₀ alkane Or benzylidene, which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ And a C ₃ -C ₁₄ alkoxycarbonyl group which is unsubstituted or substituted with one or more OR ₁₇ ; or R ₁₅ represents a C ₂ -C ₁₂ alkoxycarbonyl group which is unintercalated or Miscellaneous with one or more O and the inter- or un-doped C ₂ -C ₁₂ alkoxycarbonyl group is unsubstituted or substituted with one or more hydroxyl groups; or R ₁₅ represents a phenoxycarbonyl group, which is not Substituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, C ₁ -C _4- haloalkyl, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ represents CN, CONR ₁₉ R ₂₀ , NO ₂ , C ₁ -C ₄ haloalkyl, S(O) _m -C ₁ -C _{a 6} alkyl group, an unsubstituted or S(O) _m -phenyl group substituted with a C ₁ -C ₁₂ alkyl group or a SO ₂ -C ₁ -C ₆ alkyl group; or R ₁₅ represents a SO ₂ O-phenyl group, Is unsubstituted or substituted by C ₁ -C ₁₂ alkyl; or diphenylphosphinyl or di-(C ₁ -C ₄ alkoxy)-phosphonium; m represents 1 or 2; R' ₁₄ Has one of the meanings given for R ₁₄ ; R' ₁₅ has one of the meanings given for R ₁₅ ; X ₁ represents O, S, SO or SO ₂ ; X ₂ represents O, CO, S or Direct bond; R ₁₆ represents C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ Haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or a heterocyclic one or more C ₁ -C ₂₀ alkyl groups of O, S or NR ₂₆ ; or each of one or more C ₁ - C ₂₀ alkyl substituted, the C ₁ -C ₂₀ alkyl group being unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl , C ₃ -C _{2 0} heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl group, C ₃ -C ₂₀ heteroaryl aryloxycarbonyl group, OR _17, SR ₁₈ or NR ₁₉ R _20; or R ₁₆ represents hydrogen, C ₁ -C ₂₀ alkyl , the C ₁ -C ₂₀ alkyl group is unsubstituted or substituted with one or more of the following groups: halogen, phenyl, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ )alkyl, O(CO)-(C ₁ -C ₄ alkyl), O(CO)-phenyl, (CO)OH or (CO)O (C ₁ -C ₄ alkyl); or R ₁₆ represents C ₂ -C ₁₂ alkyl with one or more O, S or NR _{26 in between} ; or R ₁₆ represents (CH ₂ CH ₂ O) _n+1 H , (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₁₂ alkenyl or C ₃ -C ₈ cycloalkyl; or R ₁₆ represents benzene substituted by SR ₁₈ a group wherein the group R ₁₈ represents a direct bond to the phenyl or naphthyl ring to which the carbazole moiety is attached to the COR ₁₆ group; n represents 1 to 20; R ₁₇ represents hydrogen, phenyl -C ₁ -C ₃ alkyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ ) Alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C ₁ -C ₄ alkyl), C ₃ -C ₂₀ cycloalkyl, SO ₂ -(C _1- C ₄ haloalkyl Or O(C ₁ -C ₄ haloalkyl) or a C ₃ -C ₂₀ cycloalkyl group having one or more O; or R ₁₇ represents a C ₂ -C ₂₀ alkyl group, wherein one or more O, S are hetero Or NR ₂₆ ; or R ₁₇ represents (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₁ -C ₈ alkyl fluorenyl a C ₂ -C ₁₂ alkenyl group, a C ₃ -C ₆ olefinic group or a C ₃ -C ₂₀ cycloalkyl group having one or more O, S, CO or NR ₂₆ without inter or hetero-hetero; or R ₁₇ represents C _{a 1-} C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl group which is undoped or hetero-has one or more O; or R ₁₇ represents a benzamidine group which is unsubstituted or has one or more C _1- C ₆ alkyl, halogen, OH or C ₁ -C ₃ alkoxy substituted; or R ₁₇ represents phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or via one or Substituted by a plurality of groups: halogen, OH, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N (C ₁ -C ₁₂ alkyl) _2, diphenyl - group, or of formula (7) represented by Group; Formula (7); or R ₁₇ is bonded to one of the carbon atoms of the phenyl or naphthyl ring to which the group represented by the formula (2) or the group represented by the formula (7) is bonded Direct key, Formula (2) R ₁₈ represents hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl or phenyl-C ₁ -C ₃ alkyl, wherein the C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl or phenyl-C ₁ -C ₃ alkyl is one or more O, S, CO, NR ₂₆ or COOR ₁₇ without inter or hetero-hetero; or R ₁₈ is C ₁ -C ₂₀ alkyl , which is unsubstituted or substituted with one or more of the following groups: OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O (C ₁ - C ₄ alkyl), O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-(C ₁ -C ₄ alkyl), O(CO)-phenyl or (CO)OR ₁₇ ; Or R ₁₈ represents a C ₂ -C ₂₀ alkyl group with one or more O, S, CO, NR ₂₆ or COOR _{17 in between} ; or R ₁₈ represents (CH ₂ CH ₂ O) _n H, (CH ₂ CH ₂ O _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₈ alkanoyl or C ₃ -C ₆ olefin; or R ₁₈ represents a benzamidine group, which is unsubstituted or Substituted by one or more of the following: C ₁ -C ₆ alkyl, halogen, OH, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkylthio; or R ₁₈ represents phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following radicals: halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₄ haloalkoxy , C ₁ -C ₁₂ alkoxy, CN, NO _2, phenyl -C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N (C ₁ -C ₁₂ alkyl) ₂ , diphenylamino, (CO)O(C ₁ -C ₈ alkyl), (CO)-C ₁ -C ₈ alkyl, (CO)N (C ₁ -C ₈ Alkyl) ₂ or a group represented by formula (7) Formula (7); R ₁₉ and R ₂₀ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₂ -C ₁₀ alkoxyalkyl, C ₂ -C ₅ olefin , C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₈ alkanoyl, C ₁ -C ₈ alkenyloxy, C ₃ -C ₁₂ olefin , SO ₂ —(C ₁ -C ₄ haloalkyl) or benzhydryl; or R ₁₉ and R ₂₀ represent phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or Or substituted with a plurality of groups: halogen, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₁₂ alkyl, benzhydryl or C ₁ -C ₁₂ alkoxy; R ₁₉ and R ₂₀ together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which is unintermixed or intermixed with O, S or NR ₁₇ and which is a saturated or unsaturated ring of 5 or 6 members. Is unsubstituted or substituted by one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, =0, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO)R ₂₃ , NO ₂ , halogen, C ₁ -C ₄ -haloalkyl, CN, phenyl, C ₃ -C ₂₀ cycloalkyl, or a formula having one or more O, S, CO or NR ₁₇ without inter or hetero (7) indicated group Formula (7); or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkane Base, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, =0, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO)R ₂₃ , halogen, NO ₂ , CN, phenyl or not a C ₃ -C ₂₀ cycloalkyl group having one or more O, S, CO or NR ₁₇ or a group represented by the formula (7) R ₂₁ and R ₂₂ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₁₀ cycloalkyl or phenyl; or R ₂₁ and R ₂₂ Together with the N atom to which it is attached, it forms a 5- or 6-membered saturated or unsaturated ring which is not intermixed or interspersed with O, S or NR ₂₆ , and the 5 or 6 member saturated or unsaturated ring is unfused or The 5- or 6-membered saturated or unsaturated ring is fused to the benzene ring; R ₂₃ represents hydrogen, OH, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, inter-hetero or one or more O, CO or NR _a C ₂ -C ₂₀ alkyl group, a C ₃ -C ₂₀ cycloalkyl group having no O, S, CO or NR ₂₆ , or R ₂₃ representing a phenyl group, a naphthyl group, a phenyl-C ₁ group C ₄ alkyl, OR ₁₇ , SR ₁₈ or NR ₂₁ R ₂₂ ; R ₂₄ represents (CO)OR ₁₇ , CONR ₁₉ R ₂₀ , (CO)R ₁₇ ; or R ₂₄ has the meanings given for R ₁₉ and R ₂₀ One of them; R ₂₅ represents COOR ₁₇ , CONR ₁₉ R ₂₀ , (CO)R ₁₇ ; or R ₂₅ has one of the meanings given for R ₁₇ ; R ₂₆ represents hydrogen, C ₁ -C ₂₀ alkyl a C ₁ -C ₄ haloalkyl group, a C ₂ -C ₂₀ alkyl group, optionally having one or more O or CO; or a phenyl-C ₁ -C ₄ alkyl group, a C ₃ -C ₈ cycloalkyl group, Yes One or more O or CO; or (CO)R ₁₉ ; or a phenyl group which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, Halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or a group represented by the formula (7) Formula (7); but the condition is that at least one group represented by formula (2) or formula (7) is present in the molecule Formula (2) Formula (7).

In an embodiment of the invention, the alkali-soluble resin (A) comprises an alkali-soluble resin (A-1), wherein the alkali-soluble resin (A-1) is an unsaturated carboxylic acid or an unsaturated carboxylic anhydride compound (a1) and other unsaturated compounds (a2) are copolymerized

In an embodiment of the invention, the alkali-soluble resin (A) comprises a resin (A-2) having an unsaturated group, wherein the unsaturated group-containing resin (A-2) is polymerized by a mixture. And the mixture comprises an epoxy compound (a-1-1) having at least two epoxy groups and a compound (a-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group.

In an embodiment of the invention, the epoxy compound (a-1-1) having at least two epoxy groups includes the structure represented by the formula (a-1), and the formula (a-2) Structure or both structures, In the formula (a-1), in the formula (a-1), W ¹ , W ² , W ³ and W ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and a carbon number of 1 to Alkoxy group of 5, aryl group having 6 to 12 carbon atoms or aralkyl group having 6 to 12 carbon atoms, In the formula (a-2), in the formula (a-2), W ⁵ to W ¹⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms, s An integer representing 0 to 10.

In an embodiment of the invention, the alkali-soluble resin (A) comprises a polyoxyalkylene polymer (A-3) having an acid anhydride group or an epoxy group, and the polyoxyalkylene polymer (A- 3) is obtained by hydrolyzing and partially condensing at least one decane monomer represented by the structure of the formula (9): Si(U ¹ ) _w (OU ² ) _4-w (9) w represents 1 to 3 An integer, and when w represents 2 or 3, the plurality of U ¹ are each the same or different; and when 4-w represents 2 or 3, the plurality of U ² are each the same or different; at least one U ¹ represents an anhydride a C ₁ to C ₁₀ alkyl group substituted with a C ₁ to C ₁₀ alkyl group substituted with an epoxy group or an alkoxy group substituted with an epoxy group, and the remaining U ¹ represents hydrogen, C ₁ to C ₁₀ An alkyl group, a C ₂ to C ₁₀ alkenyl group or a C ₆ to C ₁₅ aryl group; and U ² represents hydrogen, a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ fluorenyl group or a C ₆ to C _{15 group;} The aromatic base.

In one embodiment of the present invention, the ethylenically unsaturated group-containing first compound (B-1) is used in an amount of 20 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). Up to 200 parts by weight.

In one embodiment of the present invention, the ethylenically unsaturated group-containing compound (B) comprises the second compound (B-2) containing an ethylenically unsaturated group represented by the following formula (III); In the formula (III), A ¹ and A ² each independently represent a hydrogen atom or a methyl group; and l represents an integer of 0 to 4.

In one embodiment of the present invention, the ethylenically unsaturated group-containing compound (B) comprises the third compound (B-3) containing an ethylenically unsaturated group represented by the following formula (IV); In the formula (IV), A ³ and A ⁴ each independently represent a hydrogen atom or a methyl group; and v represents an integer of 0 to 4.

In one embodiment of the present invention, the ethylenically unsaturated group-containing compound (B) comprises a fourth compound (B-4) having an ethylenically unsaturated group represented by the following formula (V) or the following formula (VI): ); Formula (V) In the formula (V), in the formula (V), B ¹ to B ⁸ each independently represent a hydrogen atom or a hydrocarbon group, and at least one of B ¹ to B ⁸ includes an ethylenically unsaturated group as a substituent at the end thereof; In (VI), B ¹ to B ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and at least one of B ¹ to B ⁶ includes an ethylenically unsaturated group as a substituent at the end thereof.

In an embodiment of the invention, the ethylenically unsaturated group-containing compound (B) comprises a fifth compound containing an ethylenically unsaturated group having a diacrylate or dimethacrylate of a linear diol. (B-5), and the linear diol has a carbon number of 2 to 12.

In an embodiment of the invention, wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each independently represent a hydrogen atom, a C ₁ -C ₂₀ alkyl group, or a COR ₁₆ , NO ₂ or a group represented by the formula (2), Formula (2); R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are independently of the formula (5) a group represented; Formula (5), but the condition is that at least one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are a group represented by the formula (5); X represents CO or a direct bond; R ₁₃ represents a C ₁ -C ₂₀ alkyl group, a phenyl group or a naphthyl group; when R ₁₃ represents a C ₁ -C ₂₀ alkyl group, it is Substituted or substituted with one or more of the following groups: halogen, OR ₁₇ , SR ₁₈ , COOR ₁₇ , CONR ₁₉ R ₂₀ or NR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ ; when R ₁₃ represents When C ₂ -C ₂₀ alkyl is undoped or intermixed with at least one O, S, CO or NR ₂₆ ; when R ₁₃ is phenyl or naphthyl, each is unsubstituted or substituted by COR ₁₆ Or substituted by at least one group represented by formula (7); Formula (7); R ₁₄ represents C ₁ -C ₂₀ alkyl, phenyl or C ₁ -C ₈ alkoxy; R ₁₅ represents phenyl, naphthyl, C ₃ -C ₂₀ heteroaryl or C ₁ -C ₂₀ alkyl; when R ₁₅ represents phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C _{a 4-} haloalkyl group, OR ₁₇ , SR ₁₈ , a hetero or a plurality of O, S C ₂ -C ₂₀ alkyl groups, or a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: Halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₄ -C ₂₀ heteroaryloxy a carbonyl group, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or PO(OC _k H _2k+1 ) ₂ ; when R ₁₅ represents a C ₁ -C ₂₀ alkyl group, it is unsubstituted or has one or more of the following groups Group substitution: OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ or PO(OC _k H _2k+1 ) ₂ ; R _'14 has the meanings for R ₁₄ Suo one of those given; R' ₁₅ has the meanings for R ₁₅ Suo one given by; R ₁₆ represents phenyl or C ₁ -C ₂₀ alkyl group; when R ₁₆ Benzene Substituted, which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , intervening one or more C ₂ -C ₂₀ alkyl groups of O, S or NR ₂₆ , Or a C ₁ -C ₂₀ alkyl group is unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ Heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₄ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ ; when R ₁₆ represents a C ₁ -C ₂₀ alkyl group, Is unsubstituted or substituted with one or more of the following groups: halogen, phenyl, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ (CO) O (C ₁ -C ₄ alkane , O(CO)-(C ₁ -C ₄ alkyl), or (CO)O(C ₁ -C ₄ alkyl); R ₁₇ represents C ₁ -C ₂₀ alkyl, which is unsubstituted or Substituted by one or more of the following groups: OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(C ₁ -C ₄ alkyl), (CO)O(C ₁ -C ₄ alkane a C ₃ -C ₂₀ cycloalkyl group, wherein the C ₃ -C ₁₀ cycloalkyl group is undoped or hetero-has one or more O; when R ₁₇ represents a C ₂ -C ₂₀ alkyl group, it is a hetero- Or a plurality of O; R ₁₈ represents a methyl group substituted by (CO)OR ₁₇ ; R ₁₉ And R ₂₀ are each independently hydrogen, phenyl, C ₁ -C ₂₀ alkyl, C ₁ -C ₈ alkanoyl or C ₁ -C ₈ alkenyloxy; R ₁₉ and R ₂₀ are attached thereto The atoms together form a heteroaromatic ring system which is unsubstituted or substituted with a group represented by formula (7); In the photoinitiator (C-1) having the structure represented by the formula (1), at least one group represented by the formula (2) or the formula (7) is present. Formula (2) Formula (7).

In an embodiment of the invention, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each independently represent a hydrogen atom; R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ are each independently a group represented by the formula (5); Formula (5), except that at least one of R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ is a group represented by the formula (5); R ₂ represents COR ₁₆ , NO ₂ , a group represented by the formula (2) or a group represented by the formula (3), Formula (2); Formula (3); R ₇ represents a group represented by COR ₁₆ or formula (2) R ₉ , R ₁₁ and R ₁₂ independently of each other represent a hydrogen atom; R ₁₀ represents a hydrogen atom, OR ₁₇ , COR ₁₆ ; X represents CO or a direct bond; R ₁₃ represents a C ₁ -C ₂₀ alkyl group or a benzene group; When R ₁₃ represents a C ₁ -C ₂₀ alkyl group, it is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , OR ₁₇ , SR ₁₈ or PO (OC _k H _{2k+1 2} ; when R ₁₃ represents a C ₂ -C ₂₀ alkyl group, it is a hetero or one or more O; k represents an integer 2; R ₁₄ represents a C ₁ -C ₂₀ alkyl group or a thienyl group; R ₁₅ represents a phenyl group, Naphthyl, thienyl, O or C ₁ -C ₂₀ alkyl; when R ₁₅ represents phenyl or naphthyl, it is unsubstituted or substituted with one or more OR ₁₇ or C ₁ -C ₂₀ alkyl groups; When R ₁₅ represents a C ₁ -C ₂₀ alkyl group, it is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, NR ₁₉ R ₂₀ or COOR ₁₇ ; when R ₁₅ represents a C ₂ -C ₂₀ alkyl group, it is inter-organized with SO ₂ ; R ₁₆ represents a phenyl group, a naphthyl group or a thienyl group; when R ₁₆ represents a phenyl group or a naphthyl group, it is unsubstituted. Or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl; R ₁₇ represents a hydrogen atom, a C ₁ -C ₈ alkanoyl group or a C ₁ -C ₂₀ alkyl group; when R ₁₇ represents a C ₁ -C ₂₀ alkyl group, it is unsubstituted or substituted with one or more of the following groups; a halogen, O(CO)-(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ alkenyl), or a C ₃ -C ₂₀ cycloalkyl group having one or more O; When R ₁₇ represents a C ₂ -C ₂₀ alkyl group, it is a hetero or one or more O; R ₁₈ represents a C ₃ -C ₂₀ cycloalkyl group, a C ₁ -C ₂₀ alkyl group or a phenyl group; when R ₁₈ represents C _{When 3-} C ₂₀ cycloalkyl or C ₁ -C ₂₀ alkyl, it is unsubstituted or via one or more OH, O(CO)-(C ₂ -C ₄ alkenyl) or (CO)OR ₁₇ Substituent; when R ₁₈ represents a phenyl group, which is unsubstituted or substituted by one or more halogens; R ₁₉ and R ₂₀ are each independently C ₁ -C ₈ alkylindenyl or C ₁ -C ₈ alkanoyl An oxy group; R ₁₉ and R ₂₀ together with the N atom to which they are attached form a 5- or 6-membered saturated ring in which O is interstitially; wherein the photoinitiator (C-1) of the structure represented by the formula (1) There is at least one group represented by the formula (2) Formula (2).

In one embodiment of the present invention, the photoinitiator (C-1) represented by the formula (1) is used in an amount of 2 to 20, based on 100 parts by weight of the alkali-soluble resin (A). Parts by weight.

In an embodiment of the invention, the photoinitiator (C) comprises other O-mercaptoquinone compounds (C-2).

In an embodiment of the invention, the other O-mercaptoindole compound (C-2) comprises a photoinitiator (C-2-I) represented by the following structural formula (10): Wherein D ⁴ and D ⁵ each independently represent a hydrogen atom, a cyclic, linear or branched alkyl or aryl group having 1 to 12 carbon atoms, and the alkyl group or aryl group The group is unsubstituted or substituted with a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an aryl group; D ⁶ and D ⁷ each independently represent a halogen Atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzamyl group, an alkano group having 2 to 12 carbon atoms, having 2 to 12 An alkoxycarbonyl group having a carbon number or a phenoxycarbonyl group; and e1 and e2 are integers independently representing from 0 to 5.

In an embodiment of the invention, the other O-mercaptoquinone compound (C-2) comprises a photoinitiator (C-2-II) represented by the following structural formula (11): In the formula (11), J ¹ represents a functional group of Ja, Jb-S, and Jc-O, wherein Ja, Jb, and Jc represent a hydrogen atom, an alkyl group, or an aromatic group; and J ² represents a hydrogen atom, C. _1- C ₄ alkyl or halogen.

In one embodiment of the present invention, the ethylenically unsaturated group-containing compound (B) is used in an amount of 50 to 500 parts by weight based on 100 parts by weight of the alkali-soluble resin (A); The photoinitiator (C) is used in an amount of 2 to 200 parts by weight; and the solvent (D) is used in an amount of 500 to 5000 parts by weight.

In an embodiment of the invention, the photosensitive resin composition further comprises o-naphthoquinonediazide sulfonate (E).

In an embodiment of the invention, the photosensitive resin composition further includes inorganic particles (F), and the inorganic particles (F) are mainly composed of an oxide of a Group IV element.

In an embodiment of the invention, the photosensitive resin composition further includes an organic acid (G), wherein the organic acid (G) has a molecular weight of 1,000 or less.

The present invention also provides a spacer which is obtained by sequentially applying a pre-baked treatment, an exposure treatment, a development treatment, and a post-baking treatment to a photosensitive resin composition as described above to obtain a spacer having a pattern.

The present invention also provides a protective film comprising a photosensitive resin composition as described above, which is sequentially subjected to a prebaking treatment, an exposure treatment, a development treatment, and a post-baking treatment to obtain a protective film having a pattern.

The present invention further provides a liquid crystal display element comprising the above-described interstitial body.

The present invention further provides a liquid crystal display element comprising the above protective film.

The above described features and advantages of the invention will be apparent from the following description.

< Photosensitive resin composition >

The present invention provides a photosensitive resin composition comprising an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), and a solvent (D). Further, the photosensitive resin composition may further include o-naphthoquinonediazide sulfonate (E), inorganic particles (F), organic acid (G), and additive (H). The respective components used in the photosensitive resin composition of the present invention will be described in detail below:

Here, the following description means that acrylic acid and/or methacrylic acid is represented by (meth)acrylic acid, and acrylate and/or methacrylate is represented by (meth)acrylate; similarly, (meth) The acryl fluorenyl group means an acryl fluorenyl group and/or a methacryl fluorenyl group. Alkali-soluble resin (A):

The alkali-soluble resin (A) includes a resin (A-2) having an alkali-soluble resin (A-1), an unsaturated group, and a polyoxyalkylene polymer (A-3) having an acid anhydride group or an epoxy group. Alkali soluble resin (A-1)

The alkali-soluble resin (A-1) is obtained by copolymerizing an unsaturated carboxylic acid or an unsaturated carboxylic anhydride compound (a1) and another unsaturated compound (a2) in a solvent in the presence of a suitable polymerization initiator. .

The unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) means a compound containing a carboxylic acid group or a carboxylic anhydride structure and an unsaturated bond for polymerization bonding, and the structure thereof is not particularly limited, for example, an unsaturated monocarboxylic acid compound, A saturated dicarboxylic acid compound, an unsaturated acid anhydride compound, a polycyclic unsaturated carboxylic acid compound, a polycyclic unsaturated dicarboxylic acid compound, or a polycyclic unsaturated acid anhydride compound.

In a specific example of the present invention, the unsaturated monocarboxylic acid compound is (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-(methyl)acrylic acid ethoxylated butyl Acid ester, 2-(methyl) propylene oxime ethoxy hexahydro phthalate, 2-(methyl) propylene ethoxy ethoxylate, omega-carboxy polycaprolactone polyol monoacrylic acid Ester (trade name: ARONIX M-5300, manufactured by East Asia).

In a specific example of the present invention, the unsaturated dicarboxylic acid compound is maleic acid, fumaric acid, methyl fumaric acid, itaconic acid, citraconic acid or the like. In a specific example of the present invention, the unsaturated dicarboxylic anhydride compound is an acid anhydride compound of the above unsaturated dicarboxylic acid compound.

In a specific example of the present invention, the polycyclic unsaturated carboxylic acid compound is 5-carboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2- Alkene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethyl Bicyclo [2.2.1] hept-2-ene.

In a specific example of the present invention, the polycyclic unsaturated dicarboxylic acid compound is 5,6-dicarboxylic acid bicyclo[2.2.1]hept-2-ene. In a specific example of the present invention, the polycyclic unsaturated dicarboxylic anhydride compound is an acid anhydride compound of the above polycyclic unsaturated dicarboxylic acid compound.

In a preferred embodiment of the invention, the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) is acrylic acid, methacrylic acid, maleic anhydride, 2-methylpropenyl ethoxy succinate and 2- Methyl propylene decyl ethoxy hexahydrophthalic acid. The unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) may be used singly or in combination of plural kinds.

The composition ratio of the unsaturated carboxylic acid-containing or unsaturated carboxylic anhydride compound (a1) of the present invention is from 10 to 50 parts by weight, preferably from 12 to 45 parts by weight, more preferably from 15 to 40 parts by weight.

The composition ratio of the other unsaturated compound (a2) is from 50 to 90 parts by weight, preferably from 55 to 88 parts by weight, more preferably from 60 to 85 parts by weight. Wherein the other unsaturated compound (a2) may comprise an epoxy group-containing unsaturated compound (a2-1) and other unsaturated compound (a2-2).

Specific examples of the epoxy group-containing unsaturated compound (a2-1) include an epoxy group-containing (meth) acrylate compound, an epoxy group-containing α-alkyl acrylate compound, and a glycidyl ether compound. .

In a specific example of the present invention, the epoxy group-containing (meth) acrylate compound is glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, or (meth)acrylic acid. 3,4-epoxybutyl ester, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxy ring (meth)acrylate Hexyl methyl ester.

In a specific example of the present invention, the epoxy group-containing α-alkyl acrylate compound is α-ethyl methacrylate, α-n-propyl propylene acrylate, α-n-butyl acrylate epoxy. Propyl ester, 6,7-epoxyheptyl α-ethyl acrylate.

In a specific example of the present invention, the glycidyl ether compound is o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, and P-vinylbenzylglycidylether.

Preferred examples of the epoxy group-containing unsaturated compound (a2-1) of the present invention are glycidyl methacrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and methacrylic acid 6,7 - epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether.

Specific examples of the other unsaturated compound (a2-2) are an alkyl (meth)acrylate, an alicyclic (meth)acrylate, an aryl (meth)acrylate, an unsaturated dicarboxylic acid diester, Hydroxyalkyl methacrylate, polyether of (meth) acrylate, aromatic vinyl compound and other unsaturated compounds.

In a specific example of the present invention, the alkyl (meth)acrylate is methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, or isopropyl (meth)acrylate. , n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, and tertiary butyl (meth)acrylate.

In a specific example of the present invention, the cycloaliphatic (meth)acrylate is cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.02,6]癸-8-yl (meth) acrylate (or dicyclopentanyl (meth) acrylate), dicyclopentyloxy (meth) acrylate, isobornyl (meth) acrylate, (methyl) ) tetrahydrofurfuryl acrylate.

In a specific example of the present invention, the aryl (meth)acrylate is phenyl (meth)acrylate or benzyl methacrylate.

In a specific example of the present invention, the unsaturated dicarboxylic acid diester is diethyl maleate, diethyl fumarate or diethyl itaconate.

In a specific example of the present invention, the hydroxyalkyl (meth)acrylate is 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate.

In a specific example of the present invention, the polyether of (meth) acrylate is polyethylene glycol mono(meth)acrylate or polypropylene glycol mono(meth)acrylate.

In a specific example of the present invention, the aromatic vinyl compound is styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene or p-methoxystyrene.

In a specific example of the present invention, the other unsaturated compound is acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl ethyl ester, 1,3-butadiene. , isoprene, 2,3-dimethyl1,3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide , N-butyl succinimide-3-maleimide benzoate, N-butyl succinimide-4-maleimide butyrate, N-butanediamine -6-maleimide caproate, N-butylenediamine-3-maleimide propionate, N-(9-acridinyl)maleimide.

Preferred examples of the other unsaturated compound (a2-2) of the present invention are methyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and (meth)acrylic acid Butyl methacrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentyloxy (meth) acrylate, styrene, p-methoxy styrene. Other unsaturated compounds (a2-2) according to the invention may be used singly or in combination.

Specific examples of the solvent used in the production of the alkali-soluble resin (A-1) of the present invention are alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl Ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbon, ketone, ester.

In a specific example of the present invention, the alcohol is methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, or 3-phenyl-1-propanol.

In a specific embodiment of the invention, the ether is tetrahydrofuran.

In a specific example of the present invention, the glycol ether is ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.

In a specific example of the present invention, the ethylene glycol alkyl ether acetate is ethylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate, and ethylene glycol methyl ether acetate.

In a specific example of the present invention, the diethylene glycol is diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether. , diethylene glycol methyl ether.

In a specific example of the present invention, the dipropylene glycol is dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether.

In a specific example of the present invention, the propylene glycol monoalkyl ether is propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether.

In a specific example of the present invention, the propylene glycol alkyl ether acetate is propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, or propylene glycol butyl ether acetate.

In a specific example of the present invention, the propylene glycol alkyl ether propionate is propylene glycol methyl ether propionate, propylene glycol diethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate.

In a specific example of the present invention, the aromatic hydrocarbon is toluene or xylene.

In a specific example of the present invention, the ketone is methyl ethyl ketone, cyclohexanone, or diacetone alcohol.

In a specific example of the present invention, the ester is methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxyl Ethyl 2-methylpropionate, methyl glycolate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, 3-hydroxypropionic acid Ethyl ester, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid Butyl ester, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxy acetate, methyl propoxyacetate, ethyl propoxyacetate, propionic acid propionate Ester, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 3-methoxybutyl acetate, 2- Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2- Ethyl ethoxy propionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate , methyl 2-butoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate , methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate , 3-ethoxypropionic acid ethyl ester, 3-ethoxypropionic acid propyl ester, 3-ethoxypropionic acid butyl ester, 3-propoxypropionic acid methyl ester, 3-propoxy propionate ethyl ester , propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate , butyl 3-butoxypropionate.

The solvent used in the production of the alkali-soluble resin (A-1) of the present invention is preferably diethylene glycol dimethyl ether or propylene glycol methyl ether acetate. The solvent used in the production of the other alkali-soluble resin (A-1) according to the present invention may be used singly or in combination.

The polymerization initiator used in the production of the alkali-soluble resin (A-1) according to the present invention is specifically an azo compound or a peroxide.

Specific examples of the azo compound are 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4- Methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-2-methylbutyronitrile, 4,4'-azobis(4-cyanovaleric acid), dimethyl Base 2,2'-azobis(2-methylpropionate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile).

Specific examples of the peroxide are benzamidine peroxide, dodecyl peroxide, t-butyl peroxypivalate, 1,1-bis(t-butylperoxy)cyclohexane, and hydrogen peroxide.

The polymerization initiators used in the production of the alkali-soluble resin (A-1) according to the present invention may be used singly or in combination.

The alkali-soluble resin (A-1) of the present invention has a weight average molecular weight of usually 3,000 to 100,000, preferably 4,000 to 80,000, more preferably 5,000 to 60,000. The molecular weight of the alkali-soluble resin (A-1) can be adjusted by using a single resin or by using two or more kinds of resins having different molecular weights.

In one embodiment of the present invention, the alkali-soluble resin (A-1) is used in an amount of 30 to 100 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A); preferably 35 To 95 parts by weight; more preferably 40 to 90 parts by weight. Resin with unsaturated group (A-2)

The unsaturated group-containing resin (A-2) is obtained by polymerizing a mixture, and the mixture includes an epoxy compound (a-1-1) having at least two epoxy groups and having at least one carboxylic acid group and At least one ethylenically unsaturated group compound (a-1-2).

The epoxy compound (a-1-1) having at least two epoxy groups includes a structure represented by the formula (a-1), a structure represented by the formula (a-2) or the above two structures. In the formula (a-1), in the formula (a-1), W ¹ , W ² , W ³ and W ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and a carbon number of 1 to An alkoxy group of 5, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 6 to 12 carbon atoms.

The epoxy compound having at least two epoxy groups containing the structure represented by the formula (a-1) may include a bisphenol quinoid compound having an epoxy group obtained by reacting a bisphenol quinoid compound with a halogenated propylene oxide. .

Specifically, specific examples of the bisphenol quinoid compound include: 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9 - bis(4-hydroxy-3-chlorophenyl)anthracene, 9,9-bis(4-hydroxy-3-bromophenyl)anthracene, 9,9-bis(4-hydroxy-3-fluorophenyl)anthracene 9,9-bis(4-hydroxy-3-methoxyphenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene, 9,9-bis (4 -Hydroxy-3,5-dichlorophenyl)indole, 9,9-bis(4-hydroxy-3,5-dibromophenyl)indole or an analogue thereof, or a combination of the above compounds.

Specific examples of the halogenated propylene oxide include 3-chloro-1,2-epoxypropane or 3-bromo-1,2-epoxypropane or the like, or a combination of the above compounds.

Specific examples of the bisphenol quinoid compound having an epoxy group include (1) a product manufactured by Nippon Steel Chemical Co., Ltd.: ESF-300 or the like; (2) a product manufactured by Osaka Gas: for example, PG-100, EG- 210 or an analogue thereof; (3) Commercial products manufactured by SMS Technology Co.: for example, SMS-F9PhPG, SMS-F9CrG, SMS-F914PG or the like.

In addition, specifically, the structure represented by the formula (a-2) is as follows: In the formula (a-2), in the formula (a-2), W ⁵ to W ¹⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms, s An integer representing 0 to 10.

The epoxy compound having at least two epoxy groups containing the structure represented by the formula (a-2) may include a compound having a structure of the following formula (a-2-I) and halogenated in the presence of an alkali metal hydroxide. The propylene oxide is obtained by a reaction. Of formula (a-2-I), in the formula (a-2-I), W is well defined ⁵ to W ¹⁸ s, respectively, and the definition of s in the formula W (a-2) ⁵ to W ¹⁸ The same, no further details here.

The method for synthesizing an epoxy compound having at least two epoxy groups having the structure represented by the formula (a-2) is as follows: First, in the presence of an acid catalyst, a structure having the following formula (a-2-II) is used. After the compound is subjected to a condensation reaction with a phenol, a compound having the structure of the formula (a-2-I) is formed. Next, an excess of halogenated propylene oxide is added to carry out dehydrohalogenation of the halogenated propylene oxide with a compound having the structure of the formula (a-2-I), and the obtained formula (a-2) is obtained. An epoxy compound having at least two epoxy groups. Formula (a-2-II)

In the above formula (a-2-II), W ¹⁹ and W ²⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms; B ¹ and B; ² each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. The above halogen atom is preferably chlorine or bromine. The above alkyl group is preferably a methyl group, an ethyl group or a tert-butyl group. The above alkoxy group is preferably a methoxy group or an ethoxy group.

Specific examples of the phenols include: phenol, cresol, ethylphenol, n-propanol, isobutylphenol, t-butanol, octylphenol, nonylphenol, indophenol, methylbutylphenol, di-tert-butyl Phenol, vinyl phenol, propylene phenol, acetylene phenol, cyclopentyl phenol, cyclohexyl phenol, cyclohexyl cresol or the like. The above phenols may be used singly or in combination of two or more.

The compound having the structure of the above formula (a-2-II) is used in an amount of 1 mol, and the phenol is used in an amount of from 0.5 mol to 20 mol, and preferably from 2 mol to 15 mol.

Specific examples of the acid catalyst include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminum chloride, zinc chloride or the like. The acid catalyst is preferably p-toluenesulfonic acid, sulfuric acid, hydrochloric acid or a combination of the above compounds. The acid catalysts may be used singly or in combination of two or more.

Further, the amount of the above acid catalyst used is not particularly limited. However, the use amount of the compound having the structure of the above formula (a-2-II) is 100% by weight (wt%), and the acid catalyst is preferably used in an amount of from 0.1% by weight to 30% by weight.

The above condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. Further, specific examples of the above organic solvent include toluene, xylene, methyl isobutyl ketone or the like. The above organic solvents may be used singly or in combination of two or more.

The organic solvent is used in an amount of 50% by weight to 300% by weight, preferably 100% by weight to 250% by weight based on the total weight of the compound having the formula (a-2-II) and the phenol. . Further, the above condensation reaction has an operation temperature of 40 ° C to 180 ° C, and the condensation reaction has an operation time of 1 hour to 8 hours.

After completion of the above condensation reaction, a neutralization treatment or a water washing treatment may be performed. The above neutralization treatment adjusts the pH of the solution after the reaction to pH 3 to pH 7, and preferably pH 5 to pH 7. The above water washing treatment can be carried out using a neutralizing agent, wherein the neutralizing agent is an alkaline substance, and specifically includes: an alkali metal hydroxide of sodium hydroxide, potassium hydroxide or the like; calcium hydroxide and hydrogen An alkaline earth metal hydroxide of magnesium oxide or the like; an organic amine of diethylenetriamine, triethylenetetramine, aniline, phenylenediamine or the like; ammonia, sodium dihydrogen phosphate or a combination of the above compounds . The above neutralizing agents may be used singly or in combination of two or more. The above water washing treatment can be carried out by a conventional method, for example, by adding an aqueous solution containing a neutralizing agent to the solution after the reaction, and carrying out the extraction repeatedly. After the neutralization treatment or the water washing treatment, the unreacted phenols and the solvent can be distilled off by heat treatment under reduced pressure, and concentrated, so that a compound having the structure of the formula (a-2-I) can be obtained. .

Specific examples of the halogenated propylene oxide include 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane or a combination of the above compounds. An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance or added to the reaction before the dehydrohalogenation reaction. The above dehydrohalogenation reaction has an operating temperature of from 20 ° C to 120 ° C and an operation time ranging from 1 hour to 10 hours.

In one embodiment, the alkali metal hydroxide added in the dehydrohalogenation reaction may also be an aqueous solution thereof. In this embodiment, while the above aqueous alkali metal hydroxide solution is continuously added to the dehydrohalogenation reaction system, water and halogenated propylene oxide can be continuously distilled off under reduced pressure or normal pressure, thereby separating and removing. Water, and the halogenated propylene oxide can be continuously refluxed into the reaction system.

Before the above dehydrohalogenation reaction is carried out, a quaternary ammonium salt of tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like may be added as a catalyst, and at 50 ° C to After reacting at 150 ° C for 1 hour to 5 hours, an alkali metal hydroxide or an aqueous solution thereof is added. Next, the reaction is allowed to proceed for 1 hour to 10 hours at a temperature of from 20 ° C to 120 ° C to carry out a dehydrohalogenation reaction.

The above-mentioned halogenated propylene oxide is used in an amount of from 1 equivalent to 20 equivalents, and preferably from 2 equivalents to 10 equivalents, based on 1 equivalent of the total hydroxyl group in the compound having the structure of the formula (a-2-I). The total equivalent weight of the hydroxyl group in the compound having the structure of the formula (a-2-I) is 1 equivalent, and the amount of the alkali metal hydroxide added in the above dehydrohalogenation reaction is 0.8 to 15 equivalents, and It is preferably from 0.9 equivalents to 11 equivalents.

Further, in order to allow the above-described dehydrohalogenation reaction to proceed smoothly, an alcohol of methanol, ethanol or the like may be added. In addition to this, an aprotic polar solvent of dimethylhydrazine, dimethyl hydrazine or the like may be added to carry out the reaction. In the case of using an alcohol, the total amount of the halogenated propylene oxide based on the above is 100 wt%, and the amount of the alcohol used is 2 wt% to 20 wt%, and preferably 4 wt% to 15 wt%. In the case of using an aprotic polar solvent, the total amount of the aprotic polar solvent is from 5 wt% to 100 wt%, and preferably 10 wt%, based on the total amount of the halogenated propylene oxide being 100 wt%. Up to 90 wt%.

After completion of the dehydrohalogenation reaction, a water washing treatment can be selectively performed. Thereafter, the halogenated propylene oxide, the alcohol, and the aprotic polar solvent are removed by heating and depressurizing, for example, at a temperature of 110 ° C to 250 ° C and a pressure of 1.3 kPa (10 mmHg) or less.

In order to prevent the formed epoxy resin from containing a hydrolyzable halogen, the solution after the dehydrohalogenation reaction may be added to a solvent such as toluene or methyl isobutyl ketone or an alkali metal hydroxide aqueous solution such as sodium hydroxide or potassium hydroxide. And the dehydrohalogenation reaction is carried out again. In the dehydrohalogenation reaction, the total hydroxyl group equivalent weight in the compound having the structure of the formula (a-2-I) is 1 equivalent, and the alkali metal hydroxide is used in an amount of 0.01 mol to 0.3 mol, and Good is 0.05 to 0.2 moles. Further, the above dehydrohalogenation reaction has an operating temperature in the range of 50 ° C to 120 ° C and an operation time ranging from 0.5 hour to 2 hours.

After completion of the dehydrohalogenation reaction, the salts are removed by filtration, washing, and the like. Further, by evaporating a solvent such as toluene or methyl isobutyl ketone by heating and pressure reduction, an epoxy having at least two epoxy groups having a structure represented by the formula (a-2) can be obtained. Compound. Specific examples of the epoxy compound having at least two epoxy groups having the structure represented by the formula (a-2) include the trade names NC-3000, NC-3000H, NC-3000S, and NC-3000P. Goods manufactured by medicine.

The compound (a-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is selected from one of the groups consisting of the following (1) to (3): (1) acrylic acid, methyl group Acrylic acid, 2-methacryloyloxyethyl succinic acid, 2-methylpropenyloxybutyl succinic acid, 2-methyl propylene oxyethyl adipate, 2-methyl propylene oxy butyl Adipic acid, 2-methylpropenyloxyethylhexahydrophthalic acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxypropyl maleic acid, 2-methyl Propylene oxirane maleic acid, 2-methyl propylene methoxy succinic acid, 2-methyl propylene oxypropyl adipate, 2-methyl propylene oxypropyl tetrahydrophthalic acid , 2-methacryloxypropyl phthalic acid, 2-methyl propylene oxybutyl phthalic acid, 2-methyl propylene oxybutyl phthalic acid or the like; (2 a compound obtained by reacting a (meth) acrylate having a hydroxyl group with a dicarboxylic acid compound, wherein specific examples of the dicarboxylic acid compound include adipic acid, succinic acid, maleic acid, phthalic acid or Its analogue; and (3) from having hydroxyl A half ester compound obtained by reacting a (meth) acrylate with a carboxylic anhydride compound, and specific examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylic acid. Ester, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, pentaerythritol trimethacrylate or the like. Further, the carboxylic anhydride compound described herein may be selected from one of the groups consisting of the following (1) to (2): (1) succinic anhydride, maleic anhydride, itaconic anhydride, ortho-benzene Dicarboxylic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl bridged methylene tetrahydroortylene a dicarboxylic anhydride compound of dicarboxylic anhydride, chloralic anhydride, glutaric anhydride, trimellitic anhydride or the like; and (2) benzophenone tetracarboxylic dianhydride, diphenyltetracarboxylic dianhydride, diphenyl A tetracarboxylic anhydride compound of ether tetracarboxylic dianhydride or the like.

The unsaturated group-containing resin (A-2) of the present invention has a weight average molecular weight of usually 600 to 10,000, preferably 800 to 8,000, more preferably 1,000 to 6,000. The molecular weight of the resin (A-2) having an unsaturated group can be adjusted by using a single resin or a resin of two or more different molecular weights.

The amount of the unsaturated group-containing resin (A-2) used is 0 to 70 parts by weight, preferably 5 to 60 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). It is preferably 10 to 50 parts by weight. When the photosensitive resin composition is a resin (A-2) having an unsaturated group, the hardness of the protective film/gap body obtained by the photosensitive resin composition is preferable. Polyoxyalkylene polymer having an acid anhydride group or an epoxy group (A-3)

The alkali-soluble resin (A) includes a polyoxyalkylene polymer (A-3) having an acid anhydride group or an epoxy group, and the polyoxyalkylene polymer (A-3) is polymerized by a reactant [ That is, a hydrolysis and a partial condensation reaction are formed, and the reactant may include a silane monomer, a siloxane prepolymer, or a decane monomer. A combination of polyoxyalkylene prepolymers.

The polyoxyalkylene polymer (A-3) is obtained by hydrolyzing and partially condensing at least one decane monomer having the structure of the formula (9): Si(U ¹ ) _w (OU ² ) _4-w Formula (9) w represents an integer from 1 to 3, and when w represents 2 or 3, a plurality of U ¹ are each the same or different; and when 4-w represents 2 or 3, a plurality of U ² are each the same or different; at least one of U ¹ represents a substituted anhydride-C ₁ to C ₁₀ alkyl group, the substituted alkyl group of the epoxy-C ₁ to C ₁₀ or of the epoxy-substituted alkoxy group, and the remaining U ¹ Represents hydrogen, C ₁ to C ₁₀ alkyl, C ₂ to C ₁₀ alkenyl or C ₆ to C ₁₅ aryl; and U ² represents hydrogen, C ₁ to C ₆ alkyl, C ₁ to C ₆ A thiol group or an aromatic group of C ₆ to C ₁₅ .

Specific examples of the C ₁ to C ₁₀ alkyl group substituted with an acid anhydride group are, for example, ethyl succinic anhydride, propyl succinic anhydride or propyl glutaric anhydride.

Specific examples of the C ₁ to C ₁₀ alkyl group substituted with an epoxy group, such as oxetanylpentyl or 2-(3,4-epoxycyclohexyl)ethyl [2-(3) , 4-epoxycyclohexyl)ethyl] and the like.

Specific examples of the epoxy group-substituted oxyalkyl group are, for example, glycidoxypropyl or 2-oxetanylbutoxy.

In U ² , the aforementioned alkyl group may include, but is not limited to, methyl, ethyl, n-propyl, isopropyl or n-butyl groups and the like. The thiol group can include, but is not limited to, an ethyl group. The aryl group can include, but is not limited to, a phenyl group.

The decane monomer represented by the formula (9) may include, but is not limited to, 3-glycidoxypropyltrimethoxysilane (TMS-GAA), 3-glycidoxypropyltriethoxylate. 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxy silane, 2-epoxypropoxybutoxy 2-oxetanylbutoxypropyltriphenoxysilane, 3-(triphenyloxyindenyl)propyl succinic anhydride, 3-(trimethoxydecyl)propyl glutaric anhydride (TMSG), 3-( Triethoxyindolyl propyl glutaric anhydride, 3-(triphenyloxyindenyl)propyl glutaric anhydride, diisopropoxy-bis(2-epoxypropoxybutoxypropyl)decane [diisopropoxy-di(2-oxetanylbutoxypropyl)silane; DIDOS], di(3-oxetanylpentyl)dimethoxy silane, (di-n-butoxycarbonyl) ) bis (propyl succinic anhydride), (dimethoxy fluorenyl) bis (ethyl succinic anhydride), 3-glycidoxy propyl dimethyl methoxysilane, 3 -glycidoxypropyl 3-glycidoxypropyldimethylethoxysilane, bis(2-epoxytanbutoxypentyl)-2-epoxytanbutoxypentyl-2-oxetanylpentylethoxy Silane], tris(2-oxetanylpentyl)methoxysilane, (phenoxymethyl)tris(propyl succinic anhydride), (methyl methoxy) 2-(ethyl succinic anhydride), 2-oxetanylbutoxypropyltrimethoxysilane, 2-epoxypropoxybutoxypropyltriethoxysilane (2-oxetanylbutoxypropyltriethoxysilane), 3-ethyl-3-{[3-(trimethoxyindenyl)propoxy]methyl} propylene oxide, 3-(trimethoxyindolyl)propyl succinic anhydride, 3-(triethoxyindenyl)propyl succinic anhydride or the like. The decane monomers represented by the above formula (9) may be used singly or in combination of plural kinds.

In another preferred embodiment of the present invention, the siloxane oxide monomer includes, but is not limited to, the structure represented by the following structural formula (9-1): Si(U ⁹ ) _u (OU ¹⁰ ) _4-u (9-1)

Wherein U ⁹ represents a group selected from the group consisting of a hydrogen atom, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₀ alkenyl group, and a C ₆ to C ₁₅ aryl group, wherein the C ₁ to C ₁₀ alkyl group Does not contain a carboxylic anhydride substituent; U ¹⁰ is a group independently selected from the group consisting of a hydrogen atom, a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ fluorenyl group, and a C ₆ to C ₁₅ aryl group; and u represents An integer from 1 to 3; when u represents 2 or 3, the plural U ⁹ may be the same or different; when (4-u) represents 2, 3 or 4, the plural U ¹⁰ may be the same or different.

In U ⁹ , the alkyl group may include, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, n-butyl, trifluoromethyl, 3,3 , 3-trifluoropropyl, 3-aminopropyl, 3-mercaptopropyl or 3-isocyanatopropyl, and the like. The alkenyl group may include, but is not limited to, a vinyl group, a 3-propenyloxypropyl group, a 3-methylpropenyloxypropyl group, and the like. The aryl group may include, but is not limited to, phenyl, tolyl, p-hydroxyphenyl, 1-(p-hydroxyphenyl)ethyl, 2-(p-hydroxyphenyl)ethyl, 4-hydroxy-5- ( p-Hydroxyphenylcarbonyloxy)pentyl or naphthyl and the like.

In U ¹⁰ , the alkyl group may include, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, and the like. The thiol group can include, but is not limited to, an ethyl group. The aryl group can include, but is not limited to, a phenyl group.

The decane monomer represented by the formula (9-1) may include, but is not limited to, tetramethoxy decane, tetraethoxy decane, tetraethoxy decane, tetraphenoxy decane, methyl trimethoxy decane, Triethoxy decane, methyl triisopropoxy decane, methyl tri-n-butoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl triisopropoxy decane, B Tri-n-butoxy decane, n-propyl trimethoxy decane, n-propyl triethoxy decane, n-butyl trimethoxy decane, n-butyl triethoxy decane, n-hexyl trimethoxy decane, hexane Triethoxy decane, decyl trimethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, p-hydroxyphenyl trimethyl Oxydecane, 1-(p-hydroxyphenyl)ethyltrimethoxynonane, 2-(p-hydroxyphenyl)ethyltrimethoxynonane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy) Pentyltrimethoxydecane, trifluoromethyltrimethoxydecane, trifluoromethyltriethoxydecane, 3,3,3-trifluoropropyltrimethoxydecane, 3-aminopropyl Methoxydecane, 3-aminopropyltriethoxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane, dimethyldiethoxydecane, di-n-butyldimethyl Oxydecane, diphenyldimethoxydecane, trimethylmethoxydecane, tri-n-butylethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-propenyloxypropyltrimethoxy Alkane, 3-methacryloxypropyltrimethoxydecane or 3-methylpropenyloxypropyltriethoxydecane. The decane monomers represented by the above formula (9-1) may be used singly or in combination of plural kinds.

In a specific example of the present invention, when a copolymerization reaction of a compound of the formula (9) is carried out, the carboxylic anhydride contained in the compound (9) is self-opened to have a hydrophilic carboxylate. The polyoxyalkylene polymer (A-3) obtained above has better developability to an alkaline developer. The temperature of the polymerization reaction is such that the carboxylic acid anhydride can be sufficiently opened, preferably at a temperature higher than 100 ° C for 30 minutes.

According to the present invention, when the carboxylic acid anhydride ring-opening reaction is carried out, the amount of the carboxylic acid anhydride ring opening is not limited with respect to the ruthenium atom in the polyoxyalkylene polymer (A-3), and is preferably more than 10 mol%. When the carboxylate is less than 10 mol%, the hydrophilicity of the polyoxyalkylene polymer (A-1) is insufficient. Therefore, when the applied pattern is developed in an alkaline developing solution, low photosensitivity and developability are caused. The carboxylate content can be determined, for example, but not limited to, by the methods described below.

First, 1% by weight of a benzene standard and a polyoxyalkylene polymer (A-1) are mixed for elemental analysis and ¹ H-NMR measurement, and the molar amount of the benzene molar to the Si atom is calculated in the elemental analysis. number. The peak area of the carboxylic acid and the peak area of benzene were measured by ¹ H-NMR (using ¹ H-NMR: CDCl ₃ solvent), and the carboxylic acid anhydride of the ruthenium atom in the polyoxyalkylene polymer (A-1) was opened. The amount can be calculated by the number of benzyl groups.

Preferably, the polymerization reactant of the aforementioned polyoxyalkylene polymer (A-3) having an acid anhydride group or an epoxy group may comprise a polyoxyalkylene prepolymer represented by the following formula (9-2): Equation (9-2)

Wherein, U ¹¹ , U ¹² , U ¹³ and U ¹⁴ may be the same or different and are respectively selected from a hydrogen atom, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₆ alkenyl group and a C ₆ to C ₁₅ a group consisting of aryl groups; wherein the alkyl, alkenyl or aryl group preferably contains a substituent; wherein each U ¹¹ may be the same or different, and each U ¹² may be the same or different; the aforementioned alkane The group may include, but is not limited to, methyl, ethyl or n-propyl groups and the like. The alkenyl group may include, but is not limited to, a vinyl group, a propylene methoxy propyl group, a methacryloxypropyl group, and the like. The aryl group may include, but is not limited to, a phenyl group, a tolyl group or a naphthyl group; and v is an integer of from 1 to 1000; preferably, v is an integer between 3 and 300; more preferably, v is an intermediate An integer between 5 and 200. U ¹⁵ and U ¹⁶ are each selected from the group consisting of a hydrogen atom, a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ fluorenyl group, and a C ₆ to C ₁₅ aryl group; The base or aryl group preferably contains a substituent. Preferably, the alkyl group is, for example but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, and the like; the fluorenyl group is, for example, but not limited to, an ethyl group; the aryl group is, for example, but not limited to, a phenyl group.

The polyoxyalkylene prepolymer represented by the formula (9-2) may include, but is not limited to, 1,1,3,3-tetramethyl-1,3-dimethoxydioxane, 1,1. 3,3-Tetramethyl-1,3-diethoxydioxane, 1,1,3,3-tetraethyl-1,3-diethoxydioxane or manufactured by Gelest The stanol-terminated polyoxyalkylenes are DM-S12 (molecular weight 400 to 700), DMS-S15 (molecular weight 1500 to 2000), DMS-S21 (molecular weight 4200), and DMS-S27 (molecular weight 18000). ), DMS-S31 (molecular weight 26000), DMS-S32 (molecular weight 36000), DMS-S33 (molecular weight 43500), DMS-S35 (molecular weight 49000), DMS-S38 (molecular weight 58000), DMS-S42 (molecular weight: 77000) or PDS-9931 (molecular weight: 1,000 to 1400). The polyoxyalkylene polymer represented by the formula (9-2) may be used singly or in combination of plural kinds.

Preferably, the polyoxyalkylene polymer can be prepared by polymerization by the aforementioned decane monomer and/or polydecane prepolymer, or by combining co-polymerization of silicon dioxide particles. To prepare. The average particle diameter of the cerium oxide particles is not particularly limited, and the average particle diameter thereof ranges from 2 nm to 250 nm. Preferably, the average particle size ranges from 5 nm to 200 nm. More preferably, the average particle diameter ranges from 10 nm to 100 nm.

The cerium oxide particles may include, but are not limited to, those manufactured by Catalyst Chemical Co., Ltd., model number OSCAR 1132 (particle diameter: 12 nm, and dispersant is methanol), OSCAR 1332 (particle diameter: 12 nm, and dispersant is n-propanol). ), OSCAR 105 (particle size is 60 nm, and the dispersant is γ-butyrolactone) or OSCAR 106 (particle size is 120 nm, and the dispersant is diacetone alcohol); manufactured by Fuso Chemical Co., Ltd., model Quartron PL-1-IPA (particle size 13 nm, and dispersant is isopropanone), Quartron PL-1-TOL (particle size 13 nm, and dispersant is toluene), Quartron PL-2L-PGME (particle size 18 nm, And the dispersing agent is propylene glycol monomethyl ether) or Quartron PL-2L-MEK (having a particle diameter of 18 nm and the dispersing agent is methyl ethyl ketone), etc., manufactured by Nissan Chemical Co., Ltd., model IPA-ST (particle size is 12 nm, and The dispersant is isopropanol), EG-ST (particle size is 12 nm, and the dispersant is ethylene glycol), IPA-ST-L (particle size is 45 nm, and the dispersant is isopropanol) or IPA-ST- A product such as ZL (having a particle diameter of 100 nm and a dispersing agent is isopropyl alcohol). The cerium oxide particles may be used singly or in combination of plural kinds.

The above partial condensation reaction can be carried out by a usual method, for example, by adding a solvent and water to a decane monomer, and optionally adding a catalyst. Next, the mixture is heated and stirred at 50 ° C to 150 ° C for 0.5 hour to 120 hours. When stirring, the reaction can remove by-products (alcohols or water, etc.) by distillation.

The solvent is not particularly limited and may be the same as or different from the solvent (D) contained in the photosensitive resin composition of the present invention. The total amount of the decane monomer used is 100 g, and the solvent is used in an amount of 15 g to 1200 g. Preferably, the solvent is used in an amount of from 20 grams to 1100 grams. More preferably, the solvent is used in an amount of from 30 g to 1000 g.

The water used for the hydrolysis is used in an amount of from 0.5 mol to 2 mol based on 1 mol of the hydrolyzable group contained in the decane monomer.

The above catalyst is not particularly limited. Preferably, the catalyst may be selected from an acid catalyst or a base catalyst. The acid catalyst may include, but is not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or anhydride thereof, or an ion exchange resin or the like. The base catalyst may include, but is not limited to, diethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, triheptylamine, trioctylamine, diethanolamine, triethanolamine, sodium hydroxide. And potassium hydroxide, an alkoxysilane having an amine group, an ion exchange resin, or the like.

The catalyst is used in an amount ranging from 0.005 g to 15 g based on the total amount of the decane monomer being 100 g. Preferably, the catalyst is used in an amount ranging from 0.01 grams to 12 grams. More preferably, the catalyst is used in an amount ranging from 0.05 g to 10 g.

From the viewpoint of stability, the polyoxyalkylene polymer (A-3) having an acid anhydride group or an epoxy group obtained by a condensation reaction is preferably free from by-products (such as alcohols or water) and a catalyst. Therefore, the polyoxyalkylene polymer (A-3) having an acid anhydride group or an epoxy group can be selectively purified. The purification method is not particularly limited, and it is preferred to dilute the polyoxyalkylene polymer (A-3) having an acid anhydride group or an epoxy group using a hydrophobic solvent, followed by concentrating the organic layer washed several times with water by an evaporator. To remove alcohol or water. Alternatively, the catalyst can be removed using an ion exchange resin.

The polyoxyalkylene polymer (A-3) having an acid anhydride group or an epoxy group of the present invention has a weight average molecular weight of usually 1,000 to 50,000, preferably 2,000 to 40,000, more preferably 3,000 to 30,000. The molecular weight of the polyoxyalkylene polymer (A-3) having an acid anhydride group or an epoxy group can be adjusted by using a single resin or a resin of two or more different molecular weights.

The polyoxosiloxane polymer (A-3) having an acid anhydride group or an epoxy group is used in an amount of from 0 to 70 parts by weight, preferably from 0 to 70 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). 5 to 60 parts by weight, more preferably 10 to 50 parts by weight. When the polyoxyalkylene polymer (A-3) is used as the photosensitive resin composition, the high-speed coating property of the protective film/gap body obtained by the photosensitive resin composition is preferable. Other alkali soluble resin (A-4)

The other alkali-soluble resin (A-4) according to the present invention means a resin which is soluble in an aqueous alkaline solution, and the structure thereof is not particularly limited. In a preferred embodiment of the present invention, the other alkali-soluble resin ( A-4) means a carboxylic acid group-containing resin, a phenol-novolac resin, or the like. Compound containing ethylenically unsaturated group (B)

The ethylenically unsaturated group-containing compound (B) includes a first compound (B-1) containing an ethylenically unsaturated group, a second compound (B-2) containing an ethylenically unsaturated group, and an ethylenically unsaturated group. a third compound (B-3), a fourth compound (B-4) containing an ethylenically unsaturated group, a fifth compound (B-5) containing an ethylenically unsaturated group, and other compounds having an ethylenically unsaturated group (B-6). First compound containing an ethylenically unsaturated group (B-1)

The first compound (B) containing an ethylenically unsaturated group includes the ethylenically unsaturated group-containing compound (B-1) having a structure of the formula (II). Wherein A ⁵ represents a hydrogen atom or a methyl group; A ⁶ represents a hydrogen atom, an acryloyl group or a methacryl group; and r represents 3 to 4.

In a specific example of the present invention, the ethylenically unsaturated group-containing first compound (B-1) includes, but is not limited to, pentaerythritol pentoxide (meth) acrylate, pentaerythritol deca (meth) acrylate, and five Any combination of the above compounds of pentaerythritol eleven (meth) acrylate or pentaerythritol dodeca (meth) acrylate.

The ethylenically unsaturated group-containing first compound (B-1) is used in an amount of from 20 parts by weight to 200 parts by weight, based on 100 parts by weight based on the total amount of the alkali-soluble resin (A), preferably 30 parts by weight. The portion is 150 parts by weight, more preferably 40 parts by weight to 100 parts by weight. When the photosensitive resin composition does not use the first compound (B-1) containing an ethylenically unsaturated group, the high-speed coating property and hardness of the protective film/gap body obtained by the photosensitive resin composition are not high. good. Second compound containing ethylenically unsaturated group (B-2)

The ethylenically unsaturated group-containing compound (B) includes a second compound (B-2) containing an ethylenically unsaturated group. The second compound (B-2) containing an ethylenically unsaturated group includes a (meth) acrylate compound monomer represented by the following formula (III). In the formula (III), A ¹ and A ² each independently represent a hydrogen atom or a methyl group; and l represents an integer of 0 to 4.

l In the formula (III), the average number of additions per molecule of the alkyleneoxy group is shown.

Specific examples of the above formula (III) are: p-cumylphenyl (meth)acrylate, p-cumylphenoxyethyl (meth)acrylate, and the like, among which P-cumylphenyl (meth) acrylate and p-cumylphenoxyethyl (meth) acrylate are preferred.

The second unsaturated compound-containing compound (B-2) is used in an amount of 15 to 150 parts by weight, preferably 20 to 130 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A); more preferably It is 25 to 110 parts by weight. When the second resin (B-2) containing an ethylenically unsaturated group is used as the photosensitive resin composition, the protective film/spacer obtained by the photosensitive resin composition has better adhesion and refractive index during development. good. Third compound containing an ethylenically unsaturated group (B-3)

The ethylenically unsaturated group-containing compound (B) includes a third compound (B-3) containing an ethylenically unsaturated group. The third compound (B-3) containing an ethylenically unsaturated group includes a (meth) acrylate compound monomer represented by the following formula (IV). In the formula (IV), A ³ and A ⁴ each independently represent a hydrogen atom or a methyl group; and v represents an integer of 0 to 4.

v In the formula (IV), represents the average number of additions per molecule of the alkyleneoxy group.

Specific examples of the above formula (IV) are: p-phenylphenyl (meth)acrylate, m-phenylphenyl (meth)acrylate, p-phenylbenzene (meth) acrylate, p-phenylphenyl (meth) acrylate, m-phenylphenoxyethyl (meth) acrylate, and p-benzene A phenoxyethyl (meth) acrylate or the like, wherein o-phenylphenyl (meth) acrylate and o-phenylphenoxyethyl (meth) acrylate are preferred.

The ethylenically unsaturated group-containing third compound (B-3) is used in an amount of 15 to 150 parts by weight, preferably 20 to 130 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A); more preferably It is 25 to 110 parts by weight. When the third resin (B-3) containing an ethylenically unsaturated group is used as the photosensitive resin composition, the protective film/spacer obtained by the photosensitive resin composition has better adhesion and refractive index during development. good. Fourth compound containing ethylenically unsaturated group (B-4)

The ethylenically unsaturated group-containing compound (B) includes a fourth compound (B-4) containing an ethylenically unsaturated group. The fourth unsaturated compound-containing compound (B-4) includes a dioxane-based unsaturated compound such as a 1,3-dioxane skeleton and/or a 1,3-dioxolane skeleton. . The structure of the dioxane-based unsaturated compound containing a 1,3-dioxane skeleton is represented by the following formula (V); and the dioxane-based unsaturated compound containing a 1,3-dioxolane skeleton The structure is as shown in the following formula (VI): Formula (V) In the formula (V), B ¹ to B ⁸ each independently represent a hydrogen atom or a hydrocarbon group, and at least one of B ¹ to B ⁸ includes an ethylenically unsaturated group as a substituent at the end thereof; In the above, each of B ¹ to B ⁶ independently represents a hydrogen atom or a hydrocarbon group, and at least one of B ¹ to B ⁶ includes an ethylenically unsaturated group as a substituent at the end thereof.

When B ¹ to B ⁸ are a hydrocarbon group, it is preferably a hydrocarbon group having 1 to 18 carbon atoms. Specific examples thereof are an alkyl group, an aryl group, an aralkyl group, an alkenyl group, a cycloalkyl group and the like; and among them, an alkyl group is preferred.

When B ¹ to B ⁸ are an alkyl group, it is preferably a linear or branched alkyl group having 1 to 8 carbon atoms; more preferably a linear alkyl group having 1 to 4 carbon atoms; Methyl or ethyl.

In the formula (V), at least one of B ¹ to B ⁸ contains a substituent of an ethylenically unsaturated group at its end; or in the formula (VI), at least one of B ¹ to B ⁶ contains an ethyl group at its end The substituent of the unsaturated group, wherein the use of the ethylenically unsaturated substituent is not limited.

In the formula (V), at least one of B ¹ to B ⁸ contains a substituent of an ethylenically unsaturated group at its end; or in the formula (VI), at least one of B ¹ to B ⁶ contains an ethyl group at its end a substituent of an unsaturated group, wherein the ethylenically unsaturated substituent is preferably a (meth) acryloxy or (meth) acrylamide, which is reactive and polymerized. The resulting product is preferably soft.

Preferably, the end portion of the B in the formula (V) of ¹ to B ^8, or of formula (Vl) B ¹ to B ⁶ of the substituents on a molecule containing 1-2 (meth) acrylic acid derivative, the compound The viscosity of itself and the physical properties after hardening are preferred.

In a preferred embodiment of the present invention, the ethylenic unsaturated group-containing fourth compound (B-4) has a structure represented by the following formulas (b4-1) to (b4-23): Equation (b4-1) Equation (b4-2) Formula (b4-3) Equation (b4-4) Equation (b4-5) Formula (b4-6) Formula (b4-7) Equation (b4-8) Formula (b4-9) Equation (b4-10) Equation (b4-11) Equation (b4-12) Equation (b4-13) Equation (b4-14) Equation (b4-15) Equation (b4-16) Equation (b4-17) Equation (b4-18) Equation (b4-19) Equation (b4-20) Equation (b4-21) Equation (b4-22) Formula (b4-23).

Preferred embodiments of the fourth ethylenically unsaturated group-containing compound (B-4) of the present invention are the above formula (b4-2), formula (b4-3), formula (b4-4), and formula (b4). -13) and a compound represented by the formula (b4-15).

The ethylenically unsaturated group-containing fourth compound (B-4) is used in an amount of 5 to 50 parts by weight, preferably 7 to 40 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A); more preferably It is 10 to 30 parts by weight. When the photosensitive resin composition is a fourth compound (B-4) containing an ethylenically unsaturated group, the hardness of the protective film/gap body obtained by the photosensitive resin composition is preferable. Fifth compound containing ethylenically unsaturated group (B-5)

The ethylenically unsaturated group-containing compound (B) includes a fifth compound (B-5) containing an ethylenically unsaturated group. The fifth compound (B-5) containing an ethylenically unsaturated group includes a diacrylate or dimethacrylate having a linear diol.

The diacrylate or dimethacrylate of the chain diol has two reactive unsaturated functional groups, and such functional groups are bonded by molecular chains having no cyclic structure. From the viewpoint of reactivity, the aforementioned molecular chain is preferably a straight chain and has a carbon number of 2 or more. The carbon number of the aforementioned molecular chain is preferably 12 or less from the viewpoint of mutual solubility.

The fifth compound (B-5) containing an ethylenically unsaturated group is preferably ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, and 1,4-butylene. Diol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate or 1,9-nonanediol Dimethacrylate.

The fifth unsaturated compound-containing compound (B-5) is used in an amount of 10 to 150 parts by weight, preferably 20 to 120 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A); more preferably It is 30 to 100 parts by weight. When the fifth unsaturated compound-containing compound (B-5) is used as the photosensitive resin composition, the high-speed coating property of the protective film/gap obtained by the photosensitive resin composition is preferable. Other ethylenically unsaturated group compounds (B-6)

The ethylenically unsaturated group-containing compound (B) more preferably includes other ethylenically unsaturated group-containing compound (B-6).

The other ethylenically unsaturated group-containing compound (B-6) may include, but is not limited to, dicyclopentenyl di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(methyl) ) acrylate, tris(2-hydroxyethyl)isocyanate di(meth)acrylate, tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, caprolactone modified three ( Tris(hydroxy)ethyl isocyanate, trimethylolpropyl tris(meth)acrylate, ethylene oxide (referred to as EO) modified tris(meth)acrylic acid Tripropyl methacrylate, propylene oxide modified (PO), trimethylol propyl (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol Tris (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, two Pentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, caprolactone modified season Tetraol hexa(meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, di(trimethylolpropane) tetra(meth)acrylate] Ethylene oxide modified bisphenol A di(meth) acrylate, propylene oxide modified bisphenol A di(meth) acrylate, ethylene oxide modified hydrogenated bisphenol A Di(meth)acrylate, propylene oxide modified hydrogenated bisphenol A di(meth)acrylate, propylene oxide modified glycerol tri(meth)acrylate, modified with ethylene oxide Bisphenol F di(meth) acrylate, novolak polyglycidyl ether (meth) acrylate, and the like. The other ethylenically unsaturated group-containing compound (B-6) may be used singly or in combination of plural kinds.

The total amount of the ethylenically unsaturated group-containing compound (B) to be used is 50 parts by weight to 500 parts by weight, preferably 60 parts by weight to 450 parts, based on 100 parts by weight of the total amount of the alkali-soluble resin (A). The parts by weight are more preferably from 70 parts by weight to 400 parts by weight. Photoinitiator (C)

The photoinitiator (C) includes a photoinitiator (C-1), other O-mercaptoquinone compounds (C-2), and other photoinitiators (C-3). Photoinitiator (C-1)

The photoinitiator (C) includes a photoinitiator (C-1) represented by the formula (1). Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen, C ₁ -C ₂₀ alkyl, COR ₁₆ , OR ₁₇ , halogen, NO ₂ , a group represented by the formula (2) or a group represented by the formula (3), Formula (2) ; Formula (3); or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are independently of each other via formula (4) Substituted C ₂ -C ₁₀ alkenyl group Formula (4); or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are each independently taken as —(CH ₂ ) _p —Y—(CH ₂ ) _q —; or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are independent of each other The group together is a group represented by the formula (5); Formula (5); but the condition is that at least one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are The group represented by the formula (5), R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently hydrogen, C ₁ -C ₂₀ alkyl, and the C ₁ -C ₂₀ alkyl group is unsubstituted or passed through a Or substituted with more than one of the following groups: halogen, phenyl, CN, OH, SH, C ₁ -C ₄ -alkoxy, -(CO)OH or -(CO)O-(C ₁ -C ₄ alkyl) Or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are, independently of each other, an unsubstituted phenyl group or a phenyl group substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, CN, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently halogen, CN, OR ₁₇ , SR ₁₈ , SOR ₁₈ , SO ₂ R ₁₈ or NR ₁₉ R ₂₀ , wherein The substituents OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ optionally form a 5- or 6-membered ring via a carbon atom in the naphthyl ring via the groups R ₁₇ , R ₁₈ , R ₁₉ and/or R ₂₀ ; Or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a group represented by COR ₁₆ , NO ₂ or formula (2), Formula (2); Y represents O, S, NR ₂₆ or a direct bond; p represents an integer of 0, 1, 2 or 3; q represents an integer 1, 2 or 3; X represents CO or a direct bond; R ₁₃ represents C ₁ - a C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ , NR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ or a group represented by the formula (6); Formula (6); or R ₁₃ represents a C ₂ -C ₂₀ alkyl group in which one or more of O, S, SO, SO ₂ , NR ₂₆ or CO, or a C ₂ -C ₁₂ alkenyl group, which is not Interstitial or heterozygous with one or more O, CO or NR ₂₆ , wherein the interstitial C ₂ -C ₂₀ alkyl group and the uninterstitial or interstitial C ₂ -C ₁₂ alkenyl group are unsubstituted or Or a plurality of halogen substitutions; or R ₁₃ represents a C ₄ -C ₈ cycloalkenyl group, a C ₂ -C ₁₂ alkynyl group or a C ₃ -C ₁₀ having no or hetero or hetero or one or more O, S, CO or NR ₂₆ Cycloalkyl; or R ₁₃ represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , COR ₁₆ , CN, NO ₂ , a halogen, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₄ haloalkyl group, a hetero group having one or more C ₂ -C ₂₀ alkyl groups of O, S, CO or NR ₂₆ or a group represented by the formula (7), Formula (7); each warp or a C ₃ -C ₁₀ cycloalkyl, or interrupted by one or more O, S, CO or NR ₂₆ of the C ₃ -C ₁₀ cycloalkyl; K represents integer of 1 to 10; R ₁₄ represents hydrogen, C ₃ -C ₈ cycloalkyl, C ₂ -C ₅ alkenyl, C ₁ -C ₂₀ alkoxy or C ₁ -C ₂₀ alkyl, which is unsubstituted or one or more of the following Substituents: halogen, phenyl, C ₁ -C ₂₀ alkylphenyl or CN; or R ₁₄ represents phenyl or naphthyl, each unsubstituted or substituted by one or more of the following groups: C ₁ - C ₆ alkyl, C ₁ -C ₄ haloalkyl, halogen, CN, OR ₁₇ , SR ₁₈ and/or NR ₁₉ R ₂₀ ; or R ₁₄ represents C ₃ -C ₂₀ heteroaryl, C ₁ -C ₈ alkoxy a benzyloxy group or a phenoxy group which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl and/ Or halogen; R ₁₅ represents C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ Haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ , SO-C ₁ -C ₁₀ alkyl, SO ₂ -C ₁ -C ₁₀ alkyl One or one A O, S or NR C ₂₆ of ₂ -C ₂₀ alkyl group; or each warp substituted C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkyl which is unsubstituted or substituted with one or more of the following groups Substitution: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryl Oxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ represents hydrogen, C ₂ -C ₁₂ alkenyl, unmixed or hetero-has one or more O, CO or NR ₂₆ C ₃ -C ₈ a cycloalkyl group; or R ₁₅ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, C _3- C ₂₀ Heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ , PO(OC _k H _{2k+1 2} ) a phenyl group, a group represented by the formula (6) or a group represented by the formula (8), Formula (6) Formula (8); or the C ₁ -C ₂₀ alkyl group is substituted by a phenyl group which is halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R _{20 is} substituted; or R ₁₅ represents a C ₂ -C ₂₀ alkyl group in which one or more O, SO or SO ₂ are heterogeneous, and the interstitial C ₂ -C ₂₀ alkyl group is unsubstituted or subjected to one or Substituted by a plurality of groups: halogen, OR ₁₇ , COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl or phenyl substituted with OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ represents C ₂ -C ₂₀ alkane Or benzylidene, which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ And a C ₃ -C ₁₄ alkoxycarbonyl group which is unsubstituted or substituted with one or more OR ₁₇ ; or R ₁₅ represents a C ₂ -C ₁₂ alkoxycarbonyl group which is unintercalated or Miscellaneous with one or more O and the inter- or un-doped C ₂ -C ₁₂ alkoxycarbonyl group is unsubstituted or substituted with one or more hydroxyl groups; or R ₁₅ represents a phenoxycarbonyl group, which is not Substituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, C ₁ -C _4- haloalkyl, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ represents CN, CONR ₁₉ R ₂₀ , NO ₂ , C ₁ -C ₄ haloalkyl, S(O) _m -C ₁ -C _{a 6} alkyl group, an unsubstituted or S(O) _m -phenyl group substituted with a C ₁ -C ₁₂ alkyl group or a SO ₂ -C ₁ -C ₆ alkyl group; or R ₁₅ represents a SO ₂ O-phenyl group, Is unsubstituted or substituted by C ₁ -C ₁₂ alkyl; or diphenylphosphinyl or di-(C ₁ -C ₄ alkoxy)-phosphonium; m represents 1 or 2; R' ₁₄ Has one of the meanings given for R ₁₄ ; R' ₁₅ has one of the meanings given for R ₁₅ ; X ₁ represents O, S, SO or SO ₂ ; X ₂ represents O, CO, S or Direct bond; R ₁₆ represents C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ Haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or a heterocyclic one or more C ₁ -C ₂₀ alkyl groups of O, S or NR ₂₆ ; or each of one or more C ₁ - C ₂₀ alkyl substituted, the C ₁ -C ₂₀ alkyl group being unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl , C ₃ -C _{2 0} heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl group, C ₃ -C ₂₀ heteroaryl aryloxycarbonyl group, OR _17, SR ₁₈ or NR ₁₉ R _20; or R ₁₆ represents hydrogen, C ₁ -C ₂₀ alkyl , the C ₁ -C ₂₀ alkyl group is unsubstituted or substituted with one or more of the following groups: halogen, phenyl, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ )alkyl, O(CO)-(C ₁ -C ₄ alkyl), O(CO)-phenyl, (CO)OH or (CO)O (C ₁ -C ₄ alkyl); or R ₁₆ represents C ₂ -C ₁₂ alkyl with one or more O, S or NR _{26 in between} ; or R ₁₆ represents (CH ₂ CH ₂ O) _n+1 H , (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₁₂ alkenyl or C ₃ -C ₈ cycloalkyl; or R ₁₆ represents benzene substituted by SR ₁₈ a group wherein the group R ₁₈ represents a direct bond to the phenyl or naphthyl ring to which the carbazole moiety is attached to the COR ₁₆ group; n represents 1 to 20; R ₁₇ represents hydrogen, phenyl -C ₁ -C ₃ alkyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ ) Alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C ₁ -C ₄ alkyl), C ₃ -C ₂₀ cycloalkyl, SO ₂ -(C _1- C ₄ haloalkyl Or O(C ₁ -C ₄ haloalkyl) or a C ₃ -C ₂₀ cycloalkyl group having one or more O; or R ₁₇ represents a C ₂ -C ₂₀ alkyl group, wherein one or more O, S are hetero Or NR ₂₆ ; or R ₁₇ represents (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₁ -C ₈ alkyl fluorenyl a C ₂ -C ₁₂ alkenyl group, a C ₃ -C ₆ olefinic group or a C ₃ -C ₂₀ cycloalkyl group having one or more O, S, CO or NR ₂₆ without inter or hetero-hetero; or R ₁₇ represents C _{a 1-} C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl group which is undoped or hetero-has one or more O; or R ₁₇ represents a benzamidine group which is unsubstituted or has one or more C _1- C ₆ alkyl, halogen, OH or C ₁ -C ₃ alkoxy substituted; or R ₁₇ represents phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or via one or Substituted by a plurality of groups: halogen, OH, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N (C ₁ -C ₁₂ alkyl) _2, diphenyl - group, or of formula (7) represented by Group; Formula (7); or R ₁₇ is bonded to one of the carbon atoms of the phenyl or naphthyl ring to which the group represented by the formula (2) or the group represented by the formula (7) is bonded Direct key, Formula (2) R ₁₈ represents hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl or phenyl-C ₁ -C ₃ alkyl, wherein the C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl or phenyl-C ₁ -C ₃ alkyl is one or more O, S, CO, NR ₂₆ or COOR ₁₇ without inter or hetero-hetero; or R ₁₈ is C ₁ -C ₂₀ alkyl , which is unsubstituted or substituted with one or more of the following groups: OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O (C ₁ - C ₄ alkyl), O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-(C ₁ -C ₄ alkyl), O(CO)-phenyl or (CO)OR ₁₇ ; Or R ₁₈ represents a C ₂ -C ₂₀ alkyl group with one or more O, S, CO, NR ₂₆ or COOR _{17 in between} ; or R ₁₈ represents (CH ₂ CH ₂ O) _n H, (CH ₂ CH ₂ O _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₈ alkanoyl or C ₃ -C ₆ olefin; or R ₁₈ represents a benzamidine group, which is unsubstituted or Substituted by one or more of the following: C ₁ -C ₆ alkyl, halogen, OH, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkylthio; or R ₁₈ represents phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following radicals: halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₄ haloalkoxy , C ₁ -C ₁₂ alkoxy, CN, NO _2, phenyl -C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N (C ₁ -C ₁₂ alkyl) ₂ , diphenylamino, (CO)O(C ₁ -C ₈ alkyl), (CO)-C ₁ -C ₈ alkyl, (CO)N (C ₁ -C ₈ Alkyl) ₂ or a group represented by formula (7) Formula (7); R ₁₉ and R ₂₀ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₂ -C ₁₀ alkoxyalkyl, C ₂ -C ₅ olefin , C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₈ alkanoyl, C ₁ -C ₈ alkenyloxy, C ₃ -C ₁₂ olefin , SO ₂ —(C ₁ -C ₄ haloalkyl) or benzhydryl; or R ₁₉ and R ₂₀ represent phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or Or substituted with a plurality of groups: halogen, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₁₂ alkyl, benzhydryl or C ₁ -C ₁₂ alkoxy; R ₁₉ and R ₂₀ together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which is unintermixed or intermixed with O, S or NR ₁₇ and which is a saturated or unsaturated ring of 5 or 6 members. Is unsubstituted or substituted by one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, =0, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO)R ₂₃ , NO ₂ , halogen, C ₁ -C ₄ -haloalkyl, CN, phenyl, C ₃ -C ₂₀ cycloalkyl, or a formula having one or more O, S, CO or NR ₁₇ without inter or hetero (7) indicated group Formula (7); or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkane Base, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, =0, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO)R ₂₃ , halogen, NO ₂ , CN, phenyl or not a C ₃ -C ₂₀ cycloalkyl group having one or more O, S, CO or NR ₁₇ or a group represented by the formula (7) R ₂₁ and R ₂₂ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₁₀ cycloalkyl or phenyl; or R ₂₁ and R ₂₂ Together with the N atom to which it is attached, it forms a 5- or 6-membered saturated or unsaturated ring which is not intermixed or interspersed with O, S or NR ₂₆ , and the 5 or 6 member saturated or unsaturated ring is unfused or The 5- or 6-membered saturated or unsaturated ring is fused to the benzene ring; R ₂₃ represents hydrogen, OH, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, inter-hetero or one or more O, CO or NR _a C ₂ -C ₂₀ alkyl group, a C ₃ -C ₂₀ cycloalkyl group having no O, S, CO or NR ₂₆ , or R ₂₃ representing a phenyl group, a naphthyl group, a phenyl-C ₁ group C ₄ alkyl, OR ₁₇ , SR ₁₈ or NR ₂₁ R ₂₂ ; R ₂₄ represents (CO)OR ₁₇ , CONR ₁₉ R ₂₀ , (CO)R ₁₇ ; or R ₂₄ has the meanings given for R ₁₉ and R ₂₀ One of them; R ₂₅ represents COOR ₁₇ , CONR ₁₉ R ₂₀ , (CO)R ₁₇ ; or R ₂₅ has one of the meanings given for R ₁₇ ; R ₂₆ represents hydrogen, C ₁ -C ₂₀ alkyl a C ₁ -C ₄ haloalkyl group, a C ₂ -C ₂₀ alkyl group, optionally having one or more O or CO; or a phenyl-C ₁ -C ₄ alkyl group, a C ₃ -C ₈ cycloalkyl group, Yes One or more O or CO; or (CO)R ₁₉ ; or a phenyl group which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, Halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or a group represented by the formula (7) Formula (7); but the condition is that at least one group represented by formula (2) or formula (7) is present in the molecule Formula (2) Formula (7).

The compound of formula (1) is characterized in that it comprises one or more annelated unsaturated rings on the carbazole moiety. In other words, at least one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ is represented by the formula (5). Group. Formula (5)

C ₁ -C ₂₀ alkyl group is a straight chain or branched and is _{(e.g.) C 1- C 18 -, C} 1 -C 4 -, C 1 -C 12 -, C 1 -C 8 -, C 1 -C _8- or C ₁ -C ₄ alkyl or C ₄ -C ₁₂ - or C ₄ -C ₈ alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl Amyl, 2-ethylhexyl, octyl, decyl, decyl, dodecyl, tetradecyl, fifteen, hexadecyl, octadecyl and decyl. The C ₁ -C ₆ alkyl group has the same meaning as given above for the C ₁ -C ₂₀ alkyl group and has the highest corresponding number of C atoms.

An unsubstituted or substituted C ₁ -C ₂₀ alkyl group containing one or more CC multiple bonds means an alkenyl group as explained below.

C ₁ -C ₄ haloalkyl with halogen substituted as hereinbefore defined C ₁ -C ₄ alkyl as defined below. The alkyl group is, for example, mono- or polyhalogenated until all H-atoms are replaced by halogen. It is, for example, C _z H _x Hal _y , where x+y=2z+1 and Hal is halogen, preferably F. Specific examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, especially trifluoromethyl or trichloromethyl. C ₂ -C ₄ hydroxyalkyl means a C ₂ -C ₄ alkyl group substituted with one or two O atoms. The alkyl group is straight or branched. Examples are 2-hydroxyethyl, 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl, 4-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 2,3-dihydroxypropyl or 2,4-dihydroxybutyl. C ₂ -C ₁₀ alkoxyalkyl is interrupted by O atoms of a C ₂ -C ₁₀ alkyl. The C ₂ -C ₁₀ alkyl group has the same meaning as given above for the C ₁ -C ₂₀ alkyl group and has the highest corresponding number of C atoms. Examples are methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl, Propoxypropyl.

A C ₂ -C ₂₀ alkyl group having one or more O, S, NR ₂₆ or CO intermixed with O, S, NR ₂₆ or CO (for example) 1 to 9 times, 1 to 5 times, 1 to 3 times or 1 Times or 2 times. If more than one meta-group is present, it is the same species or different. The two O atoms are separated by at least one methylene group, preferably at least two methylene groups (i.e., exoethyl groups). The alkyl group is straight or branched. For example, the following structural units will be present: -CH ₂ -CH ₂ -O-CH ₂ CH ₃ , -[CH ₂ CH ₂ O] _y -CH ₃ (where y = 1 to 9), - (CH ₂ - CH ₂ O) ₇ -CH ₂ CH ₃ , -CH ₂ -CH (CH ₃ ) -O-CH ₂ -CH ₂ CH ₃ , -CH ₂ -CH (CH ₃ )-O-CH ₂ -CH ₃ ,- CH ₂ -CH ₂ -S-CH ₂ CH ₃ , -CH ₂ -CH(CH ₃ ) -NW ²⁶ -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -COO-CH ₂ CH ₃ or -CH ₂ - CH(CH ₃ ) -OCO-CH ₂ -CH ₂ CH ₃ .

C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkyl and C ₃ -C ₈ cycloalkyl are understood in the context of the present application to mean an alkyl group containing at least one ring. It is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, pentylcyclopentyl and cyclohexyl. C ₃ -C ₁₀ cycloalkyl is also intended to encompass a bicyclic ring in the context of the present invention, in other words, a bridging ring, for example , , And the corresponding ring. Other examples are such as , , (E.g ) or Such structures, as well as rendezvous or fused ring systems, for example, the terms are also intended to cover: , , and other structures.

The C ₃ -C ₂₀ cycloalkyl group interspersed with O, S, CO, NR ₂₆ has the meaning given above wherein at least one CH ₂ - group in the alkyl group is replaced by O, S, CO or NR ₂₆ . An example is something like , , (E.g ), , , , , , , and other structures.

C ₁ -C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl is C ₃ -C ₁₀ cycloalkyl as defined above substituted with one or more alkyl groups having up to 8 carbon atoms. An example is: , Wait.

A C ₁ -C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl group having one or more O interstitials is an O-interstitial C ₃ - as defined above, substituted with one or more alkyl groups having up to 8 carbon atoms C ₁₀ cycloalkyl. An example is: , Wait.

C ₁ -C ₁₂ alkoxy is substituted by O atom of a C ₁ -C ₁₂ alkyl. The C ₁ -C ₁₂ alkyl group has the same meaning as given above for the C ₁ -C ₂₀ alkyl group and has the highest corresponding number of C atoms. C ₁ -C ₄ alkoxy is straight or branched, such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, second butoxy, isobutoxy or Tributoxy. The C ₁ -C ₈ alkoxy group and the C ₁ -C ₄ -alkoxy group have the same meanings as described above and have the highest corresponding number of C atoms.

C ₁ -C ₁₂ alkyl group is substituted by a S atom of the C ₁ -C ₁₂ alkyl. The C ₁ -C ₂₀ alkyl group has the same meaning as given above for the C ₁ -C ₂₀ alkyl group and has the highest corresponding number of C atoms. C ₁ -C ₄ alkylthio is straight-chain or branched, such as methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, second butylthio , isobutylthio group, tert-butylthio group.

Phenyl-C ₁ -C ₃ alkyl is, for example, benzyl, phenylethyl, α-methylbenzyl or α,α-dimethyl-benzyl, especially benzyl.

The phenyl-C ₁ -C ₃ alkoxy group is, for example, a benzyloxy group, a phenylethoxy group, an α-methylbenzyloxy group or an α,α-dimethylbenzyloxy group, especially a benzyloxy group.

C ₂ -C ₁₂ alkenyl is mono- or polyunsaturated and is, for example, C ₂ -C ₁₀ -, C ₂ -C ₈ -, C ₂ -C ₅ -alkenyl, such as vinyl, allyl, Methyl allyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentadienyl, 5-hexenyl, 7-Octyl or dodecenyl, especially allyl. The C ₂ -C ₅ alkenyl group has the same meaning as given above for the C ₂ -C ₁₂ alkenyl group and has the highest corresponding number of C atoms.

Miscible with one or more C ₂ -C ₁₂ alkenyl groups of O, CO or NR ₂₆ via O, S, NR ₂₆ or CO, for example, 1 to 9 times, 1 to 5 times, 1 to 3 times or 1 time or 2 times. If more than one meta-group is present, it is the same species or different. The two O atoms are separated by at least one methylene group, preferably at least two methylene groups (i.e., exoethyl groups). Alkenyl is straight or branched and is as defined above. For example, the following structural units can be formed: -CH=CH-O-CH ₂ CH ₃ , -CH=CH-O-CH=CH ₂ and the like.

The C ₄ -C ₈ cycloalkenyl group has one or more double bonds and is, for example, a C ₄ -C ₆ -cycloalkenyl group or a C ₆ -C ₈ -cycloalkenyl group. Examples are cyclobutenyl, cyclopentenyl, cyclohexenyl or cyclooctenyl, especially cyclopentenyl and cyclohexenyl, preferably cyclohexenyl.

The C ₃ -C ₆ alkenyloxy group is mono- or polyunsaturated and has one of the meanings given above for an alkenyl group, and the attached oxy group has the highest corresponding number of C atoms. Examples are allyloxy, methylallyloxy, butenyloxy, pentenyloxy, 1,3-pentadienyloxy, 5-hexenyloxy.

The C ₂ -C ₁₂ alkynyl group is a mono- or polyunsaturated straight or branched chain and is, for example, a C ₂ -C ₈ -, C ₂ -C ₆ - or C ₂ -C ₄ alkynyl group. Examples are ethynyl, propynyl, butynyl, 1-butynyl, 3-butynyl, 2-butynyl, pentynylhexynyl, 2-hexynyl, 5-hexynyl, Octyl group and the like.

The C ₂ -C ₂₀ alkanoyl group is straight or branched and is, for example, C ₂ -C ₁₈ -, C ₂ -C ₁₄ -, C ₂ -C ₁₂ -, C ₂ -C ₈ -, C ₂ - C ₆ - or C ₂ -C ₄ alkanoyl or C ₄ -C ₁₂ - or C ₄ -C ₈ alkanoyl. Examples are ethyl, propyl, butyl, isobutyl, pentylene, hexyl, decyl, octyl, fluorenyl, fluorenyl, fluorenyl, tetradecyl, fifteen Base, hexadecanyl, octadecyl, and decyl, preferably acetyl. The C ₁ -C ₈ alkano group has the same meaning as given above for the C ₂ -C ₂₀ alkano group and has the highest corresponding number of C atoms.

C ₂ -C ₁₂ alkoxycarbonyl is straight-chain or branched and is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, 1,1 - dimethylpropoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl, especially methoxy A carbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a n-butoxycarbonyl group or an isobutoxycarbonyl group is preferably a methoxycarbonyl group.

The C ₂ -C ₁₂ alkoxycarbonyl group having one or more O interstitials is linear or branched. The two O atoms are separated by at least two methylene groups (ie, an extended ethyl group). The meta-alkyloxycarbonyl group is unsubstituted or substituted with one or more hydroxyl groups. The C ₆ -C ₂₀ aryloxycarbonyl group is, for example, a phenyloxycarbonyl group [=phenyl-O-(CO)-], a naphthyloxycarbonyl group, a decyloxycarbonyl group or the like. The C ₅ -C ₂₀ heteroaryloxycarbonyl group is a C ₅ -C ₂₀ heteroaryl-O-CO- group.

The C ₃ -C ₁₀ cycloalkylcarbonyl group is a C ₃ -C ₁₀ cycloalkyl-CO- group, wherein the cycloalkyl group has one of the meanings indicated above and has the highest corresponding number of C atoms. The C ₃ -C ₁₀ cycloalkylcarbonyl group having one or more O, S, CO, NR ₂₆ refers to a trans-heterocycloalkyl-CO- wherein the inter-heterocycloalkyl group is as defined above.

The C ₃ -C ₁₀ cycloalkoxycarbonyl group is C ₃ -C ₁₀ cycloalkyl-O-(CO)-, wherein the cycloalkyl group has one of the meanings indicated above and has the highest corresponding number of C atoms. The C ₃ -C ₁₀ cycloalkoxycarbonyl group having one or more O, S, CO, NR ₂₆ refers to a transheterocycloalkyl-O-(CO)- group, wherein the interheterocycloalkyl group is as described above Defined.

The C ₁ -C ₂₀ alkylphenyl group means a phenyl group substituted by one or more alkyl groups, wherein the sum of the C atoms is at most 20.

The C ₆ -C ₂₀ aryl group is, for example, phenyl, naphthyl, anthracenyl, phenanthryl, anthracenyl, fluorenyl, tetracylphenyl, tert-triphenyl, etc., especially phenyl or naphthyl, preferably Is a phenyl group. The naphthyl group is 1-naphthyl or 2-naphthyl.

In the context of the present invention, C ₃ -C ₂₀ heteroaryl is intended to include monocyclic or polycyclic systems, such as fused ring systems. Examples are thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thioxyl, furyl, dibenzofuranyl, xanthenyl, thioxanthyl, phenothiphenyl , pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, mesoindolyl, isodecyl, decyl, oxazolyl, fluorenyl, quinazolyl, isoquinoline , quinolyl, pyridazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, porphyrinyl, acridinyl, oxazolyl, β-carboline, phenanthryl, acridinyl, Naphthalene, diphenylphenyl, phenanthroline, phenothiyl, isothiazolyl, phenothiazine, isoxazolyl, furazyl, oxo, 7-phenanthryl, indole-2-yl (=9,10-di-oxy-9,10-dihydroindol-2-yl), 3-benzo[b]thienyl, 5-benzo[b]thienyl, 2-benzo[b] Thienyl, 4-dibenzofuranyl, 4,7-dibenzofuranyl, 4-methyl-7-dibenzofuranyl, 2-indenyl, 8-methyl-2-indole Base, 3-xanthene, 2-morphothinyl, 2,7-morphothinyl, 2-pyrrolyl, 3-pyrrolyl, 5-methyl-3-pyrrolyl, 2-imidazolyl, 4 -Imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2- 4-imidazolyl, 2-ethyl-5-imidazolyl, 1H-tetrazol-5-yl, 3-pyrazolyl, 1-methyl-3-pyrazolyl, 1-propyl-4- Pyrazolyl, 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1- Isoindolyl, 1-methyl-2-indolyl, 1-methyl-3-indolyl, 1,5-dimethyl-2-indenyl, 1-methyl-3-oxazole , 2,7-dimethyl-8-fluorenyl, 2-methoxy-7-methyl-8-fluorenyl, 2-quinazinyl, 3-isoquinolinyl, 6-isoquinolinyl , 7-isoquinolyl, 3-methoxy-6-isoquinolyl, 2-quinolyl, 6-quinolyl, 7-quinolinyl, 2-methoxy-3-quinolyl , 2-methoxy-6-quinolyl, 6-pyridazinyl, 7-pyridazinyl, 1-methoxy-6-pyridazinyl, 1,4-dimethoxy-6-pyridazine 1,1,8-naphthyridin-2-yl, 2-quinoxalinyl, 6-quinoxalinyl, 2,3-dimethyl-6-quinoxalinyl, 2,3-dimethoxy -6-quinoxaline, 2-quinazolinyl, 7-quinazolinyl, 2-dimethylamino-6-quinazolinyl, 3-carbolinyl, 6-carbolinyl, 7 - porphyrinyl, 3-methoxy-7-carbolinyl, 2-acridinyl, 6-acridinyl, 7-acridinyl, 6,7-dimethoxy-2-indolyl, 2-carbazole , 3-oxazolyl, 9-methyl-2-oxazolyl, 9-methyl-3-oxazolyl, β-carboline-3-yl, 1-methyl-β-carboline-3 -yl, 1-methyl-β-carboline-6-yl, 3-phenanthryl, 2-acridinyl, 3-acridinyl, 2-naphthyldiazophenyl, 1-methyl- 5-naphthyl-dinitrophenyl, 5-phenanol, 6-phenanol, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5- Isothiazolyl, 2-phenothiazine, 3-phenothiazine, 10-methyl-3-phenothiazine, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl , 4-methyl-3-furoyl, 2-phenoxy group, 10-methyl-2-phenoxy group, and the like.

The C ₃ -C ₂₀ heteroaryl group is especially thienyl, benzo[b]thienyl, thioxyl, thioxanthyl, 1-methyl-2-indenyl or 1-methyl-3-indolyl Especially tienyl.

A C ₄ -C ₂₀ heteroarylcarbonyl group is a C ₃ -C ₂₀ heteroaryl group as defined above attached to the remainder of the molecule via a CO group.

Substituted aryl (phenyl, naphthyl, C ₆ -C ₂₀ aryl or C ₅ -C ₂₀ heteroaryl) is 1 to 7 times, 1 to 6 times or 1 to 4 times, especially 1 time, respectively , 2 or 3 substitutions. It will be apparent that the defined aryl group cannot have more substituents than the free position at the aryl ring.

The substituent on the phenyl ring is preferably in position 4 on the phenyl ring or in the 3,4-, 3,4,5-, 2,6-, 2,4- or 2,4,6-configuration .

Intermixed with one or more interstitial hetero groups (for example) 1 to 19 times, 1 to 15 times, 1 to 12 times, 1 to 9 times, 1 to 7 times, 1 to 5 times, 1 to 4 times, 1 to 3 times or 1 or 2 times (obviously, the number of heteroatoms depends on the number of C atoms in the interstitial). The substituted group substituted by one or more times has, for example, 1 to 7, 1 to 5, 1 to 4, 1 to 3 or 1 or 2 identical or different substituents.

A group substituted with one or more substituents as defined is intended to have one substituent or a plurality of substituents as defined or differently given. Halogen is fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine, preferably fluorine and chlorine. When R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ or R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ are each independently a group represented by the formula (5) group Formula (5) forms, for example, the following (Ia)-(Ii) structure: (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig) (Ih), (Ii).

Preferred is structure (Ia).

The compound of formula (1) is characterized in that at least one phenyl ring is partially fused to the carbazole to form a "naphthyl" ring. That is, one of the above structures is given by the formula (1). .

If R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are each independently taken to be -(CH ₂ ) _P -Y- (CH ₂ ) _q -, forming, for example, such as: , And other structures.

If the substituent OR ₁₇ , SR ₁₈ , SOR ₁₈ , SO ₂ R ₁₈ or NR ₁₉ R ₂₀ on the phenyl or naphthyl ring is via the radicals R ₁₇ , R ₁₈ , R ₁₉ and/or R ₂₀ and the naphthyl ring When a carbon atom forms a 5- or 6-membered ring, a structure comprising 3 or more rings including a naphthyl ring is obtained. An example is: , , , , , , , , , , and other structures.

If R ₁₇ forms a bond to have a group thereon Formula (2) or a direct bond of a carbon atom of a phenyl or naphthyl ring of formula (7), for example, such as , structure.

If R ₁₆ represents a phenyl group substituted by SR ₁₈ , wherein the group R ₁₉ represents a direct bond bonded to a phenyl or naphthyl ring to which a carbazole moiety of the COR ₁₆ group is attached, for example, such as , , , , and other structures. That is, if R ₁₆ is a phenyl group substituted by SR ₁₈ , wherein the group R ₁₈ represents a direct bond bonded to a phenyl or naphthyl ring to which a carbazole moiety of the COR ₁₆ group is attached, the thioxanthene The base moiety is formed together with a phenyl or naphthyl ring of the carbazole moiety.

If R ₁₉ and R ₂₀ together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring, optionally mixed with O, S or NR ₁₇ , a saturated or unsaturated ring, such as aziridine, is formed. Pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1,3-diazine, 1,2-diazine, hexahydropyridine or morpholine. Preferably, if R ₁₉ and R ₂₀ together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring of O, S or NR ₁₇ as appropriate, an inter- or inter-molecular O is formed. Or NR ₁₇ , especially the 5- or 6-member saturated ring of O.

If R ₂₁ and R ₂₂ together with the N atom to which they are attached, form a 5- or 6-membered saturated or unsaturated ring, optionally mixed with O, S or NR ₂₆ , and the benzene ring is optionally thicker than the saturated or unsaturated ring. To form a saturated or unsaturated ring, such as aziridine, pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1,3-diazine, 1,2-diazine, hexahydropyridine or morpholine or correspondingly Ring, for example Wait.

If R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system, the ring system is intended to contain more than one ring (eg 2 or 3 rings) and one or the same species or More than one hetero atom. Suitable heteroatoms are, for example, N, S, O or P, especially N, S or O. Examples are carbazole, anthracene, isoindole, carbazole, anthracene, isoquinoline, quinoline, porphyrin, phenothiazine and the like.

The term "and/or" or "or/and" is intended to mean in the context of the present invention that not only one of the defined substitutes (substituents) but also a plurality of defined substitutes (substituents) may be present, ie A mixture of different substitutes (substituents).

The term "at least" is intended to define one or more, such as one or both or three, preferably one or both.

The term "optionally substituted" means that the group to which it is referred is unsubstituted or substituted.

The term "as appropriate" means that the group to which it is referred is not miscellaneous or interstitial.

Throughout this specification and the claims below, the words "comprise" or variant (eg, "comprises" or "comprising") are understood to include the integer or A step or integer group or group of steps, but does not exclude any other integer or step or integer group or group of steps. The term "(meth)acrylate" is intended in the context of the present application to mean acrylate and the corresponding methacrylate.

The oxime ester of formula (1) is prepared by the methods described in the literature, for example by reacting the corresponding hydrazine with a hydrazine halide, especially a chloride or an anhydride, under the following conditions: in an inert solvent (eg, tert-butyl methyl ether, tetrahydrofuran) In (THF) or dimethylformamide, in the presence of a base such as triethylamine or pyridine, or in a basic solvent such as pyridine. The preparation of the compound of the formula Ia is illustrated below as an example, wherein R ₇ represents a oxime ester group and X represents a direct bond [the reaction of the compound (Ib)-(Ih) is carried out starting from an appropriate hydrazine]:

R ₁ , R ₂ , R ₅ , R ₆ , R ₈ , R ₁₃ , R ₁₄ and R ₁₅ are as defined above, and Hal means a halogen atom, especially Cl.

R _{14 is} preferably a methyl group.

Such reactions are well known to those skilled in the art and are typically carried out at a temperature of from -15 ° C to +50 ° C, preferably from 0 to 25 ° C.

When X represents CO, the corresponding enthalpy is by using an alkyl nitrite (such as methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite or isoamyl nitrite). Nitrification to synthesize. The esterification is then carried out under the same conditions as described above:

Thus, the subject matter of the invention is also a process for the preparation of a compound of formula (1) as defined above by reacting the corresponding hydrazine compound with a hydrazine halide of formula VI or an anhydride of formula VII in the presence of a mixture of bases or bases. (VI), (VII)

Wherein Hal is halogen, especially C1, and R ₁₄ is as defined above.

The desired starting material can be obtained by standard chemistry textbooks (eg J. March, Advanced Organic Chemistry, 4th edition, Wiley Interscience, 1992) or monographs (eg SR Sandler & W. Karo, Organic functional group preparations, A variety of methods are described in Volume 3, Academic Press).

One of the most convenient methods is to, for example, react an aldehyde or a ketone with hydroxylamine or a salt thereof in a polar solvent such as dimethylacetamide (DMA), aqueous DMA, ethanol or an aqueous ethanol solution. In this case, a base such as sodium acetate or pyridine is added to control the pH of the reaction mixture. It is well known that the reaction rate is pH dependent and the base can be added continuously at the beginning or during the reaction. An alkaline solvent such as pyridine can also be used as the base and/or solvent or co-solvent. The reaction temperature is usually from room temperature to the reflux temperature of the mixture, and is usually from about 20 ° C to 120 ° C.

The corresponding ketone intermediates are prepared, for example, by the methods described in the literature (e.g., standard chemistry textbooks, e.g., J. March, Advanced Organic Chemistry, 4th Ed., Wiley Interscience, 1992). In addition, the continuous Friedel-Crafts reaction can be effectively used to synthesize intermediates. Such reactions are well known to those skilled in the art.

Another convenient synthesis of hydrazine is the nitrosation of "active" methylene groups with nitrous acid or alkyl nitrite. Basic conditions (as described, for example, in Organic Syntheses coll., Volume VI (J. Wiley & Sons, New York, 1988), pages 199 and 840) and acidic conditions (eg, for example, Organic Synthesis coll Volume V, pages 32 and 373, coll. Volume III, pages 191 and 513, coll. Volume II, pages 202, 204 and 363) It is suitable for the preparation of hydrazine used as a starting material in the present invention. Nitrous acid is generally produced from sodium nitrite. The alkyl nitrite can be, for example, methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite or isoamyl nitrite.

Another embodiment of the invention is a free (1A) hydrazine compound Formula (1A) wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen, C ₁ -C ₂₀ alkyl, , COR ₁₆ , OR ₁₇ , halogen, NO ₂ or a group represented by the formula (3), Formula (3); or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are each independently Substituted C ₂ -C ₁₀ alkenyl; or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are independently of each other Is —(CH ₂ ) _p —Y—(CH ₂ ) _q —; or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ And R ₈ are independently of each other and are a group represented by the formula (5); Formula (5); but the condition is that at least one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are a group represented by the formula (5) R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently hydrogen, C ₁ -C ₂₀ alkyl, and the C ₁ -C ₂₀ alkyl group is unsubstituted or one or more of the following Group substitution: halogen, phenyl, CN, OH, SH, C ₁ -C ₄ -alkoxy, -(CO)OH or -(CO)O-(C ₁ -C ₄ alkyl); or R ₉ And R ₁₀ , R ₁₁ and R ₁₂ are, independently of each other, an unsubstituted phenyl group or a phenyl group substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, CN, OR ₁₇ , SR ₁₈ Or NR ₁₉ R ₂₀ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently halogen, CN, OR ₁₇ , SR ₁₈ , SOR ₁₈ , SO ₂ R ₁₈ or NR ₁₉ R ₂₀ , wherein the substitution The group OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ optionally forms a 5- or 6-membered ring with one of the carbon atoms in the naphthyl ring via the groups R ₁₇ , R ₁₈ , R ₁₉ and/or R ₂₀ ; ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independent of each other , COR ₁₆ or NO ₂ ; Y represents O, S, NR ₂₆ or a direct bond; p represents an integer of 0, 1, 2 or 3; q represents an integer of 1, 2 or 3; X represents CO or a direct bond; R ₁₃ Represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ , NR ₁₉ R ₂₀ , PO (OC _k H _2k+1 ) ₂ or a group represented by the formula (6); Formula (6); or R ₁₃ represents a C ₂ -C ₂₀ alkyl group in which one or more of O, S, SO, SO ₂ , NR ₂₆ or CO, or a C ₂ -C ₁₂ alkenyl group, which is not Interstitial or heterozygous with one or more O, CO or NR ₂₆ wherein the inter-hetero C ₂ -C ₂₀ alkyl group and the uninter or hetero-C ₂ -C ₁₂ alkenyl group are unsubstituted or Substituted by one or more halogens; or R ₁₃ represents a C ₄ -C ₈ cycloalkenyl group, a C ₂ -C ₁₂ alkynyl group or a C ₃ - having no or hetero or one or more O, S, CO or NR ₂₆ C ₁₀ cycloalkyl; or R ₁₃ represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , _{, COR 16, CN, NO 2} , halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, interrupted by one or more O, S, CO or NR C ₂₆ of ₂ -C ₂₀ alkyl group; or via their respective C ₃ -C ₁₀ cycloalkyl, or is interrupted by one or more O, S, CO or NR ₂₆ of the C ₃ -C ₁₀ cycloalkyl; K represents an integer of from 1 to 10; R ₁₅ represents a C ₆ - a C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halo, C ₁ -C ₄ haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ , SO-C ₁ -C ₁₀ alkyl, SO ₂ -C ₁ -C ₁₀ alkyl, hetero or one or more O, S or the C NR _{26 2} -C ₂₀ alkyl group; or each warp substituted C ₁ -C ₂₀ alkyl, said C ₁ -C ₂₀ alkyl group is unsubstituted or substituted with one or more of the following radicals: halogen , COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl , OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ represents hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₈ cycloalkyl, radical or hetero or one or more O, CO or NR ₂₆ ; or R ₁₅ means C ₁ a -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ , represented by formula (6) Group Equation (6), Or a phenyl group; or the C ₁ -C ₂₀ alkyl group is substituted by a phenyl group which is halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R _{20 is} substituted; or R ₁₅ represents a C ₂ -C ₂₀ alkyl group, one or more of which is O, SO or SO ₂ , and the interstitial C ₂ -C ₂₀ alkyl group is unsubstituted or Substituted by one or more of the following groups: halogen, OR ₁₇ , COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl or phenyl substituted with OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ represents C ₂ -C ₂₀ An alkanoyl or benzhydryl group which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; R ₁₅ represents a naphthylmethyl group which is unsubstituted or substituted with one or more OR ₁₇ or a C ₃ -C ₁₄ heteroarylcarbonyl group; or R ₁₅ represents a C ₂ -C ₁₂ alkoxycarbonyl group which is not Miscellaneous or heterozygous one or more O and the interstitial or unintercalated C ₂ -C ₁₂ alkoxycarbonyl group is unsubstituted or substituted with one or more hydroxyl groups; or R ₁₅ represents a phenoxycarbonyl group, Is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, Halogen, C ₁ -C ₄ haloalkyl, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ represents CN, CONR ₁₉ R ₂₀ , NO ₂ , C ₁ -C ₄ haloalkyl, S(O) _m- C ₁ -C ₆ alkyl, unsubstituted or S(O) _m -phenyl substituted by C ₁ -C ₁₂ alkyl or SO ₂ -C ₁ -C ₆ alkyl; or R ₁₅ represents SO ₂ O-phenyl which is unsubstituted or substituted by C ₁ -C ₁₂ alkyl; or diphenylphosphinyl or di-(C ₁ -C ₄ alkoxy)-phosphonium; m represents 1 Or 2; R' ₁₅ has one of the meanings given for R ₁₅ ; X ₁ represents O, S, SO or SO ₂ ; X ₂ represents O, CO, S or a direct bond; R ₁₆ represents C ₆ -C _{a 20} aryl or C ₃ -C ₂₀ heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halo, C ₁ -C ₄ haloalkyl, CN, NO ₂ , OR ₁₇ , SR _18, NR ₁₉ R ₂₀ or interrupted by one or more O, S or NR C ₂₆ of ₁ -C ₂₀ alkyl group; or each with one or more C ₁ -C ₂₀ alkyl, C ₁ a -C ₂₀ alkyl is unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl , C ₆ -C ₂₀ aryloxycarbonyl a C ₃ -C ₂₀ heteroaryloxycarbonyl group, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₆ represents hydrogen, C ₁ -C ₂₀ alkyl, said C ₁ -C ₂₀ alkyl group is not Substituted or substituted with one or more of the following groups: halogen, phenyl, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O (C ₁ - C ₄ )alkyl, O(CO)-(C ₁ -C ₄ alkyl), O(CO)-phenyl, (CO)OH or (CO)O(C ₁ -C ₄ alkyl); or R ₁₆ represents a C ₂ -C ₁₂ alkyl group in which one or more O, S or NR ₂₆ are heterogeneous; or R ₁₆ represents (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO) -(C ₁ -C ₈ alkyl), C ₂ -C ₁₂ alkenyl or C ₃ -C ₈ cycloalkyl; or R ₁₆ represents phenyl substituted by SR ₁₈ , wherein said group R ₁₈ represents a bond a direct bond to the phenyl or naphthyl ring of the oxazole moiety to which the COR ₁₆ group is attached; n represents 1 to 20; R ₁₇ represents hydrogen, phenyl-C ₁ -C ₃ alkyl a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ )alkenyl, O(CO) -benzene , (CO) OH, (CO ) O (C 1 -C 4 alkyl), C ₃ -C _{20 cycloalkyl, SO 2 - (C 1- C} 4 haloalkyl), O (C ₁ -C ₄ haloalkoxy a C ₃ -C ₂₀ cycloalkyl group having one or more O; or R ₁₇ representing a C ₂ -C ₂₀ alkyl group, wherein one or more O, S or NR ₂₆ are heterogeneous; or R _{17 is} represented by (CH) ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₁ -C ₈ alkanoyl, C ₂ -C ₁₂ alkenyl, C _{3- C6} olefinic group or C ₃ -C ₂₀ cycloalkyl group having one or more O, S, CO or NR ₂₆ without interstacking or interstacking; or R ₁₇ represents C ₁ -C ₈ alkyl-C ₃ - a C ₁₀ cycloalkyl group which has no or a hetero or one or more O; or R ₁₇ represents a benzhydryl group which is unsubstituted or has one or more C ₁ -C ₆ alkyl groups, halogen, OH Or a C ₁ -C ₃ alkoxy group; or R ₁₇ represents a phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: halogen, OH , C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, benzene Thiothio, N(C ₁ -C ₁₂ alkyl) ₂ , diphenyl-amine or Or R ₁₇ forms a bond to have a group thereon, or a direct bond of one of the carbon atoms of the phenyl or naphthyl ring; R ₁₈ represents hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl or phenyl-C ₁ -C ₃ alkyl, wherein The C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl or phenyl-C ₁ -C ₃ alkyl group is unmissoned or heterozygous with one or more O, S, CO, NR ₂₆ or COOR ₁₇ Or R ₁₈ is a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-(C ₁ -C ₄ alkyl), O ( CO)-phenyl or (CO)OR ₁₇ ; or R ₁₈ represents C ₂ -C ₂₀ alkyl with one or more O, S, CO, NR ₂₆ or COOR _{17 in between} ; or R ₁₈ represents (CH ₂ CH ₂ O) _n H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₈ alkanoyl or C ₃ -C ₆ alkenyl; or R ₁₈ represents a benzhydryl group which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, OH, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkyl sulphide group; or R ₁₈ represents phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups Generation: halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₁₂ alkoxy, CN, NO _2, phenyl -C ₁ -C ₃ alkoxy group, a phenoxy group, C ₁ -C ₁₂ alkylthio, phenylthio, N(C ₁ -C ₁₂ alkyl) ₂ , diphenylamino, (CO)O(C ₁ -C ₈ alkyl), (CO) -C ₁ -C ₈ alkyl, (CO)N(C ₁ -C ₈ alkyl) ₂ or R ₁₉ and R ₂₀ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₂ -C ₁₀ alkoxyalkyl, C ₂ -C ₅ alkenyl, C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₈ alkanoyl, C ₁ -C ₈ alkenyloxy, C ₃ -C _{1 2} alkenyl, SO ₂ - (C ₁ -C ₄ haloalkyl) or benzhydryl; or R ₁₉ and R ₂₀ represent phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or one or more of the following Group substitution: halogen, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₁₂ alkyl, benzhydryl or C ₁ -C ₁₂ alkoxy; or R ₁₉ and R ₂₀ together with the N atom to which it is attached, forms a 5- or 6-membered saturated or unsaturated ring which is not intermixed or interspersed with O, S or NR ₁₇ , and the 5 or 6 member saturated or unsaturated ring is not Substituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, =0, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO)R ₂₃ , NO ₂ , halogen, C ₁ -C ₄ -haloalkyl, CN, phenyl, Or a C ₃ -C ₂₀ cycloalkyl group having one or more O, S, CO or NR ₁₇ without interstitial or interstitial; or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system, The ring system is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, =0, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO)R ₂₃ , Halogen, NO ₂ , CN, phenyl or a C ₃ -C ₂₀ cycloalkyl group having one or more O, S, CO or NR ₁₇ without interstacking or interstitial; R ₂₁ and R ₂₂ are independently hydrogen, C _{a 1-} C ₂₀ alkyl group, a C ₁ -C ₄ haloalkyl group, a C ₃ -C ₁₀ cycloalkyl group or a phenyl group; or R ₂₁ and R ₂₂ together with the N atom to which they are attached form an unintermixed or intervening O, a 5- or 6-membered saturated or unsaturated ring of S or NR ₂₆ , and the 5- or 6-membered saturated or unsaturated ring is unfused or the 5 or 6 membered saturated or unsaturated ring is thickened with the benzene ring And R ₂₃ represents hydrogen, OH, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, hetero or one or more O, CO or C ₂ -C ₂₀ alkyl of NR ₂₆ , unintermixed or heterozygous C ₃ -C ₂₀ cycloalkyl having O, S, CO or NR ₂₆ ; or R ₂₃ represents phenyl, naphthyl, phenyl-C ₁ -C ₄ alkyl, OR ₁₇ , SR ₁₈ or NR ₂₁ R ₂₂ ; R ₂₄ represents (CO)OR ₁₇ , CONR ₁₉ R ₂₀ , (CO)R ₁₇ ; or R ₂₄ has one of the meanings given for R ₁₉ and R ₂₀ ; R ₂₅ represents COOR ₁₇ , CONR ₁₉ R ₂₀ , (CO) R ₁₇ ; or R ₂₅ has one of the meanings given for R ₁₇ ; R ₂₆ represents hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl a C ₂ -C ₂₀ alkyl group in which one or more O or CO are heterogeneous; or a phenyl-C ₁ -C ₄ alkyl group, a C ₃ -C ₈ cycloalkyl group, which is unintercalated or heterozygous or has a plurality of O or CO; or (CO)R ₁₉ ; or a phenyl group which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, halogen, C ₁ -C ₄ Haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , But the condition is that at least one group is present in the molecule or .

Preferred for the group defined by the compound of formula (1A) corresponds to that given for the compound of formula (1) as given above, except for each of the defined oxime ester groups (eg Replace with the corresponding free sulfonium group .

Each oxime ester group can exist in two configurations (Z) or (E). The isomers can be separated by conventional methods, but a mixture of isomers can also be used as, for example, a photoinitiator. Accordingly, the present invention is also directed to a mixture of configurational isomers of the compound of formula (1).

Preferable is a compound of the formula (1) as defined above, wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen, C ₁ -C ₂₀ Alkyl group, COR ₁₆ , NO ₂ or a group represented by formula (2) Formula (2), or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ independently of each other are formula (5) Represented group Formula (5); but the condition is that at least one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are a group represented by the formula (5) Formula (5); X represents CO or a direct bond; R ₁₃ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ , NR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ ; or R ₁₃ represents a C ₂ -C ₂₀ alkyl group with one or more O, S, SO, SO ₂ intermixed therebetween , NR ₂₆ or CO; or R ₁₃ represents phenyl or naphthyl, either unsubstituted or substituted by COR ₁₆ or via one or more Substituted; R ₁₄ represents C ₁ -C ₂₀ alkyl, phenyl or C ₁ -C ₈ alkoxy; R ₁₅ represents phenyl, naphthyl, C ₃ -C ₂₀ heteroaryl, each unsubstituted or via Substituted by one or more of the following groups: phenyl, halo, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ or C ₂ -C ₂₀ alkyl, interspersed with one or more O or S; one or more C ₁ -C ₂₀ alkyl, said C ₁ -C ₂₀ alkyl unsubstituted or substituted with one or more of the following radicals: _{halogen, COOR 17, CONR 19 R 20} , phenyl, C _3- C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₄ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or PO (OC _k H _2k+1 ) ₂ ; or R ₁₅ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , C ₃ -C ₈ naphthenic a group, a C ₃ -C ₂₀ heteroaryl group, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ or PO(OC _k H _2k+1 ) ₂ ; R' ₁₄ has one of the meanings given for R ₁₄ ; R _'15 has the meanings for R ₁₅ Suo one of those given; R ₁₆ represents phenyl, which is unsubstituted or substituted with one or more of the following groups: oR _17, SR ₁₈ NR ₁₉ R ₂₀ or interrupted by one or more O, S or NR ₂₆ of C ₂ -C ₂₀ alkyl group, or R ₁₆ represents phenyl substituted by one or more C ₁ -C ₂₀ alkyl, said C ₁ -C ₂₀ alkyl is unsubstituted or substituted by one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl , C ₆ -C ₂₀ aryloxycarbonyl, C ₄ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₆ represents C ₁ -C ₂₀ alkyl, which is unsubstituted or Substituted by halogen, phenyl, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-( C ₁ -C ₄ alkyl) or (CO)O(C ₁ -C ₄ alkyl); R ₁₇ represents C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted by one or more of the following groups: halogen , OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(C ₁ -C ₄ alkyl), (CO)O(C ₁ -C ₄ alkyl), C ₃ -C ₂₀ ring An alkyl group or a heteroatom having one or more C ₃ -C ₂₀ cycloalkyl groups; or R ₁₇ represents a C ₂ -C ₂₀ alkyl group having one or more O intervening; R ₁₈ is substituted by (CO)OR ₁₇ Methyl; R ₁₉ and R ₂₀ are each independently hydrogen, phenyl, C ₁ -C ₂₀ alkyl, C ₁ -C ₈ -alkanolyl or C ₁ -C ₈ alkanoyloxy; or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system which is unsubstituted or Substituting; however, the condition is that at least one group represented by the formula (2) or a group represented by the formula (7) is present in the molecule, Formula (2), Formula (7). Attention must be paid to compounds of formula (1) as defined above, wherein R ₁ , R ₂ , R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen, COR ₁₆ , NO ₂ or formula (2) Group Formula (2), R ₃ and R ₄ together are a group represented by formula (5) Formula (5); R ₉ , R ₁₀ , R ₁₁ and R ₁₂ represent hydrogen X represents a direct bond; R ₁₃ represents a C ₁ -C ₂₀ alkyl group; R ₁₄ represents a C ₁ -C ₂₀ alkyl group; R ₁₅ represents a C ₁ a -C ₂₀ alkyl or phenyl group substituted by one or more OR ₁₇ or C ₁ -C ₂₀ alkyl groups; R ₁₆ represents a phenyl group substituted by one or more C ₁ -C ₂₀ alkyl groups or OR ₁₇ ; and R ₁₇ represents an unsubstituted or substituted by one or more of halogen or C ₁ -C ₂₀ alkyl interrupted by one or more O of C ₂ -C ₂₀ alkyl group. Provided that at least one group represented by formula (2) is present in the molecule Formula (2).

The subject matter of the invention is further a compound of formula (1) as defined above, wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen, or R ₁ And R ₂ , R ₃ and R ₄ or R ₅ and R ₆ independently of each other are a group represented by the formula (5) Formula (5); but the condition is that at least one of R ₁ and R ₂ , R ₃ and R ₄ or R ₅ and R ₆ is a group represented by formula (5); Formula (5); or R ₂ represents a group represented by COR ₁₆ , NO ₂ , formula (2) or a group represented by formula (3); Formula (2); Formula (3); or R ₇ represents a group represented by COR ₁₆ or formula (2) Formula (2); R ₉ , R ₁₁ and R ₁₂ represent hydrogen; R ₁₀ represents hydrogen, OR ₁₇ or COR ₁₆ ; X represents CO or a direct bond; R ₁₃ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or Substituted by one or more of the following groups: halogen, R ₁₇ , OR ₁₇ , SR ₁₈ or PO(OC _k H _2k+1 ) ₂ ; or R ₁₃ represents a C ₂ -C ₂₀ alkyl group with one or more O; or R ₁₃ represents a phenyl group; k represents an integer of 2; R ₁₄ represents a C ₁ -C ₂₀ alkyl group or a thienyl group; R ₁₅ represents a phenyl group or a naphthyl group, each of which is unsubstituted or has one or more ORs ₁₇ or C ₁ -C ₂₀ alkyl substituted; or R ₁₅ represents thienyl, hydrogen, C ₁ -C ₂₀ alkyl, said C ₁ -C ₂₀ alkyl being unsubstituted or substituted by one or more of the following groups :OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, NR ₁₉ R ₂₀ or COOR ₁₇ ; or R ₁₅ represents a C ₂ -C ₂₀ alkyl group, interspersed with SO ₂ ; R ₁₆ represents a phenyl or naphthyl group Each of which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl; or R ₁₆ represents thienyl; R ₁₇ represents hydrogen, C ₁ -C ₈ alkylalkyl, C ₁ -C ₂₀ alkyl, unsubstituted or via one or more of the following groups: halogen, O(CO)-(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ )alkenyl or a C ₃ -C ₂₀ cycloalkyl group having one or more O; or R ₁₇ represents a C ₂ -C ₂₀ alkyl group, There are one or more O's in between; R ₁₈ represents a C ₃ -C ₂₀ cycloalkyl group, a C ₁ -C ₂₀ alkyl group, which is unsubstituted or has one or more OH, O(CO)-(C ₂ -C ₄ ) alkenyl or (CO)OR ₁₇ substituted; or R ₁₈ represents phenyl which is unsubstituted or substituted by one or more halogens; R ₁₉ and R ₂₀ are each independently C ₁ -C ₈ alkyl fluorenyl or a C ₁ -C ₈ alkylalkyloxy group; or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a 5- or 6-membered saturated ring interspersed with O; provided that at least one is present in the molecule (2) the indicated group Formula (2).

Examples of compounds of the invention are the compounds of formula (Ia)-(Ig) as defined above. Compounds of formula (Ia), (Ib), (Ic), especially formula (Ia) or (Ic), or formula (Ia), (Ic) or (Id), especially formula (Ia) are of interest.

For example, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen, COR ₁₆ or a group represented by formula (2) Formula (2), or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ or R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ are independently of the formula (5) Represented group Formula (5).

For example, R ₃ and R ₄ or R ₁ and R ₂ together are a group represented by formula (5) Formula (5) or R ₃ and R ₄ and R ₅ and R ₆ together are a group represented by formula (5) Formula (5); R ₃ and R _{4 are in} particular a group represented by formula (5) Formula (5).

For example, R ₁ , R ₅ , R ₆ and R ₈ represent hydrogen.

R _{7 is} especially hydrogen, a group represented by formula (2) Formula (2), or COR ₁₆ . Or R ₇ is a group represented by formula (2) Formula (2) or COR _{16 is} especially a group represented by formula (2).

R _{2 is} especially a group represented by the formula (2) Formula (2), COR ₁₆ or a group represented by formula (3) Formula (3) or R ₂ together with R ₁ is a group represented by formula (5) Formula (5). R _{2 is} especially COR ₁₆ .

X is preferably a direct bond.

For example, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are, independently of each other, hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl or phenyl substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, OR ₁₇ or SR ₁₈ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently halogen, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ wherein the substituent OR ₁₇ SR ₁₈ or NR ₁₉ R ₂₀ optionally via a group R _17, R _18, R ₁₉ and / or R ₂₀ form a 5 or 6-membered ring with a carbon atom naphthyl ring; or R _9, R _10, R ₁₁ And R ₁₂ are each independently a group represented by COR ₁₆ or formula (2) Formula (2).

Specifically, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl or phenyl substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, OR ₁₇ or SR ₁₈ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are, independently of each other, halogen, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₉ , R ₁₀ And R ₁₁ and R ₁₂ are each independently a group represented by COR ₁₆ or formula (2) Formula (2).

For example, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are, independently of each other, hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl or substituted by one or more C ₁ -C ₆ alkyl groups. Phenyl group; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a group represented by COR ₁₆ or formula (2) Formula (2).

In another embodiment, for example, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are, independently of each other, hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl or one or more of the following groups a substituted phenyl group: C ₁ -C ₆ alkyl, halogen, OR ₁₇ or SR ₁₈ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently halogen, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ Wherein the substituent OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ optionally forms a 5- or 6-membered ring via a group R ₁₇ , R ₁₈ , R ₁₉ and/or R ₂₀ with one carbon atom of the naphthyl ring.

Further, for example, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl or phenyl substituted with one or more of the following groups C ₁ -C ₆ alkyl, halogen, OR ₁₇ or SR ₁₈ , or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently halogen, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or COR ₁₆ .

Or by way of example, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are, independently of each other, hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl or phenyl substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, OR ₁₇ or SR ₁₈ , or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently halogen, OR ₁₇ , COR ₁₆ or NR ₁₉ R ₂₀ .

Preferably, R ₉ , R ₁₁ and R ₁₂ represent hydrogen and R ₁₀ represents hydrogen, OR ₁₇ or COR ₁₆ .

R ₁₃ represents, for example, a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ or CONR ₁₉ R ₂₀ ; or R ₁₃ represents C ₂ -C ₂₀ alkyl In the meantime, one or more of O, S, SO, SO2, NR ₂₆ or CO, or a C ₂ -C ₁₂ alkenyl group, optionally having one or more O, CO or NR ₂₆ or R ₁₃ representing C ₃ -C ₁₀ cycloalkyl, which is optionally interrupted by one or more _{O, S, CO, NR 26} , or R ₁₃ represents a phenyl or naphthyl group, both of which unsubstituted or substituted with one or more of the following groups Substitution: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , COR ₁₆ , NO ₂ , halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl, with one or more Or O, or a group represented by formula (7) Formula (7); or a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ or PO (OC _k H _2k+1 ) ₂ ; or a C ₂ -C ₂₀ alkyl group in which one or more O are heterogeneous.

Further, R ₁₃ represents, for example, a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ or PO(OC _k H _2k+1 ) ₂ ; or a C ₂ -C ₂₀ alkyl group in which one or more O is hetero; or a C ₂ -C ₁₂ alkenyl group, a C ₃ -C ₁₀ cycloalkyl group; or R ₁₃ represents a phenyl or naphthyl group which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , COR ₁₆ , NO ₂ , halogen, C ₁ -C ₂₀ alkane a C ₁ -C ₄ haloalkyl group, a C ₂ -C ₂₀ alkyl group, having one or more O or a group represented by the formula (7) Formula (7).

In another embodiment, R ₁₃ represents, for example, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following: halo, R ₁₇ , OR ₁₇ , SR ₁₈ or PO (OC _k H _2k+1 ) ₂ ; or a C ₂ -C ₂₀ alkyl group in which one or more O is hetero; or a C ₂ -C ₁₂ alkenyl group, a C ₃ -C ₁₀ cycloalkyl group, a phenyl group or a naphthyl group; .

Or R ₁₃ represents, for example, a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , OR ₁₇ , SR ₁₈ or PO(OC _k H _2k+1 ) ₂ ; or a C ₂ -C ₂₀ alkyl group having one or more O; or a phenyl group, a C ₂ -C ₁₂ alkenyl group or a C ₃ -C ₁₀ cycloalkyl group.

Or R ₁₃ represents, for example, a C ₁ -C ₂₀ alkyl group, a phenyl group, a C ₂ -C ₁₂ alkenyl group or a C ₃ -C ₁₀ cycloalkyl group.

Or R ₁₃ represents, for example, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₁₂ alkenyl group or a C ₃ -C ₁₀ cycloalkyl group.

Preferably, R ₁₃ represents a C ₁ -C ₂₀ alkyl group, especially a C ₁ -C ₈ alkyl group, such as 2-ethylhexyl.

R ₁₄ represents, for example, hydrogen, C ₃ -C ₈ cycloalkyl, C ₂ -C ₅ alkenyl, C ₁ -C ₂₀ alkoxy or C ₁ -C ₂₀ alkyl, which is unsubstituted or subjected to one or Multiple halogen or phenyl substituted; or R ₁₄ represents phenyl or naphthyl, both unsubstituted or substituted by one or more of the following groups: C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl , halogen, OR ₁₇ , SR ₁₈ and/or NR ₁₉ R ₂₀ ; or R ₁₄ represents a C ₃ -C ₅ heteroaryl group, for example a thienyl group, or a C ₁ -C ₈ alkoxy group, a benzyloxy group or a phenoxy group base.

Or R ₁₄ represents, for example, a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more halogen or phenyl groups; or R ₁₄ represents a C ₃ -C ₅ heteroaryl group (e.g., thienyl) or a phenyl group which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl, halogen, OR ₁₇ , SR ₁₈ and/or NR ₁₉ R ₂₀ ; R ₁₄ represents a C ₁ -C ₈ alkoxy group, a benzyloxy group or a phenoxy group.

In another embodiment, R ₁₄ represents C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with phenyl; or R ₁₄ represents phenyl, which is unsubstituted or via one or more C ₁ -C ₆ Alkyl substitution.

Preferably, R ₁₄ represents C ₁ -C ₂₀ alkyl, C ₃ -C ₅ heteroaryl (such as thienyl), or phenyl, especially C ₁ -C ₂₀ alkyl or thienyl, especially C _1- C ₈ alkyl.

R ₁₅ represents, for example, a C ₆ -C ₂₀ aryl group or a C ₅ -C ₂₀ heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkane a group, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , C ₁ -C ₂₀ alkyl; or R ₁₅ represents hydrogen, C ₃ -C ₈ cycloalkyl, said C ₃ -C ₈ naphthenic One or more O, CO or NR ₂₆ ; or R ₁₅ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, OR ₁₇ , C ₃ - C ₈ cycloalkyl, C ₅ -C ₂₀ heteroaryl, C ₈ -C ₂₀ phenoxycarbonyl, C ₅ -C ₂₀ heteroaryloxy-carbonyl, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ , a group represented by the formula (6), a phenyl group or a phenyl group substituted by a halogen group, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₄ haloalkyl group , OR ₁₇ or NR ₁₉ R ₂₀ ; Formula (6) or R ₁₅ represents a C ₂ -C ₂₀ alkyl group in which one or more O, S or SO ₂ are mixed, or R ₁₅ represents a C ₂ -C ₂₀ alkanoyl group, a benzamidine group, a C ₂ - C ₁₂ alkoxycarbonyl, phenoxycarbonyl, CONR ₁₉ R ₂₀ , NO ₂ or C ₁ -C ₄ haloalkyl.

Further, R ₁₅ represents, for example, hydrogen, C ₆ -C ₂₀ aryl, especially phenyl or naphthyl, each unsubstituted or substituted by C ₁ -C ₁₂ alkyl; or C ₃ -C ₅ hetero An aryl group, such as a thienyl group; or a C ₃ -C ₈ cycloalkyl group, a C ₁ -C ₂₀ alkyl group, which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₇ , C ₃ - C ₈ -cycloalkyl, NR ₁₉ R ₂₀ or COOR ₁₇ ; or R ₁₅ represents C ₂ -C ₂₀ alkyl with one or more O or SO ₂ heteromixed therebetween.

Compounds of formula (1) are of interest, wherein R ₁₅ represents, for example, hydrogen, phenyl, naphthyl, each unsubstituted or substituted by C ₁ -C ₈ alkyl; or R ₁₅ represents thienyl, C ₁ - a C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₇ , C ₃ -C ₈ -cycloalkyl, NR ₁₉ R ₂₀ or COOR ₁₇ ; or R ₁₅ represents C ₂ a -C ₂₀ alkyl group in which one or more O or SO ₂ are heterogeneous.

R _{15 is} especially, for example, C ₃ -C ₈ cycloalkyl or C ₁ -C ₂₀ alkyl, especially C ₁ -C ₂₀ alkyl, especially C ₁ -C ₁₂ alkyl.

The preferred of R' ₁₄ and R' ₁₅ are as given above for R ₁₄ and R ₁₅ , respectively.

X ₁ represents, for example, O, S or SO, such as O or S, especially O.

R ₁₆ represents, for example, a C ₆ -C ₂₀ aryl group (especially phenyl or naphthyl, especially phenyl) or a C ₅ -C ₂₀ heteroaryl (especially thienyl), each unsubstituted or via one or more Substituted for: phenyl, halogen, C ₁ -C ₄ haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or a C ₁ -C ₂₀ alkyl group having one or more O; or each with one or more C ₁ -C ₂₀ alkyl, said C ₁ -C ₂₀ alkyl unsubstituted or substituted with one or more of the following radicals: _{halogen, COOR 17, CONR 19 R 20} , Phenyl, C ₃ -C ₈ cycloalkyl, C ₅ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₅ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R _20; or R ₁₆ represents hydrogen, C ₁ -C ₂₀ alkyl, said C ₁ -C ₂₀ alkyl unsubstituted or substituted with one or more of the following groups: halogen, phenyl, OH, SH, C _3- C ₆ alkenyloxy, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), O(CO)-phenyl, ( CO) OH or (CO)O(C ₁ -C ₄ alkyl); or R ₁₆ represents C ₂ -C ₁₂ alkyl with one or more O in between; or (CH ₂ CH ₂ O) _{n+1 H, (CH 2 CH 2 O} ) n (CO) - (C 1 -C 8 alkyl), C ₂ -C ₁₂ alkenyl Or C ₃ -C ₈ cycloalkyl group, and n is 1 to 20, e.g. 1-12 or 1-8, in particular 1 or 2.

Furthermore, R ₁₆ represents, for example, phenyl or naphthyl, especially phenyl, thienyl or oxazole, each unsubstituted or substituted by one or more of the following groups: phenyl, halogen, C ₁ -C _{a 4-} haloalkyl group, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl; or R ₁₆ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted with one or more of the following groups: Halogen, phenyl, OH, SH, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl) , O(CO)-phenyl, (CO)OH or (CO)O(C ₁ -C ₄ alkyl); or R ₁₆ represents a C ₂ -C ₁₂ alkyl group, wherein one or more O are heterogeneous; (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₁₂ alkenyl or C ₃ -C ₈ cycloalkyl And n is from 1 to 20, such as from 1 to 12 or from 1 to 8, especially 1 or 2.

Further, R ₁₆ represents, for example, phenyl or naphthyl, especially phenyl, each unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl; or R ₁₆ represents a C ₃ -C ₅ heteroaryl group, especially a thienyl group.

R _{16 is} especially, for example, phenyl which is unsubstituted or substituted by one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl, or R ₁₆ represents thienyl .

Preferably, R ₁₆ represents, for example, phenyl or naphthyl, each of which is unsubstituted or substituted with one or more C ₁ -C ₂₀ alkyl groups.

R _{16 is} especially phenyl which is substituted by one or more C ₁ -C ₂₀ alkyl groups.

R ₁₇ represents, for example, hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, OH, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-benzene group, (CO) OH, (CO ) O (C 1 -C 4 alkyl), C ₃ -C ₂₀ cycloalkyl interrupted by one or more O or of C ₃ -C ₂₀ cycloalkyl; or R ₁₇ represents a C ₂ -C ₂₀ alkyl group having one or more O in between; (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl) a C ₁ -C ₈ alkyl fluorenyl group, a C ₂ -C ₁₂ alkenyl group, a C ₃ -C ₆ olefin group or a C ₃ -C ₂₀ cycloalkyl group, optionally having one or more O; or R ₁₇ a benzhydryl group which is unsubstituted or substituted by one or more C ₁ -C ₆ alkyl, halogen, OH or C ₁ -C ₃ alkoxy groups; or R ₁₇ represents phenyl, naphthyl or C ₅ - a C ₂₀ heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: halogen, OH, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl -C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N(C ₁ -C ₁₂ alkyl) ₂ , diphenyl-amine or formula 7) Table Group; Formula (7).

In another embodiment, R ₁₇ represents, for example, hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following: halogen , O(CO)-(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ alkenyl) or a C ₂ -C ₂₀ alkyl group having one or more O; or C ₁ -C ₈ alkyl fluorenyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₆ olefinic group, heterochromic one or more C ₂ -C ₂₀ alkyl groups, optionally with one or more C ₃ a -C ₂₀ cycloalkyl group; or a benzylidene group which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, OH or C ₁ -C ₃ alkoxy; Or phenyl or naphthyl, each unsubstituted or substituted by one or more of the following: halo, C ₁ -C ₁₂ alkyl or C ₁ -C ₁₂ alkoxy.

R ₁₇ is also, for example, hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₈ alkanoyl, C ₁ -C ₂₀ alkyl, unsubstituted or via one or more of the following groups Substitution: halogen, C ₃ -C ₂₀ cycloalkyl, O(CO)-(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ alkenyl) or miscellaneous one or more O C ₂ -C ₂₀ alkyl, or R ₁₇ represents C ₂ -C ₂₀ alkyl with one or more O intervening.

R _{17 is} especially hydrogen, C ₁ -C ₈ alkanoyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted by one or more of the following groups: O(CO)-(C ₁ -C ₄ alkane a group of O(CO)-(C ₂ -C ₄ alkenyl) or a C ₂ -C ₂₀ alkyl group having one or more O, or R ₁₇ representing a C ₂ -C ₂₀ alkyl group, wherein one or more O.

R ₁₈ represents, for example, a C ₃ -C ₂₀ cycloalkyl group which has no or a hetero or one or more O; or R ₁₈ represents a C ₁ -C ₂₀ alkyl group which is unsubstituted or one or more of the following Group substitution: OH, O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-(C ₁ -C ₄ alkyl) or (CO)OR ₁₇ ; or R ₁₈ represents C ₂ -C _{a 20} alkyl group having one or more of O, S, CO, NR ₂₆ or COOR _{17 in between} ; or R ₁₈ represents a C ₂ -C ₈ alkanoyl group or a C ₃ -C ₆ alkenyl group, a benzamidine group; R ₁₈ represents a phenyl group, a naphthyl group or a C ₃ -C ₂₀ heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₄ haloalkane Base, C ₁ -C ₁₂ alkoxy or NO ₂ .

In another embodiment, R ₁₈ represents, for example, C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: OH, O (CO )-(C ₂ -C ₄ )alkenyl, O(CO)-(C ₁ -C ₄ alkyl) or (CO)OR ₁₇ ; or R ₁₈ represents phenyl or naphthyl, each unsubstituted or via One or more halogen or C ₁ -C ₁₂ alkyl groups, especially halogen.

R ₁₈ represents, for example, C ₁ -C ₂₀ alkyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl, C ₂ -C ₈ alkanoyl , benzylidene, phenyl or naphthyl.

For example, R ₁₈ represents C ₁ -C ₂₀ alkyl substituted with one or more of the following groups: OH, O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-(C ₁ -C ₄ alkyl) or (CO)OR ₁₇ , or R ₁₈ represents a phenyl group which is substituted by one or more halogens.

Preferably, R ₁₈ represents C ₁ -C ₈ alkyl, which is substituted as defined above.

For example, R ₁₉ and R ₂₀ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkane a phenyl or naphthyl group, a C ₁ -C ₈ alkanoyl group, a C ₁ -C ₈ alkenyloxy group, a C ₃ -C ₁₂ alkenyl group or a benzhydryl group; or R ₁₉ and R ₂₀ The attached N atoms together form a 5- or 6-membered saturated or unsaturated ring heterogeneously interspersed with O, S or NR ₁₇ ; or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system, The ring system is unsubstituted or substituted with one or more of the following groups: a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₄ haloalkyl group, or a group represented by the formula (7); Formula (7).

Further, for example, R ₁₉ and R ₂₀ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C _{a 3} alkyl group, a C ₁ -C ₈ alkyl fluorenyl group, a C ₁ -C ₈ alkyl fluorenyloxy group, a C ₃ -C ₁₂ olefinic fluorenyl group or a benzhydryl group; or R ₁₉ and R ₂₀ are attached thereto The atoms together form a 5- or 6-membered saturated ring, optionally mixed with O or NR ₁₇ ; or R ₁₉ and R ₂₀ together with the N atom to which they are attached form an indazole ring.

For example, R ₁₉ and R ₂₀ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkane a C ₁ -C ₈ alkanoyl group, a C ₁ -C ₈ alkanoyloxy group, a C ₃ -C ₁₂ alkenyl group or a benzhydryl group; or R ₁₉ and R ₂₀ together with the N atom to which it is attached Form a 5- or 6-membered saturated ring with O or NR ₁₇ as appropriate.

Preferably, R ₁₉ and R ₂₀ are, independently of each other, a C ₁ -C ₈ alkanoyl group, a C ₁ -C ₈ alkenyloxy group; or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a morpholine ring.

For example, R ₂₁ and R ₂₂ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₁₀ cycloalkyl or phenyl; or R ₂₁ and R ₂₂ The attached N atoms together form a morpholine ring. R ₂₁ and R _{22 are, in} particular, independently of one another hydrogen or C ₁ -C ₂₀ alkyl.

R ₂₃ represents, for example, hydrogen, OH, phenyl or C ₁ -C ₂₀ alkyl. R _{23 is} especially hydrogen, OH or C ₁ -C ₄ alkyl.

The preferred of R ₂₄ is as given for R ₁₉ and R ₂₀ . The preferred of R ₂₅ is as given for R ₁₇ .

R ₂₆ represents, for example, hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl, heterogeneously having one or more O or CO; or phenyl-C ₁ - a C ₄ alkyl group, a C ₃ -C ₈ cycloalkyl group optionally having one or more O or CO; or (CO)R ₁₉ or a phenyl group which is unsubstituted or has one or more of the following groups Substitution: C ₁ -C ₂₀ alkyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ .

Or R ₂₆ represents, for example, hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl; phenyl-C ₁ -C ₄ alkyl, C ₃ -C ₈ cycloalkyl, (CO)R ₁₉ or a phenyl group which is unsubstituted or substituted by one or more C ₁ -C ₂₀ alkyl groups. Further, R ₂₆ represents, for example, hydrogen or a C ₁ -C ₂₀ alkyl group, especially a C ₁ -C ₄ alkyl group.

Examples of the compound of the formula (1) of the invention include the following compounds represented by the formula (1-1) to the formula (1-84): , , formula (1-1), formula (1-2) , , formula (1-3), formula (1-4) , , formula (1-5), formula (1-6) , , formula (1-7), formula (1-8) , , formula (1-9), formula (1-10) , , formula (1-11), formula (1-12) , , formula (1-13), formula (1-14) , , formula (1-15), formula (1-16) , , formula (1-17), formula (1-18) , , formula (1-19), formula (1-20) , , (1-21), (1-22) , , formula (1-23), formula (1-24) , , formula (1-25), formula (1-26) , , formula (1-27), formula (1-28) , , formula (1-29), formula (1-30) , , formula (1-31), formula (1-32) , , formula (1-33), formula (1-34) , , formula (1-35), formula (1-36) , , formula (1-37), formula (1-38) , , formula (1-39), formula (1-40) , , formula (1-41), formula (1-42) , , formula (1-43), formula (1-44) , , formula (1-45), formula (1-46) , , formula (1-47), formula (1-48) , , formula (1-49), formula (1-50) , , formula (1-51), formula (1-52) , , formula (1-53), formula (1-54) , , formula (1-55), formula (1-56) , , formula (1-57), formula (1-58) , , formula (1-59), formula (1-60) , , formula (1-61), formula (1-62) , , formula (1-63), formula (1-64) , , formula (1-65), formula (1-66) , , formula (1-67), formula (1-68) , , formula (1-69), formula (1-70) , , (1-71) (1-72) , , Equation (1-73), Equation (1-74) , , Equation (1-75), Equation (1-76) , , (1-77), (1-78) , , (1-79), (1-80) , , (1-81), (1-82) , Formula (1-83) Formula (1-84).

The photoinitiator (C-1) represented by the formula (1) is used in an amount of 2 to 20 parts by weight, preferably 2 parts by weight to 15 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). The parts by weight are more preferably 2 parts by weight to 10 parts by weight. When the photosensitive resin composition does not use the photoinitiator (C-1), the protective film/gap body obtained by the photosensitive resin composition has poor adhesion and resolution during development. Other O- mercaptopurines (C-2)

The photoinitiator (C) further includes other O-mercaptoquinone compounds (C-2). The other O-mercaptoquinone compound (C-2) includes a photoinitiator (C-2-I) represented by the following structural formula (10): Wherein D ⁴ and D ⁵ each independently represent a hydrogen atom, a cyclic, linear or branched alkyl or aryl group having 1 to 12 carbon atoms, and the alkyl group or aryl group The group is unsubstituted or substituted with a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an aryl group; D ⁶ and D ⁷ are each independently represented a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms (alkanoyl) An alkoxycarbonyl group having 2 to 12 carbon atoms, or a phenoxycarbonyl group; and e1 and e2 are integers independently representing from 0 to 5.

A specific example of the photoinitiator (C-2-I) is: 1-[4-(phenylthio)phenyl]-propane-3-cyclopentane-1,2-dione 2-( O-benzoinyl), 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-phenylhydrazinyl), 1-[4-(benzene Thio)phenyl]-octane-1,2-dione 2-(O-phenylhydrazinyl); the above photoinitiator (C-2-I) may be used alone or in combination of plural kinds. Depending on actual needs.

The other O-mercaptoquinone compound (C-2) further includes a photoinitiator (C-2-II) represented by the following structural formula (11): In the formula (11), J ¹ represents a functional group of Ja, Jb-S, and Jc-O, wherein Ja, Jb, and Jc represent a hydrogen atom, an alkyl group, or an aromatic group; and J ² represents a hydrogen atom, C. _1- C ₄ alkyl or halogen.

The photoinitiator (C-2-II) of the present invention is preferably specifically exemplified by: ethane ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9hydro-carbazole- 3-Substituent]-, 1-(oxy-acetamidine) (Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl) Oxime)) (formula as shown in formula (11-1)), ethane ketone, 1-[9-ethyl-6-(2-chloro-4benzenesulfonylbenzylidene)-9-hydrogen-oxime Ethylene-3-substituted 1-(9-ethyl-6-(2-chloro-4-benzyl sulfonyl benzoyl)-9H-carbazole-3-yl] -, 1-(O-acetyl oxime)) (the structural formula is as shown in formula (11-2)). Formula (11-1) Formula (11-2)

The other O-mercaptoquinone compound (C-2) is used in an amount of 5 to 50 parts by weight, preferably 5 parts by weight to 45 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). More preferably, it is 5 parts by weight to 40 parts by weight. When a photoinitiator of another O-mercaptoquinone compound (C-2) is used as the photosensitive resin composition, the adhesion of the protective film/gap body obtained by the photosensitive resin composition is higher. Preferably, the hardness of the protective film/gap body obtained is better. Other photoinitiators (C-3)

The photoinitiator (C) further includes other photoinitiators (C-3). Specific examples of the other photoinitiator (C-3) include, but are not limited to, triazabenzene compounds, acetophenone compounds, diimidazole compounds, benzophenone compounds, and α-diketone compounds. A ketone alcohol compound, a keto alcohol ether compound, a phosphonium oxide compound, an anthraquinone compound, a halogen-containing compound, a peroxide, or the like.

The above triazabenzene compounds may include, but are not limited to, vinyl-halomethyl-s-triazabenzene compounds, 2-(naphtho-1-substituted)-4,6-bis-halo A bis-s-triazabenzene compound and a 4-(p-aminophenyl)-2,6-di-halomethyl-s-triazabenzene compound.

Specific examples of the aforementioned vinyl-halomethyl-s-triazabenzene compound are: 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triaza Benzene, 2,4-bis(trichloromethyl)-3-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazabenzene, 2-trichloro Methyl-3-amino-6-p-methoxystyryl-s-triazabenzene and the like.

Specific examples of the aforementioned 2-(naphtho-1-substituted)-4,6-bis-halomethyl-s-triazabenzene compound are: 2-(naphtho-1-substituted)-4 ,6-bis-trichloromethyl-s-triazabenzene, 2-(4-methoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazole Heterobenzene, 2-(4-ethoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(4-butoxy-naphtho -l-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-[4-(2-methoxyethyl)-naphtho-1-yl]-4 ,6-bis-trichloromethyl-s-triazabenzene, 2-[4-(2-ethoxyethyl)-naphthyl-1-substituted]-4,6-bis-trichloromethyl Base-s-triazabenzene, 2-[4-(2-butoxyethyl)-naphthyl-1-substituted]-4,6-bis-trichloromethyl-s-triazabenzene , 2-(2-methoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(6-methoxy-5-methyl -naphtho-2-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(6-methoxy-naphtho-2-substituted)-4,6- Bis-trichloromethyl-s-triazabenzene, 2-(5-methoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(4,7-dimethoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazabenzene 2-(6-ethoxy-naphtho-2-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(4,5-dimethoxy-naphtho -1-Substituent)-4,6-bis-trichloromethyl-s-triazabenzene and the like.

Specific examples of the aforementioned 4-(p-aminophenyl)-2,6-di-halomethyl-s-triazabenzene compound are: 4-[p-N,N-di(ethoxy) Carbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-di(ethoxycarbonyl) Aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[p-N,N-bis(chloroethyl)aminophenyl]-2, 6-bis(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(three Chloromethyl)-s-triazabenzene, 4-(p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4-( p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[p-N,N-di(phenyl)amine Phenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(p-N-chloroethylcarbonylaminophenyl)-2,6-di(trichloromethane) -s-triazabenzene, 4-[p-N-(p-methoxyphenyl)carbonylaminophenyl]-2,6-di(trichloromethyl)-s-triaza Benzene, 4-[m-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[inter- Bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6- (trichloromethyl)-s-triazabenzene, 4-[m-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloro) Methyl)-s-triazabenzene, 4-[m-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl) -s-triazabenzene, 4-[o-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s- Triazabenzene, 4-[o-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl-2,6-di(trichloromethyl)-s-triazabenzene 4-[o-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4- [o-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-chloro-pair -N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-fluoro-p-N,N-di (chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-bromo-p-N,N-bis(chloroethyl)amine Phenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2 ,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2 ,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethane) -s-triazabenzene, 4-(m-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triaza Benzene, 4-(m-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-bromo-bromo -p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-chloro-p-N-ethoxyl Carbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-bromo-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl) )-s-triazabenzene, 4-(m-chloro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4- (m-fluoro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-bromo-p-N-chloroethyl) Aminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-chloro-p-N-chloroethylaminophenyl)-2,6- Bis(trichloromethyl)-s-triazabenzene, 4-(o-fluoro-p-N-chloro Aminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 2,4-bis(trichloromethyl)-6-[3-bromo-4-[N, N-bis(ethoxycarbonylmethyl)amino]phenyl]-1,3,5-triazabenzene and the like.

The aforementioned triazabenzene compound is 4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s Triazine, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene and the like are preferred. The above-mentioned triazabenzene compounds may be used singly or in combination of plural kinds, depending on actual needs.

Specific examples of the above-mentioned acetophenone compounds are: p-dimethylaminophenone, α,α'-dimethoxyoxyazopropenone, 2,2'-dimethyl-2- Phenylacetophenone, p-methoxyacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl- 2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone or the like. The aforementioned acetophenone compound is 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-N,N-dimethyl Amine-1-(4-morpholinophenyl)-1-butanone or the like is preferred. The above-mentioned acetophenone compounds may be used singly or in combination of plural kinds, depending on actual needs.

Specific examples of the above diimidazole compounds are: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o- Fluorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyl Imidazole, 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-ethylphenyl)-4 , 4',5,5'-tetraphenyldiimidazole, 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2 '-Bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl) )-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole Wait. The above second imidazole compound is preferably 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole. The above-mentioned diimidazole compounds may be used singly or in combination of plural kinds, depending on actual needs.

Specific examples of the above benzophenone compounds are: thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-oxime, benzophenone, 4,4'-bis(dimethyl Amine) benzophenone, 4,4'-bis(diethylamine) benzophenone, and the like. The above benzophenone compound is preferably 4,4'-bis(diethylamine)benzophenone. The above benzophenone compounds may be used singly or in combination of plural kinds, depending on actual needs.

Specific examples of the above-mentioned α-diketone compound are benzoin, ethenyl and the like. A specific example of the above ketone alcohol compound is benzophenone. Specific examples of the above ketol ether compound are benzophenone methyl ether, benzophenone ethyl ether, and diphenylethanol ketone isopropyl ether. Specific examples of the above fluorinated phosphonium oxide compound are: 2,4,6-trimethylphenylhydrazine diphenylphosphine oxide, bis-(2,6-dimethoxybenzoquinone)-2,4, 4-trimethylphenylphosphine oxide or the like. Specific examples of the above terpenoids are: hydrazine, 1,4-naphthoquinone, and the like. Specific examples of the above halogen-containing compound are benzoquinone methyl chloride, tribromomethylphenylhydrazine, tris(trichloromethyl)-s-triazabenzene, and the like. Specific examples of the above peroxides include di-tert-butyl peroxide and the like. The above-mentioned α-diketone compound, keto alcohol compound, keto alcohol ether compound, phosphine oxide compound, quinone compound, halogen-containing compound, peroxide, or the like may be used singly or in combination of plural kinds. Depending on actual needs.

The photoinitiator (C) is used in an amount of 2 to 200 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). Organic solvent (D)

The organic solvent (D) of the present invention means an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), and the following o-naphthoquinonediazidesulfonic acid. The organic solvent in which the ester (E), the inorganic particles (F), and the organic acid (G) are dissolved but does not react with the above components. The organic solvent preferably has a suitable volatility.

The organic solvent (D) may include, but is not limited to, ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, Triethylene glycol ether, propylene glycol methyl ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol diethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol (tripropylene glycol) Monomethyl ether) or tripropylene glycol monoethyl ether (poly)alkylene glycol monoalkyl ether solvent; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol single a (poly)alkylene glycol monoalkyl ether acetate solvent such as methyl ether acetate or propylene glycol monoethyl ether acetate; diglyme, diethylene glycol methyl ether, diethylene glycol diethyl ether or tetrahydrofuran Other ether solvent; ketone solvent such as methyl ethyl ketone, cyclohexanone, 2-heptanone or 3-heptanone; alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate Solvent; methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, 3-methoxy Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy- Methyl 3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, Isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, butyric acid Other ester solvents such as n-butyl ester, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate or ethyl 2-oxybutyrate; toluene or two An aromatic hydrocarbon solvent such as toluene; a carboxylic acid guanamine solvent such as nitrogen-methylpyrrolidone, nitrogen, nitrogen-dimethylformamide or nitrogen or nitrogen-dimethylacetamide. The organic solvent (D) may be used singly or in combination of plural kinds.

The organic solvent (D) is used in an amount of 500 to 5000 parts by weight, preferably 600 parts by weight to 4,500 parts by weight, more preferably 700 parts by weight to 4,000 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). Parts by weight. O-naphthoquinonediazide sulfonate (E)

The photosensitive resin composition of the present invention further comprises o-naphthoquinonediazide sulfonate (E). The o-naphthoquinonediazide sulfonate (E) is not particularly limited and may be generally used. The o-naphthoquinonediazide sulfonate (E) may be a fully esterified or partially esterified esterified product. Preferably, the o-naphthoquinonediazide sulfonate (E) is prepared by reacting o-naphthoquinonediazidesulfonic acid or a salt thereof with a hydroxy compound. More preferably, the o-naphthoquinonediazide sulfonate (E) is prepared by reacting o-naphthoquinonediazidesulfonic acid or a salt thereof with a polyvalent hydroxy compound.

The aforementioned o-naphthoquinonediazidesulfonic acid may include, but is not limited to, o-naphthoquinonediazide-4-sulfonic acid, o-naphthoquinonediazide-5-sulfonic acid, o-naphthoquinonediazide-6-sulfonic acid. Wait. The above salts of o-naphthoquinonediazidesulfonic acid may include, but are not limited to, o-naphthoquinonediazidesulfonic acid halide salts.

The aforementioned hydroxy compound may be used singly or in combination, and the hydroxy compound may include, but is not limited to: (1) Hydroxybenzophenone compound: Specific examples of the hydroxybenzophenone compound may include, but are not limited to, 2, 3 ,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxydiphenyl Methyl ketone, 2,4,2',4'-tetrahydroxybenzophenone, 2,4,6,3',4'-pentahydroxybenzophenone, 2,3,4,2',4' - pentahydroxybenzophenone, 2,3,4,2',5'-pentahydroxybenzophenone, 2,4,5,3',5'-pentahydroxybenzophenone, 2,3, 4,3',4',5'-hexahydroxybenzophenone and the like. (2) A hydroxyaryl compound, which may include, but is not limited to, a hydroxyaryl compound represented by the following formula (E-1): In the formula (E-1), Q ¹ to Q ³ represent a hydrogen atom or a C ₁ to C ₆ alkyl group; and Q ⁴ to Q ⁹ represent a hydrogen atom, a halogen atom, a C ₁ to C ₆ alkyl group, C ₁ to C alkoxy (alkoxy) _6, the aliphatic alkenyl group (alkenyl of) a C ₁ to C ₆ or a cycloalkyl group (cycloalkyl); Q ¹⁰ and Q ¹¹ represents a hydrogen atom, a halogen atom and a C ₁ to C ₆ Alkyl; g, h and i represent an integer from 1 to 3; j represents 0 or 1.

Specific examples of the hydroxyaryl compound represented by the above formula (E-1) may include, but are not limited to, tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)- 4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2- Hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxybenzene Methane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxy Phenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2, 4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)-3-methoxy- 4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, double (3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-2-hydroxyphenylmethane, bis(3- Cyclohexyl-4-hydroxyl -6-methylphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl- 4-hydroxy-6-methylphenyl)-3,4-dihydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl- 6-Hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methyl Phenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxy-4- Methylphenyl)-3,4-dihydroxyphenylmethane, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl Benzene, 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene, etc. .

(3) (Hydroxyphenyl) hydrocarbon compound, which may include, but is not limited to, a (hydroxyphenyl) hydrocarbon compound represented by the following formula (E-2): In the formula (E-2), Q ¹² and Q ¹³ represent a hydrogen atom or a C ₁ to C ₆ alkyl group, and c and d represent an integer of 1 to 3.

Specific examples of the (hydroxyphenyl) hydrocarbon compound represented by the above formula (E-2) may include, but are not limited to, 2-(2,3,4-trihydroxyphenyl)-2-(2',3', 4'-trihydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2 -(4'-Hydroxyphenyl)propane, bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, and the like.

(4) Other aromatic hydroxy compounds: Specific examples of other aromatic hydroxy compounds may include, but are not limited to, phenol, p-methoxyphenol, dimethyl phenol, hydroquinone, bisphenol A, naphthol, Catechol, 1,2,3-benzenetriol methyl ether, 1,2,3-benzenetriol-1,3-dimethyl ether, 3,4,5-trihydroxybenzoic acid, partial ester Or partially etherified 3,4,5-trihydroxybenzoic acid, 4,4'-[1-[4[-1-(4-hydroxyphenyl)-1-methylethyl]phenyl] Ethylene] bisphenol and the like.

Preferably, the above hydroxy compound is selected from the group consisting of 4,4'-[1-[4[-1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene] Phenol, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2-(2,3,4-trihydroxyphenyl)-2-(2) ',3',4'-trihydroxyphenyl)propane and a combination of any of the above.

The above-mentioned o-naphthoquinonediazidesulfonic acid or a salt thereof is usually reacted with the above-mentioned hydroxy compound in dioxane, N-pyrrolidone, acetamide or the like. It is preferably carried out in an organic solvent while being carried out in the presence of an alkaline condensing agent such as triethanolamine, an alkali metal carbonate or an alkali metal hydrogencarbonate.

Preferably, the degree of esterification of the aforementioned o-naphthoquinonediazide sulfonate (E) is 50% or more, that is, the total amount of hydroxyl groups in the aforementioned hydroxy compound is 100 mol% (mol%). More than 50 mol% of the hydroxyl groups in the hydroxy compound are esterified with o-naphthoquinonediazidesulfonic acid or a salt thereof. More preferably, the quinonediazide compound (B) has a degree of esterification of 60% or more.

The o-naphthoquinonediazide sulfonate (E) is used in an amount of 0.2 to 15 parts by weight, preferably 0.3 parts by weight to 10 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). It is preferably from 0.4 parts by weight to 6 parts by weight. When the orthoquinone diazide sulfonate (E) is used as the photosensitive resin composition, the resolution of the protective film/gap body obtained by the photosensitive resin composition is preferable. Inorganic particles (F)

The photosensitive resin composition of the present invention further includes inorganic particles (F). The inorganic particles (F) are mainly composed of an oxide of a Group IV element.

In one embodiment of the invention, the inorganic particles (F) have a particle size of from 1 nm to 100 nm. The measurement method of the particle diameter may be a conventional measurement method, for example, measured by dynamic light scattering particles, and the particle diameter thereof is preferably from 1 nm to 50 nm; more preferably from 5 nm to 15 nm. When the particle diameter is less than 1 nm, the obtained film is liable to undergo secondary aggregation and may cause whitening; when the particle diameter is larger than 100 nm, the uniformity of the surface of the formed film may be affected.

In the specific example of the present invention, the oxide particles which can be used as the inorganic particles (F) are preferably titanium oxide, zirconium oxide, cerium oxide, and composite particles of these metal oxides and cerium oxide and tin oxide, and the obtained film product The refractive index is increased, and more preferably titanium oxide or zirconium oxide, that is, the fourth group element of the inorganic particles (F) is titanium or zirconium.

On the other hand, the crystalline form of titanium oxide has both an anatase type and a rutile type, preferably a rutile type, which has a high refractive index and excellent light resistance.

Further, since titanium oxide has photocatalytic activity, it is difficult to be used as an optical application, and therefore it is preferred to cover the surface of the particles with cerium oxide.

The inorganic particles (F) according to the present invention may be in the form of a powder or a dispersed sol form in which oxide particles are dispersed in a dispersion medium. The dispersion medium is, for example, methanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether, or ethoxyethanol.

In a specific example of the present invention, the commercially available titanium oxide particles are manufactured by CI Kasei, Japan, NanoTek TiO ₂ (dispersant is methyl isobutyl ketone, anatase type); South Korea NanoCMS, Lot No.: S111109 ( Dispersing agent is ethoxyethanol, rutile type); Japan's daily wave catalytic formation, Red Lake series (dispersant is methanol, anatase type); manufactured by Tayca, TS series (dispersant is methyl ethyl ketone, Rutile type). Commercially available zirconia particles are manufactured by Osaka Cement Co., Japan, HXU-120JC (dispersant is methyl ethyl ketone) or Mikuni Color Ltd., and have an average particle diameter of 13.00 nm.

The inorganic particles (F) are used in an amount of 40 to 300 parts by weight, preferably 50 parts by weight to 250 parts by weight, more preferably 60 parts by weight to 200 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). Parts by weight. When the inorganic particles (F) are used as the photosensitive resin composition, the refractive index of the protective film/gap body obtained by the photosensitive resin composition is preferable. Organic acid (G)

The photosensitive resin composition of the present invention further includes an organic acid (G) in which the molecular weight of the organic acid (G) is 1,000 or less.

In a specific example of the present invention, the organic acid having a molecular weight of 1,000 or less includes, but is not limited to, an aliphatic carboxylic acid, an alicyclic carboxylic acid or an aromatic carboxylic acid.

Examples of the aliphatic carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, and pivalic acid. ), caproic acid, diethyl acetic acid, heptanoic acid, octanoic acid, 2-furoic acid, etc.; oxalic acid Acid), malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid , azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethyl malonate acid, dimethyl Dimethyl malonic acid, methyl succinic acid, tetramethyl succinic acid, itaconic acid, methyl methacrylate Citraconic acid, maleic acid, fumaric acid, methyl fumaric acid Isocarboxylic acid; 1,2,3-propanetricarboxylic acid, aconitic acid, camphoronic acid, etc.

Examples of the alicyclic carboxylic acid include a carboxylic acid derivative having a steroid structure such as cholic acid, deoxycholic acid, and lithocholate, and an adamantanecarboxylic acid derivative. (adamantane carboxylic acid derivatives), adamantane dicarboxylic acid, cyclohexyl carboxylic acid, cyclohexyl dicarboxylic acid, and the like.

The aromatic carboxylic acid may, for example, be an aromatic carboxylic acid in which a carboxyl group is directly bonded to a phenyl group or a carboxylic acid in which a carboxyl group is bonded to a phenyl group via a carbon chain, and specific examples thereof include benzoic acid. , toluic acid, cumin acid, 2,3-dimethylbenzoic acid, 3,5-dimethylbenzoic acid An aromatic monocarboxylic acid; an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid or terephthalic acid; trimellitic acid, 1,3,5-benzene tricarboxylic acid, 1,2,3,5-pyromellitic acid, pyromellitic acid (1,2,3,5-pyromellitic acid) Pyromellitic acid) or more than 3 or more aromatic polycarboxylic acids; and phenyl acetic acid, hydrogenic acid, hydrocinnamic acid, mandelic acid, phenyl Phenyl succinic acid, atropic acid, cinnaimic acid, cinnamylideneacetic acid, coumaric Acid), other aromatic carboxylic acids such as umbellic acid. The aforementioned organic acids may be used singly or in combination. The organic acid is preferably malonic acid, adipic acid, or methylene, from the viewpoints of improvement in transparency of the coating film, alkali solubility, solubility in a solvent, and residue in a region other than a portion where a pixel is formed. Succinic acid, methyl maleic acid, 2-furancarboxylic acid, fumaric acid, methyl fumaric acid.

The organic acid (G) is used in an amount of 1 to 10 parts by weight, preferably 1.5 parts by weight to 9 parts by weight, more preferably 2 parts by weight to 8 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). Parts by weight. When the organic acid (G) is used as the photosensitive resin composition, the resolution of the obtained protective film/gap body is preferable. Additive (H)

The photosensitive resin composition of the present invention may optionally contain the additive (H) without affecting the effects of the present invention. The additive (H) may include a filler, a polymer other than the alkali-soluble resin (A), an adhesion promoter, an antioxidant, an ultraviolet absorber, or an anti-aggregation agent.

Specific examples of the aforementioned filler may include, but are not limited to, glass or aluminum.

Specific examples of the aforementioned polymer may include, but are not limited to, polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate or any combination of the above polymers.

Specific examples of the adhesion promoter may include, but are not limited to, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, and nitrogen-(2-amino B. 3-aminopropylmethyldimethoxydecane, nitrogen-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane , 3-glycidylpropyltrimethoxydecane, 3-glycidylpropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3 -chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-thiolpropyltrimethoxydecane or the above compounds Any combination.

Specific examples of the aforementioned antioxidant may include, but are not limited to, 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-t-butylphenol, or any combination of the above compounds. .

Specific examples of the aforementioned ultraviolet absorber may include, but are not limited to, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide or alkoxyphenone (alkoxy phenone). Or any combination of the above compounds.

Specific examples of the anti-agglomerating agent may include, but are not limited to, sodium polyacrylate or the like.

The additive (H) is used in an amount of 0.01 to 5 parts by weight, preferably 0.05 parts by weight to 5 parts by weight, more preferably 0.1 parts by weight to 5 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). Share. Method for preparing photosensitive resin composition

A method for preparing a photosensitive resin composition, for example, placing an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), and a solvent (D) in a stirrer for stirring , uniformly mixing into a solution state, and if necessary, adding o-naphthoquinonediazide sulfonate (E), inorganic particles (F), organic acid (G), and additive (H), and uniformly mixing them. A photosensitive resin composition in a solution state can be obtained.

Further, the method for preparing the photosensitive resin composition is not particularly limited. The photosensitive resin composition is prepared by, for example, dispersing a part of the alkali-soluble resin (A) and the ethylenically unsaturated group-containing compound (B) in a part of the organic solvent (D) to form a dispersion solution; and then Mixing the remaining alkali-soluble resin (A), the ethylenically unsaturated group-containing compound (B), the photoinitiator (C), the organic solvent (D), the o-naphthoquinonediazide sulfonate (E), and the inorganic Particle (F), organic acid (G), and additive (H). Protective film and spacer formation

The present invention provides a protective film and a spacer which are formed using the above-described photosensitive resin composition. The preparation method thereof will be described in detail below.

The protective film of the present invention is formed by forming a pixel layer composed of a red, green, and blue colored layer on a transparent substrate, and then coating the transparent photosensitive resin composition described above to form red, green, and blue. After the substrate of the pixel-colored layer is subjected to a step of exposure, development, and post-baking, the solvent is removed to form a color filter layer protective film.

In the method of forming a spacer according to the present invention, a transparent conductive film is formed on a transparent substrate on which a protective film and a pixel layer have been formed, and the transparent photosensitive resin composition is applied onto the transparent conductive film, and then The steps of exposure, development, and post-baking are performed, thereby removing the solvent therein to form a spacer.

In other words, if a protective film is to be formed, the photosensitive resin composition is applied onto the pixel layer on the substrate; and if the spacer is to be formed, the photosensitive resin composition is applied to the transparent conductive film on the substrate. on.

The coating method described above may be, for example, a spray method, a roller coating method, a spin coating method, a bar coating method, or an ink jet method. . The above coating method may preferably be carried out by a spin coater, a spin loess coating machine, a slit-die coating machine or the like.

The pre-bake conditions described above vary depending on the type of each component and the blending ratio. Usually, the pre-baking is carried out at a temperature of 70 ° C to 90 ° C for 1 minute to 15 minutes. After the prebaking, the thickness of the prebaked coating film is from 0.15 μm to 8.5 μm, preferably from 0.15 μm to 6.5 μm, more preferably from 0.15 μm to 4.5 μm. It can be understood that the thickness of the above pre-baked coating film refers to the thickness after removing the solvent.

After the prebaking coating film is formed, it is heat-treated by a heating device such as a hot plate or an oven. The heat treatment temperature is usually from 150 to 250 ° C, wherein the heating time using the hot plate is from 5 minutes to 30 minutes, and the heating time using the oven is from 30 minutes to 90 minutes.

When a photoinitiator is used as the curable resin composition, if necessary, a curable resin composition may be applied onto the surface of the substrate, and the solvent may be removed by pre-baking to form a pre-baked coating film. The prebaked coating film is subjected to exposure treatment.

The light used for the above exposure treatment may be, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like, and light containing ultraviolet light having a wavelength of 190 nm to 450 nm is preferable.

The exposure amount of the above exposure treatment is preferably from 100 J/m ² to 20,000 J/m ^{2 , more} preferably from 150 J/m ² to 10,000 J/m ² .

After the above exposure treatment, it is possible to selectively perform heat treatment using a heating device such as a hot plate or an oven. The heat treatment temperature is usually from 150 to 250 ° C, wherein the heating time using the hot plate is from 5 minutes to 30 minutes, and the heating time using the oven is from 30 minutes to 90 minutes.

The protective film and the spacer of the present invention are not limited to being formed on the pixel layer or the transparent conductive film, but may be formed on various elements on the substrate or on the substrate. Method for preparing color filter

Specifically, the method for producing a color filter of the present invention is, for example, after forming a pixel colored layer such as red, green, or blue, and a protective film, in a vacuum environment having a temperature between 220 ° C and 250 ° C. Sputtering on the surface of the protective film layer to form an ITO protective film, if necessary, etching the ITO protective film, wiring, and then applying an alignment film on the surface of the ITO protective film, thereby producing the present invention A color filter of a cured product obtained by curing a photosensitive resin composition. Method of manufacturing liquid crystal display device

First, a color filter formed by the above-described method of manufacturing a color filter and a substrate provided with a thin film transistor are disposed to face each other, and a gap (cell gap) is provided between the two. Next, the color filter is attached to the peripheral portion of the above substrate with an adhesive and the injection hole is left. Then, liquid crystal is injected from the injection hole in the gap between the surface of the substrate and the adhesive, and finally the injection hole is sealed to form a liquid crystal layer. Subsequently, a liquid crystal display device is fabricated by providing a polarizing plate on the other side of the color filter that contacts the liquid crystal layer and the other side of the substrate that contacts the liquid crystal layer. The liquid crystal used as described above, that is, a liquid crystal compound or a liquid crystal composition, is not particularly limited herein. However, any liquid crystal compound and liquid crystal composition can be used.

Further, the liquid crystal alignment film used in the production of the color filter is used to restrict the alignment of the liquid crystal molecules, and is not particularly limited, and any of inorganic substances or organic substances may be used, and the present invention is not limited thereto.

The invention will be described in detail below by way of examples, but the invention is not limited by the examples. Alkali-soluble resin Synthesis Example (A-1) embodiment

Synthesis Example A-1-1 to Synthesis Example A-1-6 of the alkali-soluble resin (A-1): Synthesis Example A-1-1

A nitrogen inlet, a stirrer, a heater, a condenser and a thermometer were placed on a four-necked flask of 1000 ml volume, and after introducing nitrogen, 10 parts by weight of acrylic acid, 30 parts by weight of glycidyl acrylate, and 20 parts by weight were added. 2-hydroxyethyl methacrylate, 35 parts by weight of styrene, 5 parts by weight of 1,3-butadiene, 2.4 parts by weight of 2,2'-azobis-2-methylbutyronitrile and 240 Parts by weight of diethylene glycol dimethyl ether solvent. Next, the above ingredients were slowly stirred to raise the temperature to 85 ° C, and polymerization was carried out at this temperature for 5 hours. Then, after the solvent is devolatilized, an alkali-soluble resin (A-1-1) can be obtained. Synthesis Example A-1-2 to Synthesis Example A-1-6

The alkali-soluble resin of Synthesis Example A-1-2 to Synthesis Example A-1-6 was prepared in the same manner as in Synthesis Example A-1-1, and was distinguished by changing the kind of the component of the alkali-soluble resin and The amount used, the reaction time, and the reaction temperature (as shown in Table 1).

The compounds corresponding to the abbreviations in Table 1 are as follows. Table 1 Synthesis example of resin (A-2) having an unsaturated group

Hereinafter, Synthesis Example A-2-1 to Synthesis Example A-2-3 of Resin (A-2) having an unsaturated group will be described: Synthesis Example A-2-1

100 parts by weight of an antimony epoxy compound (Model ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 part by weight 2,6-di-t-butyl-p-cresol, and 130 parts by weight of propylene glycol methyl ether acetate were continuously added to a 500 mL four-necked flask, and the feed rate was controlled at 25 parts by weight/min. The temperature of the reaction process is maintained at 100 ̊C to 110 ̊C, and the reaction is carried out for 15 hours to obtain a pale yellow transparent mixture having a solid concentration of 50% by weight.

Next, 100 parts by weight of the above-obtained pale yellow transparent mixed solution was dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate, and 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of diphenyl were simultaneously added. The ketone tetracarboxylic dianhydride is heated to 110 ̊C to 115 ̊C, and the reaction is carried out for 2 hours to obtain an unsaturated group-containing resin having an acid value of 98.0 mgKOH/g (hereinafter referred to as A-2-1). . Synthesis Example A-2-2

100 parts by weight of an antimony epoxy compound (Model ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 part by weight 2,6-di-t-butyl-p-cresol, and 130 parts by weight of propylene glycol methyl ether acetate were continuously added to a 500 mL four-necked flask, and the feed rate was controlled at 25 parts by weight/min. The temperature of the reaction was maintained at 100 ̊C to 110 ̊C, and the reaction was carried out for 15 hours to obtain a pale yellow transparent mixture having a solid concentration of 50% by weight.

Next, 100 parts by weight of the above-obtained pale yellow transparent mixed solution was dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate, and 13 parts by weight of benzophenone tetracarboxylic dianhydride was added at 90 ̊C to 95 The reaction was carried out for 2 hours at ̊C, and then 6 parts by weight of tetrahydrophthalic anhydride was added and reacted at 90 ̊C to 95 ̊C for 4 hours to obtain an acid value of 99.0 mgKOH/g. A saturated group of resins (hereinafter abbreviated as A-2-2). Synthesis Example A-2-3

400 parts by weight of an epoxy compound [Model NC-3000, manufactured by Nippon Kayaku Co., Ltd.; epoxy equivalent 288], 102 parts by weight of acrylic acid, 0.3 parts by weight of methoxyphenol, and 5 parts by weight Triphenylphosphine, and 264 parts by weight of propylene glycol methyl ether acetate were placed in a reaction flask, and the temperature of the reaction was maintained at 95 ° C for 9 hours to obtain an acid value of 2.2 mg KOH / g. product. Next, 151 parts by weight of tetrahydrophthalic anhydride was added and reacted at 95 ̊C for 4 hours to obtain an acid value of 102 mgKOH/g and a weight average molecular weight of 3,200. Base resin (hereinafter referred to as A-2-3). Synthesis example of polyoxyalkylene polymer (A-3)

The synthesis example A-3-1 to the synthesis example A-3-4 of the polyoxyalkylene polymer (A-3) will be described below: Synthesis Example A-3-1

In a 500 ml three-necked flask, 0.23 mol of dimethyldimethoxydecane (hereinafter abbreviated as DMDMS), 0.7 mol of phenyltrimethoxydecane (hereinafter referred to as PTMS), and 0.07 mo were added. 3-glycidoxypropyltrimethoxydecane (hereinafter abbreviated as TMS-GLY) and 200 g of diacetone alcohol (hereinafter abbreviated as DAA), and added oxalic acid in 30 minutes while stirring at room temperature Aqueous solution (0.35 g of oxalic acid dissolved in 75 g of water). Next, the flask was immersed in an oil bath of 30 ° C, and after stirring for 30 minutes, the above reaction solution was heated to 105 ° C, and stirring was continued to carry out a polycondensation reaction. After reacting for 6 hours, the solvent in the solution was removed by distillation to obtain a polyoxyalkylene polymer (A-3-1). Synthesis Example A-3-2 to Synthesis Example A-3-4

The polysiloxane polymer of Synthesis Example A-3-2 to Synthesis Example A-3-4 was prepared in the same manner as in Synthesis Example A-3-1, and was distinguished by changing the polymerization of polysiloxane. The type and amount of raw materials used and the polymerization conditions (as shown in Table 2).

The compounds corresponding to the abbreviations in Table 2 are as follows. Table 2 Example of photosensitive resin composition

Hereinafter, Examples 1 to 15 and Comparative Examples 1 to 7 of the photosensitive resin composition will be described: Example 1

100 parts by weight of an alkali-soluble resin of Synthesis Example A-1-1 (hereinafter abbreviated as A-1-1), 20 parts by weight of pentaerythritol 九(meth)acrylate (hereinafter abbreviated as B-1-1), 30 parts by weight of p-cumylcumylphenyl (meth) acrylate (hereinafter abbreviated as B-2-1), and 1 part by weight of a compound represented by the formula (1-1) (hereinafter abbreviated as C) -1-1), 0.2 parts by weight of 4,4'-[1-[4[-1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol and its neighbors The o-naphthoquinonediazide sulfonate (hereinafter abbreviated as E-1) formed by naphthoquinonediazide-5-sulfonic acid is added to 500 parts by weight of propylene glycol methyl ether acetate (hereinafter abbreviated as D-1). Further, the photosensitive resin composition of Example 1 was obtained by stirring uniformly with a shaking type stirrer. The obtained photosensitive resin composition was evaluated for each evaluation method described later, and the results are shown in Table 3. Embodiment 2 to Embodiment 15

The photosensitive resin compositions of Examples 2 to 15 were prepared in the same manner as in Example 1, and were different in that the composition of the photosensitive resin composition and the amount thereof were changed (as shown in Table 3). ), wherein the compounds corresponding to the labels in Table 3 are as follows. The obtained photosensitive resin composition was evaluated for each evaluation method described later, and the results are shown in Table 3. Comparative Example 1 to Comparative Example 7

The photosensitive resin compositions of Comparative Examples 1 to 7 were prepared in the same manner as in Example 1, and were distinguished by changing the kinds of components of the photosensitive resin composition and the amounts thereof used (as shown in Table 4). ). The obtained photosensitive resin composition was evaluated for each evaluation method described later, and the results are shown in Table 4.

The compounds corresponding to the abbreviations in Tables 3 and 4 are as follows. Evaluation method (a) High speed coating property

The above photosensitive resin composition was coated on a rectangular glass substrate of 100 mm x 100 mm by a screen printing machine (manufactured by Toyo Seiki Co., Ltd., AT-45PA) with a coating film of 80 mm x 80 mm. The surface of the coating film was observed, and the evaluation criteria were as follows: ◎: The surface after coating was flat, and no irregular lines appeared. ○: The surface after coating was flat, but a few irregular lines appeared. △: The surface was flat after coating. Shape, but there are serious irregular lines appearing: the surface is not flat after coating, and there are serious irregular lines (b) adhesion during development

The prebaked coating film was placed between the specified mask patterns, and irradiated with ultraviolet light (exposure model AG500-4N; manufactured by M&R Nano Technology) having an energy of 100 mJ/cm ² to perform an exposure process. Thereafter, the exposed coating film was immersed in a 0.05% KOH aqueous solution for 45 seconds, and after removing the unexposed portion, 100 cylinders having a diameter of 15 μm were developed. After washing with pure water, the number of developable cylinders was observed with a microscope (for example, Eclipse 50i, manufactured by Nikon). ◎: The number of broken bars in the cylinder <5 ○: 5≦ The number of broken bars in the cylinder<10 △: 10≦ The number of broken bars in the cylinder<15 ╳: 15≦ The number of broken bars in the cylinder<20 ( c) Hardness

The photosensitive resin composition was applied by spin coating to a glass substrate of 100 mm × 100 mm, and dried under reduced pressure at a pressure of 100 mmHg for 30 seconds, and then pre-baked at a temperature of 80 ̊C, time. After 3 minutes, it was irradiated with ultraviolet light (exposure machine Canon PLA-501F) at a light amount of 300 mJ/cm ² , and then immersed in a developing solution of 23 ̊C for 2 minutes, washed with pure water, and baked at 200 ̊C for 80 minutes. A photosensitive resin layer having a film thickness of 2.0 μm was formed on a glass substrate, and the photosensitive resin layer was analyzed by a pencil hardness tester (Mitsubishi/P-247). The measurement was performed using a weight of 500 g, and a pencil was used to divide the lens at a rate of 0.5 mm/s at six angles of 60 degrees, 120 degrees, 180 degrees, 240 degrees, 300 degrees, and 360 degrees, respectively. Long, when more than two of the six lines (including two) draw a score, the judge is unqualified. ◎: ≧ 4H; ○: 3H; Δ: 2H; ╳: <2H. (d) refractive index

The refractive index of the film formed on the ruthenium substrate was measured using a PC-2010 稜鏡 coupling type (manufactured by Metricon Co., Ltd.) in a thermostatic chamber at 25 °C. In addition, the light source is a laser of 633 nm. ◎: refractive index ≧1.65 ○: 1.65>refractive index ≧1.60 △: 1.60>refractive index ≧1.55 ╳: refractive index <1.55 (e) resolution

The obtained photosensitive resin composition was applied by spin coating on a glass substrate, and prebaked at 100 ° C for 2 minutes to obtain a prebaked coating film of about 1 μm. The pre-baked film was placed in a line and space mask (manufactured by Filcon, Japan), and irradiated with ultraviolet light of 50 mJ/cm ² (exposure model AG500-4N; manufactured by M&R Nano Technology). Then, it was developed with a 0.84% potassium hydroxide aqueous solution at 23 ° C for 1 minute to remove the unexposed portion of the coating film on the substrate, and then washed with pure water, and the minimum line width formed was determined as an analysis. degree. ◎: minimum pattern width ≦ 10 μm ○: 10 μm < minimum pattern width ≦ 15 μm Δ: 15 μm < minimum pattern width ≦ 20 μm ╳: 20 μm < minimum pattern line table 3 Table 3 ( continued ) Table 4 Evaluation results

It is understood from Tables 3 and 4 that the photosensitive resin composition including the first compound (B-1) containing an ethylenically unsaturated group (Examples 1 to 15) does not include ethylene-containing properties. The photosensitive resin composition (Comparative Example 1 to Comparative Example 4) of the saturated first compound (B-1) had poor high-speed coatability and hardness.

Further, a photosensitive film containing no photoinitiator (C-1) was used as compared with a film formed using a photosensitive resin composition containing a photoinitiator (C-1) (Examples 1 to 15). The film formed of the resin composition (Comparative Example 4 to Comparative Example 7) had poor adhesion and resolution at high temperature and development.

As described above, the photosensitive resin composition of the present invention includes the alkali-soluble resin (A), the ethylenically unsaturated group-containing compound (B), and the specific structure of the photoinitiator (C), ortho-naphthoquinone Since the sulfonate (E), the inorganic particles (F), and the organic acid (G) can form a photosensitive resin having high-speed coating properties, adhesion during development, hardness, refractive index, and resolution. Composition.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

no.

no.

Claims (22)

A photosensitive resin composition comprising: an alkali-soluble resin (A); an ethylenically unsaturated group-containing compound (B); a photoinitiator (C); a solvent (D); an inorganic particle (F), the inorganic The particles (F) are mainly composed of an oxide of a Group IV element; wherein the ethylenically unsaturated group-containing compound (B) comprises a first compound having an ethylenically unsaturated group having a structure of the formula (II) (B-1), Wherein A ⁵ represents a hydrogen atom or a methyl group; A ⁶ represents a hydrogen atom, an acryloyl group or a methacryl group; and r represents 3 to 4; and the photoinitiator (C) includes a formula (1) Photoinitiator (C-1) Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen, C ₁ -C ₂₀ alkyl, COR ₁₆ , NO ₂ , by formula (2) Represented group, R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are each independently a group represented by the formula (5); However, the condition is that at least one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ is represented by the formula (5) The group represented, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently hydrogen, C ₁ -C ₂₀ alkyl, the C ₁ -C ₂₀ alkyl group being unsubstituted or having one or more of the following groups Group substitution: halogen, phenyl, CN, OH, SH, C ₁ -C ₄ -alkoxy, -(CO)OH or -(CO)O-(C ₁ -C ₄ alkyl); or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are, independently of each other, an unsubstituted phenyl group or a phenyl group substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, CN, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently halogen, CN, OR ₁₇ , SR ₁₈ , SOR ₁₈ , SO ₂ R ₁₈ or NR ₁₉ R ₂₀ , wherein the substituents OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ optionally forms a 5- or 6-membered ring with one of the carbon atoms in the naphthyl ring via the groups R ₁₇ , R ₁₈ , R ₁₉ and/or R ₂₀ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a group represented by COR ₁₆ , NO ₂ or formula (2), X represents CO or a direct bond; R ₁₃ represents a C ₁ -C ₂₀ alkyl group, a phenyl group or a naphthyl group; when R ₁₃ represents a C ₁ -C ₂₀ alkyl group, it is unsubstituted or has one or more of the following groups. Group substitution: halogen, R ₁₇ , OR ₁₇ , SR ₁₈ , COOR ₁₇ , CONR ₁₉ R ₂₀ or NR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ ; when R ₁₃ represents C ₂ -C ₂₀ alkyl , which is undoped or intermixed with at least one O, S, CO or NR ₂₆ ; when R ₁₃ represents a phenyl or naphthyl group, each of which is unsubstituted or substituted by COR ₁₆ or represented by at least one formula (7) Substituted by the group; k represents an integer of 1 to 10; R ₁₄ represents a C ₁ -C ₂₀ alkyl group, a phenyl group or a C ₁ -C ₈ alkoxy group; and R ₁₅ represents a phenyl group, a naphthyl group, a C ₃ -C ₂₀ heteroaryl group or C ₁ -C ₂₀ alkyl; when R ₁₅ represents phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , intervening one or more O, S C ₂ -C ₂₀ alkyl; or C ₁ -C ₂₀ alkyl is unsubstituted or via one or more of the following groups Substitution: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₄ -C ₂₀ heteroaryl An oxycarbonyl group, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ or PO(OC _k H _2k+1 ) ₂ ; when R ₁₅ represents a C ₁ -C ₂₀ alkyl group, it is unsubstituted or one or more Substituted by the following groups: OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ or PO (OC _k H _{2k+1 2} ; R' ₁₄ has one of the meanings given for R ₁₄ ; R' ₁₅ has one of the meanings given for R ₁₅ ; R ₁₆ represents phenyl or C ₁ -C ₂₀ alkyl; R ₁₆ table Phenyl, which is unsubstituted or substituted with one or more of the following _{groups: OR 17, SR 18, NR} 19 R 20, interrupted by one or more O, S or NR C ₂₆ alkyl group of ₂ -C ₂₀ Or a C ₁ -C ₂₀ alkyl group is unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl group, C ₄ -C ₂₀ aryloxycarbonyl group heteroaryl, oR _17, SR ₁₈ or NR ₁₉ R _20; when R ₁₆ represents a C ₁ -C ₂₀ alkyl, It is unsubstituted or substituted with one or more of the following groups: halogen, phenyl, OH, SH, CN, C ₃ -C ₆ alkenoxy, OCH ₂ CH ₂ (CO)O (C ₁ -C ₄ Alkyl), O(CO)-(C ₁ -C ₄ alkyl) or (CO)O(C ₁ -C ₄ alkyl); R ₁₇ represents C ₁ -C ₂₀ alkyl, which is unsubstituted or Substituted by one or more of the following groups: halogen, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), O(CO)- (C ₂ -C ₄ alkenyl), (CO)O(C ₁ -C ₄ alkyl) or C ₃ -C ₂₀ cycloalkyl, wherein the C ₃ -C ₁₀ cycloalkyl group is uninterstitial or heterozygous a plurality of O; when R ₁₇ represents a C ₂ -C ₂₀ alkyl group, one or more O is heterogeneous therein; or R ₁₇ represents C ₁ -C ₈ alkyl fluorenyl, C ₃ -C ₆ olefinic group or C ₃ -C ₂₀ cycloalkyl having one or more O, S, CO or NR ₂₆ without inter or hetero-hetero; R ₁₈ means trans (CO a methyl group substituted with OR ₁₇ ; R ₁₉ and R ₂₀ are each independently hydrogen, phenyl, C ₁ -C ₂₀ alkyl, C ₁ -C ₈ alkanoyl or C ₁ -C ₈ alkenyloxy; Or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system which is unsubstituted or substituted with a group represented by formula (7); Wherein at least one group represented by formula (2) or formula (7) is present in the photoinitiator (C-1) having the structure represented by the formula (1) The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) comprises an alkali-soluble resin (A-1), wherein the alkali-soluble resin (A-1) is an unsaturated carboxyl group The acid or unsaturated carboxylic anhydride compound (a1) and other unsaturated compounds (a2) are obtained by copolymerization. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) comprises a resin (A-2) having an unsaturated group, wherein the resin having an unsaturated group (A- 2) is obtained by polymerizing a mixture, and the mixture comprises an epoxy compound (a-1-1) having at least two epoxy groups and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (a-1-2). The photosensitive resin composition according to claim 3, wherein the epoxy compound (a-1-1) having at least two epoxy groups includes the structure and formula represented by the formula (a-1). (a-2) the structure shown above or the above two structures, In the formula (a-1), W ¹ , W ² , W ³ and W ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and carbon. An aryl group of 6 to 12 or an aralkyl group having a carbon number of 6 to 12, In the formula (a-2), W ⁵ to W ¹⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms, and s represents an integer of 0 to 10. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) comprises a polyoxyalkylene polymer (A-3) having an acid anhydride group or an epoxy group, and the polymerization The siloxane polymer (A-3) is obtained by hydrolyzing and partially condensing at least one decane monomer represented by the structure of the formula (9): Si(U ¹ ) _w (OU ² ) _4-w (9) w represents an integer from 1 to 3, and when w represents 2 or 3, the plurality of U ¹ are each the same or different; and when 4-w represents 2 or 3, the plurality of U ² are each the same or different ; substitution of at least one of U ¹ represents a substituted anhydride-C ₁ to C ₁₀ alkyl group, the substituted alkyl group of the epoxy-C ₁ to C _10, or of epoxy-alkoxy, and the remainder represents a U ¹ Hydrogen, C ₁ to C ₁₀ alkyl, C ₂ to C ₁₀ alkenyl or C ₆ to C ₁₅ aromatic; and U ² represents hydrogen, C ₁ to C ₆ alkyl, C ₁ to C ₆ Mercapto or an aromatic group of C ₆ to C ₁₅ . The photosensitive resin composition according to claim 1, wherein the ethylenically unsaturated group-containing first compound (B- is used based on 100 parts by weight of the alkali-soluble resin (A). 1) is used in an amount of from 20 parts by weight to 200 parts by weight. The photosensitive resin composition according to claim 1, wherein the ethylenically unsaturated group-containing compound (B) comprises a second compound containing an ethylenically unsaturated group represented by the following formula (III) (B-2); Wherein: in the formula (III), A ¹ and A ² each independently represent a hydrogen atom or a methyl group; and l represents an integer of 0 to 4. The photosensitive resin composition according to claim 1, wherein the ethylenically unsaturated group-containing compound (B) comprises a third compound containing an ethylenically unsaturated group represented by the following formula (IV) ( B-3); In the formula (IV), A ³ and A ⁴ each independently represent a hydrogen atom or a methyl group; and v represents an integer of 0 to 4. The photosensitive resin composition according to claim 1, wherein the ethylenically unsaturated group-containing compound (B) comprises an ethylenic unsaturated group represented by the following formula (V) or the following formula (VI); a fourth compound (B-4); Wherein: in the formula (V), B ¹ to B ⁸ each independently represent a hydrogen atom or a hydrocarbon group, and at least one of B ¹ to B ⁸ includes an ethylenically unsaturated group at its end as a substituent; and in the formula (VI) B ¹ to B ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and at least one of B ¹ to B ⁶ includes an ethylenically unsaturated group as a substituent at the end thereof. The photosensitive resin composition according to claim 1, wherein the ethylenically unsaturated group-containing compound (B) comprises an ethylene-containing or dimethacrylate having a linear diol. The fifth compound (B-5) which is unsaturated, and the linear diol has a carbon number of 2 to 12. The patentable scope of the application of paragraph 1 photosensitive resin composition, wherein said _{R 1, R 2, R 3} , R 4, R 5, R 6, R 7 and R ₈ each independently represent a hydrogen atom; R & lt ₁ And R ₂ , R ₃ and R ₄ , R ₅ and R ₆ are each independently a group represented by the formula (5); However, the condition is that at least one of R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ is a group represented by the formula (5); and R ₂ represents COR ₁₆ , NO ₂ , or 2) the group represented, R ₇ represents a group represented by COR ₁₆ or formula (2); R _9, R ₁₁ and R ₁₂ independently of one another represent a hydrogen atom; R ₁₀ represents a hydrogen atom, OR _17, COR _16; X is CO or a direct bond; R ₁₃ represents a C ₁ -C ₂₀ alkyl or phenyl; and when R ₁₃ When C ₁ -C ₂₀ alkyl is represented, it is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , OR ₁₇ , SR ₁₈ or PO(OC _k H _2k+1 ) ₂ ; ₁₃ represents a C ₂ -C ₂₀ alkyl group which is hetero or one or more O; k is an integer 2; R ₁₄ represents a C ₁ -C ₂₀ alkyl group; and R ₁₅ represents a phenyl group, a naphthyl group, a thienyl group or a C ₁ group _; -C ₂₀ alkyl; when R ₁₅ represents phenyl or naphthyl, it is unsubstituted or substituted with one or more OR ₁₇ or C ₁ -C ₂₀ alkyl; when R ₁₅ represents C ₁ -C ₂₀ alkane Substituted, which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, NR ₁₉ R ₂₀ or COOR ₁₇ ; R ₁₆ represents phenyl, which is Substituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl; R ₁₇ represents C ₁ -C ₈ alkanoyl, C ₃ -C ₆ An fluorenyl group, a C ₁ -C ₂₀ alkyl group or a C3-C20 cycloalkyl group having one or more O, S, CO or NR ₂₆ without inter or hetero-hetero; when R ₁₇ represents C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, O(CO)-(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ alkenyl), or a C ₃ -C ₂₀ cycloalkyl group having one or more O; when R ₁₇ represents a C ₂ -C ₂₀ alkyl group, it is a hetero or one or more O; R ₁₈ represents a a methyl group substituted by OR ₁₇ ; R ₁₉ and R ₂₀ are each independently a C ₁ -C ₈ alkanoyl group or a C ₁ -C ₈ alkenyloxy group; R ₁₉ and R ₂₀ together with the N atom to which they are attached Forming a 5-membered or 6-membered saturated ring interposed with O; wherein at least one group represented by the formula (2) exists in the photoinitiator (C-1) of the structure represented by the formula (1) The photosensitive resin composition according to claim 1, wherein the photoinitiator (C- represented by the formula (1) is used based on 100 parts by weight of the alkali-soluble resin (A). 1) is used in an amount of 2 to 20 parts by weight. The photosensitive resin composition according to claim 1, wherein the photoinitiator (C) includes other O-mercaptoquinone compounds (C-2). The photosensitive resin composition according to claim 13, wherein the other O-mercaptoquinone compound (C-2) comprises a photoinitiator represented by the following structural formula (10) (C) -2-I): Wherein D ⁴ and D ⁵ each independently represent a hydrogen atom, a cyclic, linear or branched alkyl or aryl group having 1 to 12 carbon atoms, and the alkyl or aryl group is not Substituted or substituted with a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an aryl group; D ⁶ and D ⁷ each independently represent a halogen atom, having 1 An alkyl group having 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzamyl group, an alkano group having 2 to 12 carbon atoms, and having 2 to 12 carbon atoms An alkoxycarbonyl group, or a phenoxycarbonyl group; and e1 and e2 are independently an integer representing from 0 to 5. The photosensitive resin composition according to claim 13, wherein the other O-mercaptoquinone compound (C-2) comprises a photoinitiator represented by the following structural formula (11) (C) -2-II): In the formula (11), J ¹ represents a functional group of Ja, Jb-S, and Jc-O, wherein Ja, Jb, and Jc represent a hydrogen atom, an alkyl group, and an aromatic group; and J ² represents a hydrogen atom, C ₁ - C ₄ Alkyl or halogen. The photosensitive resin composition according to the first aspect of the invention, wherein the use amount of the ethylenically unsaturated group-containing compound (B) is 100 parts by weight based on the amount of the alkali-soluble resin (A). The amount is 50 to 500 parts by weight; the light The starting agent (C) is used in an amount of 2 to 200 parts by weight; the solvent (D) is used in an amount of 500 to 5000 parts by weight. The photosensitive resin composition according to claim 1, further comprising o-naphthoquinonediazide sulfonate (E). The photosensitive resin composition according to claim 1, further comprising an organic acid (G), wherein the organic acid (G) has a molecular weight of 1,000 or less. A gap body which is obtained by sequentially applying a pre-baked treatment, an exposure treatment, a development treatment, and a post-baking treatment to the photosensitive resin composition according to any one of claims 1 to 18. There is a gap body with a pattern. A protective film which is prepared by sequentially applying a prebaking treatment, an exposure treatment, a development treatment, and a post-baking treatment to the photosensitive resin composition according to any one of claims 1 to 18. A protective film having a pattern is obtained. A liquid crystal display element comprising the interposer as described in claim 19. A liquid crystal display element comprising the protective film according to claim 20 of the patent application.